Co-reporter:Gan Ye, Dan Zhang, Xiangfu Li, Kunyue Leng, Wenjuan Zhang, Jun Ma, Yinyong Sun, Wei Xu, and Shengqian Ma
ACS Applied Materials & Interfaces October 11, 2017 Volume 9(Issue 40) pp:34937-34937
Publication Date(Web):September 18, 2017
DOI:10.1021/acsami.7b10337
The control of defects in crystalline materials has long been of significance since the defects are correlated with the performances of the materials. Yet such control remains a challenge for metal–organic frameworks (MOFs), which are usually well-crystallized under hydro-/solvothermal conditions. In this contribution, we demonstrate for the first time how to increase the defects of MOF via a facile and green approach as exemplified in the context of solvent-free synthesis of UiO–66(Zr). Such increase of defects leads to drastic enhancement of catalysis performance when compared to UiO–66(Zr) prepared from conventional hydro-/solvothermal synthesis. Our work therefore not only opens a new door for boosting the catalytic activities of MOFs but also contributes a new approach to control the defects in crystalline materials for various applications.Keywords: defect sites; desulfurization; oxidation; solvent-free; UiO−66(Zr);
Co-reporter:Yao Chen, Seongmin Hong, Chung-Wei Fu, Tran Hoang, Xiao Li, Veronica Valencia, Zhenjie Zhang, Jason A. Perman, and Shengqian Ma
ACS Applied Materials & Interfaces March 29, 2017 Volume 9(Issue 12) pp:10874-10874
Publication Date(Web):March 6, 2017
DOI:10.1021/acsami.7b00588
Mesoporous materials, Tb-mesoMOF and MCM-41, were used to study the transport phenomena of biomolecules entering the interior pores from solution. Vitamins B12 and B2 were successfully encapsulated into these mesoporous materials, whereas Tb-mesoMOF (0.33 g of B12/g, 0.01 g of B2/g) adsorbed a higher amount of vitamin per mass than MCM-41 (0.21 g of B12/g, 0.002 g of B2/g). The diffusion mechanism of the biomolecules entering Tb-mesoMOF was evaluated using a mathematical model. The Raman spectroscopy studies showed vitamin B12 has been encapsulated within Tb-mesoMOF’s pores, and evaluation of the peak shifts indicated strong interactions linking vitamin B12’s pyrroline moiety with Tb-mesoMOF’s triazine and benzoate rings. Because of these stronger interactions between the vitamins and Tb-mesoMOF, longer egress times were observed than with MCM-41.Keywords: biomolecules; mesoporous metal−organic framework; Raman spectroscopy; transport phenomena; vitamin B12 and B2;
Co-reporter:Rong Cai, Xiaohan Ye, Qi Sun, Qiuqin He, Ying He, Shengqian Ma, and Xiaodong Shi
ACS Catalysis February 3, 2017 Volume 7(Issue 2) pp:1087-1087
Publication Date(Web):December 30, 2016
DOI:10.1021/acscatal.6b03211
Stability and reactivity have been recognized as some critical issues for gold(I) catalysts. Such issues can be well-circumvented by anchoring the gold(I) complex onto the backbones of porous organic polymer (POP) followed by coordination with a triazole ligand as illustrated in the present work via a series of gold(I)-catalyzed reactions. In this strategy, 1,2,3-triazole was used as the special “X-factor” to avoid the formation of solid AgCl involved in typical gold-activation processes. The catalyst could be readily recycled without loss of reactivity. Moreover, compared with the PPh3-modified polystyrene beads, the POP support was advantageous by providing high surface area, hierarchical porosity, and better stabilization of cations. In some cases, significantly improved reactivity was observed, even more so than using the homogeneous system, which further highlighted the great potential of this heterogeneous gold catalyst.Keywords: alkyne activation; heterogeneous gold catalysis; porous organic polymer; recyclable gold catalyst; triazole-gold catalyst;
Co-reporter:Qi Sun, Briana Aguila, Jason Perman, Lyndsey D. Earl, Carter W. Abney, Yuchuan Cheng, Hao Wei, Nicholas Nguyen, Lukasz Wojtas, and Shengqian Ma
Journal of the American Chemical Society February 22, 2017 Volume 139(Issue 7) pp:2786-2786
Publication Date(Web):February 13, 2017
DOI:10.1021/jacs.6b12885
A key challenge in environmental remediation is the design of adsorbents bearing an abundance of accessible chelating sites with high affinity, to achieve both rapid uptake and high capacity for the contaminants. Herein, we demonstrate how two-dimensional covalent organic frameworks (COFs) with well-defined mesopore structures display the right combination of properties to serve as a scaffold for decorating coordination sites to create ideal adsorbents. The proof-of-concept design is illustrated by modifying sulfur derivatives on a newly designed vinyl-functionalized mesoporous COF (COF-V) via thiol–ene “click” reaction. Representatively, the material (COF-S-SH) synthesized by treating COF-V with 1,2-ethanedithiol exhibits high efficiency in removing mercury from aqueous solutions and the air, affording Hg2+ and Hg0 capacities of 1350 and 863 mg g–1, respectively, surpassing all those of thiol and thioether functionalized materials reported thus far. More significantly, COF-S-SH demonstrates an ultrahigh distribution coefficient value (Kd) of 2.3 × 109 mL g–1, which allows it to rapidly reduce the Hg2+ concentration from 5 ppm to less than 0.1 ppb, well below the acceptable limit in drinking water (2 ppb). We attribute the impressive performance to the synergistic effects arising from densely populated chelating groups with a strong binding ability within ordered mesopores that allow rapid diffusion of mercury species throughout the material. X-ray absorption fine structure (XAFS) spectroscopic studies revealed that each Hg is bound exclusively by two S via intramolecular cooperativity in COF-S-SH, further interpreting its excellent affinity. The results presented here thus reveal the exceptional potential of COFs for high-performance environmental remediation.
Co-reporter:Baiyan Li, Qi Sun, Yiming Zhang, Carter W. Abney, Briana Aguila, Wenbin Lin, and Shengqian Ma
ACS Applied Materials & Interfaces April 12, 2017 Volume 9(Issue 14) pp:12511-12511
Publication Date(Web):March 28, 2017
DOI:10.1021/acsami.7b01711
We demonstrate the successful functionalization of a porous aromatic framework for uranium extraction from water as exemplified by grafting PAF-1 with the uranyl chelating amidoxime group. The resultant amidoxime-functionalized PAF-1 (PAF-1-CH2AO) exhibits a high uranium uptake capacity of over 300 mg g–1 and effectively reduces the uranyl concentration from 4.1 ppm to less than 1.0 ppb in aqueous solutions within 90 min, well below the acceptable limit of 30 ppb set by the US Environmental Protection Agency. The local coordination environment of uranium in PAF-1-CH2AO is revealed by X-ray absorption fine structure spectroscopic studies, which suggest the cooperative binding between UO22+ and adjacent amidoxime species.Keywords: amidoxime chelating group; porous aromatic framework; postsynthetic modification; radionuclide migration; uranium adsorption;
Co-reporter:Weijie Zhang;Briana Aguila
Journal of Materials Chemistry A 2017 vol. 5(Issue 35) pp:18896-18896
Publication Date(Web):2017/09/12
DOI:10.1039/C7TA90189E
Retraction of ‘Potential applications of functional porous organic polymer materials’ by Weijie Zhang et al., J. Mater. Chem. A, 2017, 5, 8795–8824.
Co-reporter:Jason A. Perman;Meng Chen;Antony A. Mikhail;Zheng Niu
CrystEngComm (1999-Present) 2017 vol. 19(Issue 29) pp:4171-4174
Publication Date(Web):2017/07/27
DOI:10.1039/C7CE00405B
The ubiquitous [Cu(O2CR)4] paddlewheel molecular building block (MBB) is renowned for producing highly porous metal–organic frameworks (MOFs), yet some carboxylate based ligands can result in supramolecular isomers. We show that it is possible to manipulate the synthesis conditions to favor one isomer over another yielding MOFs with either an lvt or nbo topology. These isomers exist because the 4-connected paddlewheel MBB and isophthalate based ligand can form either a square grid or a Kagomé lattice, where layers can join to give their respective framework topologies. Topology differences and accessible Cu(II) centers in isomers of [Cu2L]n were evaluated for their porous properties towards CO2 and their abilities to transform CO2 into value added chemicals under ambient conditions.
Co-reporter:Yuxiu Sun;Qi Sun;Hongliang Huang;Briana Aguila;Zheng Niu;Jason A. Perman
Journal of Materials Chemistry A 2017 vol. 5(Issue 35) pp:18770-18776
Publication Date(Web):2017/09/12
DOI:10.1039/C7TA05800D
In this work, we demonstrate a facile molecular-level modification method that imparts superhydrophobic character to Zr-based MOFs, while retaining their high porosity. Alkyl phosphonic acids, such as n-octadecylphosphonic acid (OPA), interact with the zirconium oxide clusters situated near and on the surface of the MOF. The octadecyl alkyl chains reduce the surface free energy on the MOF's exterior, yielding a superhydrophobic material with a contact angle greater than 150°. After exposure to aqueous solutions with a high pH and high ionic strength, the OPA-MOFs retain nearly identical surface areas. Notably, the OPA-MOFs are capable of separating organic liquids from water, which could facilitate oil/water separation applications in the event of an oil spill.
Co-reporter:Briana Aguila;Qi Sun;Jason A. Perman;Lyndsey D. Earl;Carter W. Abney;Radwan Elzein;Rudy Schlaf
Advanced Materials 2017 Volume 29(Issue 31) pp:
Publication Date(Web):2017/08/01
DOI:10.1002/adma.201700665
The primary challenge in materials design and synthesis is achieving the balance between performance and economy for real-world application. This issue is addressed by creating a thiol functionalized porous organic polymer (POP) using simple free radical polymerization techniques to prepare a cost-effective material with a high density of chelating sites designed for mercury capture and therefore environmental remediation. The resulting POP is able to remove aqueous and airborne mercury with uptake capacities of 1216 and 630 mg g−1, respectively. The material demonstrates rapid kinetics, capable of dropping the mercury concentration from 5 ppm to 1 ppb, lower than the US Environmental Protection Agency's drinking water limit (2 ppb), within 10 min. Furthermore, the material has the added benefits of recyclability, stability in a broad pH range, and selectivity for toxic metals. These results are attributed to the material's physical properties, which include hierarchical porosity, a high density of chelating sites, and the material's robustness, which improve the thiol availability to bind with mercury as determined by X-ray photoelectron spectroscopy and X-ray absorption fine structure studies. The work provides promising results for POPs as an economical material for multiple environmental remediation applications.
Co-reporter:Yang Wang;Lu Wang;Wei Huang;Ting Zhang;Xiaoya Hu;Jason A. Perman
Journal of Materials Chemistry A 2017 vol. 5(Issue 18) pp:8385-8393
Publication Date(Web):2017/05/10
DOI:10.1039/C7TA01066D
In this work, a conductive electrochemical sensor, UiO-66-NH2@PANI, was successfully prepared by polymerizing the conductive polyaniline (PANI) polymer around the metal–organic framework UiO-66-NH2. Fourier transform infrared spectra, X-ray diffraction patterns, and X-ray photoelectron spectral data support the formation of UiO-66-NH2@PANI. Additionally, scanning and transmission electron microscopy investigations confirm that PANI uniformly coated the surface of UiO-66-NH2. The resultant material was applied to construct a novel electrochemical sensor for the reliable detection of cadmium ions due to the chelation mechanism between metal cations and amine groups. Under optimized conditions, a linear detection of Cd2+ concentration range of 0.5–600 μg L−1 was repeatable with a 0.3 μg L−1 lowest level detection limit. Little to no interference effects from other co-existing ions allow the sensor to work in varying environments for practical application. This method of coating metal–organic frameworks may show utility for constructing highly sensitive electrochemical sensors for the detection of heavy metal ions and more.
Co-reporter:Qi Sun;Briana Aguila
Materials Chemistry Frontiers 2017 vol. 1(Issue 7) pp:1310-1316
Publication Date(Web):2017/06/28
DOI:10.1039/C6QM00363J
A bifunctional covalent organic framework (COF) has been illustrated in the context of partial metalation of a highly porous and chemically robust pyridine containing COF (COF-TpPa-Py) with Pd species and by taking advantage of the base catalytic behavior of pyridine. The resultant bifunctionalized COF exhibits excellent performance in catalyzing one-pot cascade aerobic oxidation–Knoevenagel condensation reactions, outperforming the corresponding homogeneous and porous organic polymer based catalytic systems, thereby opening a new avenue for multifunctional COFs as a promising platform for heterogeneous cascade catalysis.
Co-reporter:Weijie Zhang;Briana Aguila
Journal of Materials Chemistry A 2017 vol. 5(Issue 19) pp:8795-8824
Publication Date(Web):2017/05/16
DOI:10.1039/C6TA11168H
Porous materials are important in established processes, such as catalysis and molecular separations, and in emerging technologies for energy and health. Porous organic polymers (POPs), a class of highly crosslinked, amorphous polymers possessing nanopores, have recently emerged as a versatile platform for potential applications. As an emerging material, POPs offer high flexibility for the molecular design and post-synthetic modification of their conjugated skeletons and nanopores. They have shown great potential for challenging energy and environmental issues, as exemplified by their excellent performance in gas storage/separation, catalysis, environmental remediation, and sensing. This review article summarizes the recent frontiers of functional exploration and potential applications of porous organic polymers.
Co-reporter:Qi Sun;Meng Chen;Briana Aguila;Nicholas Nguyen
Faraday Discussions 2017 (Volume 201) pp:317-326
Publication Date(Web):2017/09/06
DOI:10.1039/C7FD00015D
In this work, the influence of the hydrophilic/hydrophobic nature of metal–organic framework (MOF) materials on the catalytic performance of supported Pd nanoparticles for biofuel upgrade was studied. We show that the introduction of hydrophilic groups on a MOF can greatly enhance the performance of the resultant catalyst. Specifically, Pd nanoparticles supported on MIL-101–SO3Na with superhydrophilicity (Pd/MIL-101–SO3Na) far outperforms pristine MIL-101 and the benchmark catalyst Pd/C in the hydrodeoxygenation reaction of vanillin, a model component of pyrolysis oil derived from the lignin fraction. This is attributed to a favorable mode of adsorption of the highly water soluble reactants on the more hydrophilic support in the vicinity of the catalytically active Pd nanoparticles, thereby promoting their transformation.
Co-reporter:Wilarachchige D. C. B. Gunatilleke;Kaya Wei;Zheng Niu;Lukasz Wojtas;George Nolas
Dalton Transactions 2017 vol. 46(Issue 39) pp:13342-13344
Publication Date(Web):2017/10/10
DOI:10.1039/C7DT02927F
We report for the first time the investigation of thermal conductivity for a perovskite-type MOF crystal. In situ single crystal X-ray diffraction technology was employed to track the phase transition of a newly synthesized perovskite MOF. The perovskite MOF crystal exhibits a low thermal conductivity of 1.3 W (K m)−1 in comparison to most of the bulk crystal materials at room temperature.
Co-reporter:Baiyan Li, Matthew Chrzanowski, Yiming Zhang, Shengqian Ma
Coordination Chemistry Reviews 2016 Volume 307(Part 2) pp:106-129
Publication Date(Web):15 January 2016
DOI:10.1016/j.ccr.2015.05.005
•Strategies developed thus far to include MFSs within a single MOF system are summarized.•The applications of MFS–MOFs for catalysis, gas adsorption/separation, optics, and proton-conductivity are reviewed.Metal-organic frameworks (MOFs), a class of porous materials bring great promise for a diverse array of applications ranging from gas storage and separation to heterogeneous catalysis. The ability to incorporate multiple functional sites into a single system enhances the interest seen in MOFs. The solid, well-defined nature of MOFs allow for the engineering of materials capable of performing multiple functions through multiple independent processes or cooperative and synergetic interactions or pathways. In this review, we aim to encompass and summarize research that introduces techniques and strategies to incorporate multiple functional sites within a single MOF system, highlight exceptional examples of work that exploits MFS–MOFs to perform noteworthy processes, and give direction to further enhance our ability to move MFS–MOFs forward in a way that addresses current problems faced by our society.
Co-reporter:Qi Sun, Briana Aguila, Jason Perman, Nicholas Nguyen, and Shengqian Ma
Journal of the American Chemical Society 2016 Volume 138(Issue 48) pp:15790-15796
Publication Date(Web):November 17, 2016
DOI:10.1021/jacs.6b10629
The combination of two or more reactive centers working in concert on a substrate to facilitate the reaction is now considered state of the art in catalysis, yet there still remains a tremendous challenge. Few heterogeneous systems of this sort have been exploited, as the active sites spatially separated within the rigid framework are usually difficult to cooperate. It is now shown that this roadblock can be surpassed. The underlying principle of the strategy presented here is the integration of catalytic components with excellent flexibility and porous heterogeneous catalysts, as demonstrated by the placement of linear ionic polymers in close proximity to surface Lewis acid active sites anchored on the walls of a covalent organic framework (COF). Using the cycloaddition of the epoxides and CO2 as a model reaction, dramatic activity improvements have been achieved for the composite catalysts in relation to the individual catalytic component. Furthermore, they also clearly outperform the benchmark catalytic systems formed by the combination of the molecular organocatalysts and heterogeneous Lewis acid catalysts, while affording additional recyclability. The extraordinary flexibility and enriched concentration of the catalytically active moieties on linear polymers facilitate the concerted catalysis, thus leading to superior catalytic performance. This work therefore uncovers an entirely new strategy for designing bifunctional catalysts with double-activation behavior and opens a new avenue in the design of multicapable systems that mimic biocatalysis.
Co-reporter:Baiyan Li, Yiming Zhang, Dingxuan Ma, Zhenyu Xing, Tianliang Ma, Zhan Shi, Xiulei Ji and Shengqian Ma
Chemical Science 2016 vol. 7(Issue 3) pp:2138-2144
Publication Date(Web):2015/12/14
DOI:10.1039/C5SC04507J
Ion-exchange materials, currently dominated by resins, are widely used in a plethora of areas. However, the drawbacks of conventional resins necessitate the creation of a new model of ion exchange materials that feature controllable swelling, easily accessible ion exchange sites, high ion exchange capacity, fast ion exchange kinetics, and high chemical stability as illustrated herein in the context of functionalizing a porous organic polymer (POP) with ion exchange groups. The advantages of POP-based ion exchange materials in comparison with conventional resins and other types of ion exchange materials have been highlighted through an evaluation of their performances in scavenging precious metals at trace concentrations, removal of nuclear waste model ions, and size-selective ion capture. Our work thereby provides a new perspective to develop ion functionalized POPs as a versatile type of ion exchange materials for various applications.
Co-reporter:Baiyan Li, Dingxuan Ma, Yi Li, Yiming Zhang, Guanghua Li, Zhan Shi, Shouhua Feng, Michael J. Zaworotko, and Shengqian Ma
Chemistry of Materials 2016 Volume 28(Issue 13) pp:4781
Publication Date(Web):June 13, 2016
DOI:10.1021/acs.chemmater.6b01898
The introduction of bi- or multifunctionality into different cages of metal–organic frameworks (MOFs) has been of great interest because such MOF materials can demonstrate unique properties for various applications. Herein, we report a general strategy for creating different types of functionalized cages in MOFs by exerting control of the size of cage windows. Selective cage decoration was thereby enabled in such a manner that dual functional MOFs with different types of cages and pores can be created. The resultant different pore function MOF, DPF-MOF, is illustrated as a “proof of concept” in MOF MIL-101-Cr. An intermediate of a cascade reaction was successfully trapped and controlled the desired reaction direction. This DPF-MOF represents a new type of platform that, by trapping intermediates during the reaction processes, enhances our fundamental understanding of reaction chemistry in porous materials.
Co-reporter:Xiuli Wang, Wen-Yang Gao, Jian Luan, Lukasz Wojtas and Shengqian Ma
Chemical Communications 2016 vol. 52(Issue 9) pp:1971-1974
Publication Date(Web):10 Dec 2015
DOI:10.1039/C5CC09432A
Framework fragility upon the removal of guest solvent molecules has remained an issue for a substantial amount of metal–organic frameworks (MOFs). To address this issue, in this work we illustrate a strategy for the introduction of size-matching ligands as braces that are deliberately anchored onto the open metal sites to support and segment the pores thereby boosting the framework robustness. This is exemplified by employing 4,4′-bipyridine as a brace to bridge two trigonal prismatic clusters of Co3(μ3-O)(COO)6, generating a robust MOF that exhibits permanent porosity and selective gas adsorption behaviors.
Co-reporter:Yang Wang, Lu Wang, Huanhuan Chen, Xiaoya Hu, and Shengqian Ma
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 28) pp:18173-18181
Publication Date(Web):June 28, 2016
DOI:10.1021/acsami.6b04819
This paper describes the immobilization of gold nanoparticles on metal–metalloporphyrin frameworks (AuNPs/MMPF-6(Fe)) through electrostatic adsorption. The composites were characterized by powder X-ray diffraction, zeta potential, transmission electron microscopy, electrochemical impedance spectroscopy, and voltammetric methods. MMPF-6(Fe) exhibited a pair of redox peaks of the Fe(III)TCPP/Fe(II)TCPP redox couple. The AuNPs/MMPF-6(Fe)-based electrochemical sensor demonstrates a distinctly higher electrocatalytic response to the oxidation of hydroxylamine due to the synergic effect of the gold metal nanoparticles and metal–metalloporphyrin matrix. The voltammetric current response exhibits two linear dynamic ranges, 0.01–1.0 and 1.0–20.0 μmol L–1, and the detection limit was as low as 0.004 μmol L–1 (S/N = 3). Moreover, the biosensor exhibits high reproducibility and stability in acid solution. Our work not only offers a simple way to achieve the direct electrochemical behavior of metalloporphyrin but also expands the potential applications of MOFs-based composites in bioanalysis.
Co-reporter:Hongming He, Fuxing Sun, Shengqian Ma, and Guangshan Zhu
Inorganic Chemistry 2016 Volume 55(Issue 17) pp:9071
Publication Date(Web):August 24, 2016
DOI:10.1021/acs.inorgchem.6b01592
We reported a series of HKUST-like MOFs based on multiple copper-containing secondary building units (SBUs). Compound 1 is constructed by two SBUs: Cu2(CO2)4 paddle-wheel SBUs and Cu2I2 dimer SBUs. Compound 2 has Cu2(CO2)4 paddle-wheel SBUs and Cu4I4 SBUs. Furthermore, compound 3 possesses Cu2(CO2)4 paddle-wheel SBUs, Cu2I2 dimer SBUs, and Cu(CO2)4 SBUs. These compounds are promising materials for CO2 capture and separation, because they all display commendable adsorption of CO2 and high selectivity for CO2 over CH4 and N2. It is worthy to note that compound 1 exhibits the highest Brunauer–Emmett–Teller surface area (ca. 901 m2 g–1) among the MOF materials based on CuxIy SBUs. In addition, compound 3 is the first case that three copper SBUs coexist in MOFs.
Co-reporter:Wen-Yang Gao, Chen-Yen Tsai, Lukasz Wojtas, Timmy Thiounn, Chu-Chieh Lin, and Shengqian Ma
Inorganic Chemistry 2016 Volume 55(Issue 15) pp:7291
Publication Date(Web):June 23, 2016
DOI:10.1021/acs.inorgchem.6b00937
Herein we report a robust primitive cubic (pcu)-topology metal–metalloporphyrin framework (MMPF), MMPF-18, which was constructed from a ubiquitous secondary building unit of a tetranuclear zinc cluster, Zn4(μ4-O)(−COO)6, and a linear organic linker of 5,15-bis(4-carboxyphenyl)porphyrin (H2bcpp). The strong π–π stacking from porphyrins and the lengthy H2bcpp ligand affords a 4-fold-interpenetrating network along with reduced void spaces and confined narrow channels. Thereby, MMPF-18 presents segmented pores and high-density metalloporphyrin centers for selective CO2 uptake over CH4 and size-selective chemical transformation of CO2 with epoxides forming cyclic carbonates under ambient conditions.
Co-reporter:Weijie Zhang, Wenyang Gao, Tony Pham, Pingping Jiang, and Shengqian Ma
Crystal Growth & Design 2016 Volume 16(Issue 2) pp:1005-1009
Publication Date(Web):January 4, 2016
DOI:10.1021/acs.cgd.5b01548
Herein we report the construction of a robust metal-metalloporphyrin framework that is based upon a rare secondary building unit of infinite nickel oxide chain. The constructed MMPF-20 exhibits permanent porosity and selective adsorption of CO2 over CH4 as well as demonstrates interesting catalytic performances in the context of olefin epoxidation.
Co-reporter:Yao Chen and Shengqian Ma
Dalton Transactions 2016 vol. 45(Issue 24) pp:9744-9753
Publication Date(Web):15 Mar 2016
DOI:10.1039/C6DT00325G
Metal–organic frameworks (MOFs) have attracted great attention as a new type of prospective material with various merits and functionalities. MOFs can either act as biomimetic catalysts to mimic enzymatic activities or serve as hosts to encapsulate bio-active species for biomimetic catalysis. However, in comparison with the dramatic development of MOFs in other catalytic fields, MOF-based biomimetic catalysis is still in its infancy and is yet to be systematically and comprehensively explored. Herein, the principles and strategies for the design and synthesis of MOF-based biomimetic catalysts, especially the structural features of representative MOFs that are related to biomimetic catalysis, are summarized and reviewed. In addition, recent advances in biomimetic catalysis of MOFs and the relationships between their catalytic performances and the structural specificities are discussed in detail as well.
Co-reporter:Wen-Yang Gao;Haifan Wu;Kunyue Leng; Yinyong Sun; Shengqian Ma
Angewandte Chemie International Edition 2016 Volume 55( Issue 18) pp:5472-5476
Publication Date(Web):
DOI:10.1002/anie.201511484
Abstract
Described for the first time is that carbon dioxide (CO2) can be successfully inserted into aryl C−H bonds of the backbone of a metal–organic framework (MOF) to generate free carboxylate groups, which serve as Brønsted acid sites for efficiently catalyzing the methanolysis of epoxides. The work delineates the very first example of utilizing CO2 for heterogeneous C−H activation and carboxylation reactions on MOFs, and opens a new avenue for CO2 chemical transformations under mild reaction conditions.
Co-reporter:Wen-Yang Gao;Haifan Wu;Kunyue Leng; Yinyong Sun; Shengqian Ma
Angewandte Chemie 2016 Volume 128( Issue 18) pp:5562-5566
Publication Date(Web):
DOI:10.1002/ange.201511484
Abstract
Described for the first time is that carbon dioxide (CO2) can be successfully inserted into aryl C−H bonds of the backbone of a metal–organic framework (MOF) to generate free carboxylate groups, which serve as Brønsted acid sites for efficiently catalyzing the methanolysis of epoxides. The work delineates the very first example of utilizing CO2 for heterogeneous C−H activation and carboxylation reactions on MOFs, and opens a new avenue for CO2 chemical transformations under mild reaction conditions.
Co-reporter:Wen-Yang Gao;Timmy Thiounn;Lukasz Wojtas;Yu-Sheng Chen
Science China Chemistry 2016 Volume 59( Issue 8) pp:980-983
Publication Date(Web):2016 August
DOI:10.1007/s11426-016-0071-8
Herein we report two highly porous Zr-based metal-organic frameworks (MOFs, 1 and 2) constructed by the truncated octahedral secondary building unit (SBU) of Zr6O4(OH)4(CO2)12 and the organic linear ligand of 4,4'-stilbenedicarboxylic acid (H2sbdc) or 4,4'-azobenezenedicarboxylic acid (H2abdc). Both Zr-based MOFs are obtained as single crystals of suitable size for single-crystal X-ray diffraction analysis. Furthermore, these two Zr-based MOFs have been fully characterized by powder X-ray diffraction (PXRD) studies, thermogravimetric analysis (TGA), infrared spectroscopy (IR) and gas adsorption analysis. In particular, their CO2 gas adsorption behaviors have been investigated and discussed.
Co-reporter:Zheng Niu; Sheng Fang; Xiao Liu; Jian-Gong Ma; Shengqian Ma;Peng Cheng
Journal of the American Chemical Society 2015 Volume 137(Issue 47) pp:14873-14876
Publication Date(Web):November 12, 2015
DOI:10.1021/jacs.5b10815
Controlled assembly of 0D supramolecular nanocages into 2D or 3D architectures has been demonstrated for the first time via a coordination-driven polymerization approach, and the conversion from a 2D to 3D supramolecular architecture has also been successfully achieved via a temperature-induced crystal transformation. The boost of dimensionality for the supramolecular architecture has led to steady yet remarkable enhancement of properties, as reflected from the gas adsorption studies.
Co-reporter:Baiyan Li; Kunyue Leng; Yiming Zhang; James J. Dynes; Jian Wang; Yongfeng Hu; Dingxuan Ma; Zhan Shi; Liangkui Zhu; Daliang Zhang; Yinyong Sun; Matthew Chrzanowski
Journal of the American Chemical Society 2015 Volume 137(Issue 12) pp:4243-4248
Publication Date(Web):March 16, 2015
DOI:10.1021/jacs.5b01352
We report a strategy of combining a Brønsted acid metal–organic framework (MOF) with Lewis acid centers to afford a Lewis acid@Brønsted acid MOF with high catalytic activity, as exemplified in the context of MIL-101-Cr-SO3H·Al(III). Because of the synergy between the Brønsted acid framework and the Al(III) Lewis acid centers, MIL-101-Cr-SO3H·Al(III) demonstrates excellent catalytic performance in a series of fixed-bed reactions, outperforming two benchmark zeolite catalysts (H-Beta and HMOR). Our work therefore not only provides a new approach to achieve high catalytic activity in MOFs but also paves a way to develop MOFs as a new type of highly efficient heterogeneous catalysts for fixed-bed reactions.
Co-reporter:Wen-Yang Gao, Rong Cai, Tony Pham, Katherine A. Forrest, Adam Hogan, Patrick Nugent, Kia Williams, Lukasz Wojtas, Ryan Luebke, Łukasz J. Weseliński, Michael J. Zaworotko, Brian Space, Yu-Sheng Chen, Mohamed Eddaoudi, Xiaodong Shi, and Shengqian Ma
Chemistry of Materials 2015 Volume 27(Issue 6) pp:2144
Publication Date(Web):March 13, 2015
DOI:10.1021/acs.chemmater.5b00084
Copper paddlewheel based molecular building blocks (MBBs) are ubiquitous and have been widely employed for the construction of highly porous metal–organic frameworks (MOFs). However, most copper paddlewheel based MOFs fail to retain their structural integrity in the presence of water. This instability is directly correlated to the plausible displacement of coordinating carboxylates in the copper paddlewheel MBB, [Cu2(O2C−)4], by the strongly coordinating water molecules. In this comprehensive study, we illustrate the chemical stability control in the rht-MOF platform via strengthening the coordinating bonds within the triangular inorganic MBB, [Cu3O(N4–x(CH)xC−)3] (x = 0, 1, or 2). Remotely, the chemical stabilization propagated into the paddlewheel MBB to afford isoreticular rht-MOFs with remarkably enhanced water/chemical stabilities compared to the prototypal rht-MOF-1.
Co-reporter:Yang Wang, Guiqin Ye, Huanhuan Chen, Xiaoya Hu, Zheng Niu and Shengqian Ma
Journal of Materials Chemistry A 2015 vol. 3(Issue 29) pp:15292-15298
Publication Date(Web):26 Jun 2015
DOI:10.1039/C5TA03201F
In this work, we illustrate how to anchor –SO3H functional groups onto the pore surface of MOF for cadmium removal from aqueous solution via the approach of sequential post-synthetic modification and oxidation as exemplified in the context of functionalizing the MOF, Cu3(BTC)2 with sulfonic acid. The resultant sulfonic acid functionalized MOF, Cu3(BTC)2–SO3H demonstrates a high cadmium uptake capacity of 88.7 mg g−1, surpassing that of the benchmark adsorbents. In addition, it exhibits a fast kinetics with the kinetic rate constant k2 of 0.6818 g mg−1 min, which is 1–3 orders of magnitude higher than existing adsorbent materials for adsorbing cadmium ions from aqueous solution. Moreover, it demonstrates high selectivity of cadmium ions in the presents of other background metal ions, and can be readily regenerated and recycled without significant loss of cadmium uptake capacity. Our work thus paves a way for developing functionalized MOFs as a new type of platform for removing cadmium from wastewater.
Co-reporter:Qi Sun, Shengqian Ma, Zhifeng Dai, Xiangju Meng and Feng-Shou Xiao
Journal of Materials Chemistry A 2015 vol. 3(Issue 47) pp:23871-23875
Publication Date(Web):21 Oct 2015
DOI:10.1039/C5TA07267K
In this work we demonstrate for the first time the construction of a hierarchical porous ionic organic polymer via the polymerization of the vinyl-functionalized quaternary phosphonium salt monomer under solvothermal conditions. The resultant polymerized quaternary phosphonium (PQP) salt features a hierarchical porous structure and excellent amphiphilicity. After anion-exchange with peroxotungstate, the afforded W2O11/PQP demonstrates excellent performances as a heterogeneous phase-transfer catalyst in the context of epoxidation of olefin and oxidation of dibenzothiophene when using the environmentally benign H2O2 as the oxidant, superior to the homogeneous counterparts and other types of phase-transfer catalysts. Our work thereby paves a way to advance hierarchical porous ionic organic polymers as a new type of platform for heterogeneous phase transfer catalysis.
Co-reporter:Baiyan Li, Yiming Zhang, Dingxuan Ma, Liangkui Zhu, Daliang Zhang, Matthew Chrzanowski, Zhan Shi and Shengqian Ma
Chemical Communications 2015 vol. 51(Issue 41) pp:8683-8686
Publication Date(Web):16 Apr 2015
DOI:10.1039/C5CC01828E
In this work, we illustrate a template strategy to create extra pores in microporous carbon for enhancing ambient-pressure CO2 uptake, as exemplified in the context of carbonizing the silicon-containing POP, PPN-4, followed by removal of the silicon template. The resultant PPN-4/C600 demonstrates a remarkable enhancement of CO2 uptake capacity at 295 K and 1 bar by a factor of 2.3 compared to the parent PPN-4.
Co-reporter:Wen-Yang Gao, Kunyue Leng, Lindsay Cash, Matthew Chrzanowski, Chavis A. Stackhouse, Yinyong Sun and Shengqian Ma
Chemical Communications 2015 vol. 51(Issue 23) pp:4827-4829
Publication Date(Web):10 Feb 2015
DOI:10.1039/C4CC09410G
A series of prototypal metal–organic frameworks (MOFs) consisting of polyhedral cages with accessible Lewis-acid sites, have been systematically investigated for Friedländer annulation reaction, a straightforward approach to synthesizing quinoline and its derivatives. Amongst them MMCF-2 demonstrates significantly enhanced catalytic activity compared with the benchmark MOFs, HKUST-1 and MOF-505, as a result of a high-density of accessible Cu(II) Lewis acid sites and large window size in the cuboctahedral cage-based nanoreactor of MMCF-2.
Co-reporter:Yiming Zhang, Baiyan Li, Rajamani Krishna, Zili Wu, Dingxuan Ma, Zhan Shi, Tony Pham, Katherine Forrest, Brian Space and Shengqian Ma
Chemical Communications 2015 vol. 51(Issue 13) pp:2714-2717
Publication Date(Web):09 Jan 2015
DOI:10.1039/C4CC09774B
The introduction of the combination of open metal site (OMS) and π-complexation into MOF has led to very high ethylene–ethane adsorption selectivity at 318 K, as illustrated in the context of MIL-101–Cr–SO3Ag. The interactions with ethylene from both OMS and π-complexation in MIL-101–Cr–SO3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest that π-complexation contributes dominantly to the high ethylene–ethane adsorption selectivity.
Co-reporter:Wen-Yang Gao, Tony Pham, Katherine A. Forrest, Brian Space, Lukasz Wojtas, Yu-Sheng Chen and Shengqian Ma
Chemical Communications 2015 vol. 51(Issue 47) pp:9636-9639
Publication Date(Web):07 May 2015
DOI:10.1039/C5CC02573G
Two rht-type metal–organic frameworks (MOFs) based upon the tetrazolate moiety and pyrazolate moiety, respectively, have been investigated for carbon dioxide (CO2) adsorption and selective adsorption of CO2 over CH4, which shows that the rht-MOF featuring the pyrazolate moiety demonstrates superior performances compared to the rht-MOF based on the tetrazolate moiety. In spite of more exposed nitrogen atoms in the tetrazolate-based rht-MOF, the counter-intuitive observations of CO2 capture in the two rht-MOFs were interpreted by computational studies, which reveal that the local electric field favours more than the richness of exposed nitrogen atoms for the interactions with CO2 molecules.
Co-reporter:Lacey Lux, Kia Williams and Shengqian Ma
CrystEngComm 2015 vol. 17(Issue 1) pp:10-22
Publication Date(Web):09 Sep 2014
DOI:10.1039/C4CE01499E
Increasing population, global climate change, and dwindling fossil fuel reserves have led to a green energy revolution in the past few years, particularly in the fields of green energy generation and storage. While fuel cell, lithium-ion batteries, and supercapacitors are far from technical jargon in today's world, the sheer number of these devices is not accurately exhibited in the consumer market. Metal–organic frameworks (MOFs) are an emerging class of crystalline materials consisting of metal ion nodes and organic linkers that has shown promise in the fields of gas capture, gas storage, separations, catalysis, magnetism, fluorescence, and sensing to name only a few. The use of these materials as self-sacrificing templates, via calcination or pyrolysis, for the design of green energy generation and storage devices is the focus of this review.
Co-reporter:Wen-Yang Gao, Matthew Chrzanowski and Shengqian Ma
Chemical Society Reviews 2014 vol. 43(Issue 16) pp:5841-5866
Publication Date(Web):28 Mar 2014
DOI:10.1039/C4CS00001C
This review presents comprehensively recent progress in metal–metalloporphyrin frameworks (MMPFs) with an emphasis on versatile functionalities. Following a brief introduction of basic concepts and the potential virtues of MMPFs, we give a snapshot of the historical perspective of MMPFs since 1991. We then summarize four effective strategies implemented frequently to construct prototypal MMPFs. MMPFs represent a resurging class of promising functional materials, highlighted with diverse applications including guest-molecule adsorption and separation, catalysis, nano-thin films and light-harvesting.
Co-reporter:Baiyan Li ; Yiming Zhang ; Rajamani Krishna ; Kexin Yao ; Yu Han ; Zili Wu ; Dingxuan Ma ; Zhan Shi ; Tony Pham ; Brian Space ; Jian Liu ; Praveen K. Thallapally ; Jun Liu ; Matthew Chrzanowski
Journal of the American Chemical Society 2014 Volume 136(Issue 24) pp:8654-8660
Publication Date(Web):June 5, 2014
DOI:10.1021/ja502119z
In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane.
Co-reporter:Baiyan Li ; Yiming Zhang ; Dingxuan Ma ; Tianliang Ma ; Zhan Shi
Journal of the American Chemical Society 2014 Volume 136(Issue 4) pp:1202-1205
Publication Date(Web):January 15, 2014
DOI:10.1021/ja410868r
In this work, a new strategy is developed to encapsulate a metal-functionalized guest molecule into a metal–organic framework (MOF) via metal-cation-directed de novo assembly from the component fragments of the guest molecule. This strategy, as illustrated in proof-of-principle studies on the de novo assembly of metal(II) phthalocyanine molecules into bio-MOF-1, can circumvent some drawbacks of existing approaches for encapsulating guest molecules into MOFs, such as inaccessibility for larger guest molecules due to limitations of the MOF window size and disruption of the MOF framework structure by functionalized guest molecules. Overall, this work provides a general yet versatile approach for encapsulating a broader range of metal-functionalized guest molecules into MOFs for various applications.
Co-reporter:Xi-Sen Wang, Matthew Chrzanowski, Daqiang Yuan, Brandon S. Sweeting, and Shengqian Ma
Chemistry of Materials 2014 Volume 26(Issue 4) pp:1639
Publication Date(Web):February 11, 2014
DOI:10.1021/cm403860t
Although the active centers of many metalloenzymes have been well-studied, the ability for chemists to imitate the iron porphyrin heme found in these enzymes remains a challenge. Herein, we report a water/chemical-stable nanoporous covalent heme framework (CHF-1) that can be synthesized via the Yamamoto homocoupling reaction. Unlike other artificial enzymes, CHF-1 neatly arranges the heme centers to form a graphene-like two-dimensional framework bearing a high surface area (1620 m2/g) and high density of active sites. Biomimetic catalytic reactions show that CHF-1 catalyst is an effective heterogeneous catalyst with exceptionally high binding affinities and high catalytic efficiency approaching that of natural heme-based enzymes.
Co-reporter:Yiming Zhang, Baiyan Li and Shengqian Ma
Chemical Communications 2014 vol. 50(Issue 62) pp:8507-8510
Publication Date(Web):11 Jun 2014
DOI:10.1039/C4CC04012K
Dual functionalization of porous aromatic frameworks (PAFs) has been illustrated in the context of incorporating two antagonistic sites of strong acid and strong base into the highly porous and highly robust PAF-1 via stepwise post-synthetic modification. The resulting bifunctionalized PAF-1 exhibits excellent performances in catalyzing a series of cascade reactions and demonstrates superior chemical stability compared to the counterparts of mesoporous silica and MOFs, thereby opening the door for dual functionalization of PAFs as a new platform for heterogeneous cascade catalysis.
Co-reporter:Wen-Yang Gao, Lukasz Wojtas and Shengqian Ma
Chemical Communications 2014 vol. 50(Issue 40) pp:5316-5318
Publication Date(Web):27 Nov 2013
DOI:10.1039/C3CC47542E
Self-assembly of the custom-designed octatopic porphyrin ligand of tetrakis(3,5-dicarboxybiphenyl)porphine with the in situ generated Cu2(CO2)4 paddlewheel moieties afforded a porous metal–metalloporphyrin framework, MMPF-9, which features a high density of Cu(II) sites confined within nanoscopic channels and demonstrates excellent performances as a heterogeneous Lewis-acid catalyst for chemical fixation of CO2 to form carbonates at room temperature under 1 atm pressure.
Co-reporter:Yao Chen, Sungyub Han, Xiao Li, Zhenjie Zhang, and Shengqian Ma
Inorganic Chemistry 2014 Volume 53(Issue 19) pp:10006-10008
Publication Date(Web):September 19, 2014
DOI:10.1021/ic501062r
The strong interactions between microperoxidase (MP-11) and Tb-mesoMOF were identified via Raman spectroscopic studies, which revealed that MP-11 molecules interact with the framework of Tb-mesoMOF through π···π interactions between the heme of MP-11 and the conjugated triazine and benzene rings in the organic ligand of Tb-mesoMOF. The strong interactions facilitate the retention of MP-11 molecules within the metal–organic framework (MOF) pores, which is in striking contrast with the severe leaching of MP-11 from MCM-41 due to the lack of specific interactions between enzyme molecules and the mesoporous silica material.
Co-reporter:Wen-Yang Gao;Yao Chen;Youhong Niu;Kia Williams;Lindsay Cash;Pastor J. Perez;Lukasz Wojtas; Jianfeng Cai;Yu-Sheng Chen; Shengqian Ma
Angewandte Chemie International Edition 2014 Volume 53( Issue 10) pp:2615-2619
Publication Date(Web):
DOI:10.1002/anie.201309778
Abstract
Crystal engineering of the nbo metal–organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N′,N′′,N′′′-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu2(Cu-tactmb)(H2O)3(NO3)2]. This MOF demonstrates high catalytic activity for the chemical fixation of CO2 into cyclic carbonates at room temperature under 1 atm pressure.
Co-reporter:Wen-Yang Gao;Yao Chen;Youhong Niu;Kia Williams;Lindsay Cash;Pastor J. Perez;Lukasz Wojtas; Jianfeng Cai;Yu-Sheng Chen; Shengqian Ma
Angewandte Chemie 2014 Volume 126( Issue 10) pp:2653-2657
Publication Date(Web):
DOI:10.1002/ange.201309778
Abstract
Crystal engineering of the nbo metal–organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N′,N′′,N′′′-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu2(Cu-tactmb)(H2O)3(NO3)2]. This MOF demonstrates high catalytic activity for the chemical fixation of CO2 into cyclic carbonates at room temperature under 1 atm pressure.
Co-reporter:Xi-Sen Wang, Jian Liu, Jean M. Bonefont, Da-Qiang Yuan, Praveen K. Thallapally and Shengqian Ma
Chemical Communications 2013 vol. 49(Issue 15) pp:1533-1535
Publication Date(Web):04 Jan 2013
DOI:10.1039/C2CC38067F
A highly porous porphyrin-based organic polymer, PCPF-1, was constructed via homo-coupling reaction of the custom-designed porphyrin ligand, 5,10,15,20-tetrakis(4-bromophenyl)porphyrin. PCPF-1 possesses a large BET surface area of over 1300 m2 g−1 (Langmuir surface area of over 2400 m2 g−1) and exhibits strong hydrophobicity with a water contact angle of 135°, and these features afford it the highest adsorptive capacities for saturated hydrocarbons and gasoline among sorbent materials reported thus far, as well as render it the capability to remove oil from water.
Co-reporter:Wen-Yang Gao, Rong Cai, Le Meng, Lukasz Wojtas, Wei Zhou, Taner Yildirim, Xiaodong Shi and Shengqian Ma
Chemical Communications 2013 vol. 49(Issue 89) pp:10516-10518
Publication Date(Web):18 Sep 2013
DOI:10.1039/C3CC45986A
A strategy for building highly connected robust MOFs from linear ligands is exemplified by the construction of MTAF-4, a rare (6,9)-connected MOF, based on the custom-designed bifunctional linear ligand, 4-(1,2,3-triazol-4-yl)-benzoate, that connects two types of highly connected zinc cluster moieties generated in situ. MTAF-4 is robust and permanently microporous and is capable of adsorbing CO2, H2 and CH4 under high pressures.
Co-reporter:Yiming Zhang, Baiyan Li, Kia Williams, Wen-Yang Gao and Shengqian Ma
Chemical Communications 2013 vol. 49(Issue 87) pp:10269-10271
Publication Date(Web):10 Sep 2013
DOI:10.1039/C3CC45252B
Pre-introducing an extra carbon source into the porous aromatic framework of PAF-1 followed by thermolysis affords a new microporous carbon material, which demonstrates a CO2 uptake capacity of 93 cm3 g−1 (equivalent to 4.1 mmol g−1 or 18.2 wt%) at 295 K and 1 bar.
Co-reporter:Wen-Yang Gao, Zhuxiu Zhang, Lindsay Cash, Lukasz Wojtas, Yu-Sheng Chen and Shengqian Ma
CrystEngComm 2013 vol. 15(Issue 45) pp:9320-9323
Publication Date(Web):11 Jul 2013
DOI:10.1039/C3CE41090K
Two rare indium-based porous metal–metalloporphyrin frameworks (MMPFs), MMPF-7 and MMPF-8, were constructed by self-assembly of In(III) and two custom-designed porphyrin–tetracarboxylate ligands. MMPF-7 and MMPF-8 possess the pts topology and exhibit interesting CO2 adsorption properties.
Co-reporter:Dr. Xi-Sen Wang;Matthew Chrzanowski;Dr. Lukasz Wojtas;Dr. Yu-Sheng Chen;Dr. Shengqian Ma
Chemistry - A European Journal 2013 Volume 19( Issue 10) pp:3297-3301
Publication Date(Web):
DOI:10.1002/chem.201204358
Co-reporter:Yao Chen ; Vasiliki Lykourinou ; Carissa Vetromile ; Tran Hoang ; Li-June Ming ; Randy W. Larsen
Journal of the American Chemical Society 2012 Volume 134(Issue 32) pp:13188-13191
Publication Date(Web):August 3, 2012
DOI:10.1021/ja305144x
It has been demonstrated for the first time that the heme protein cytochrome c (Cyt c) can enter the interior of a MOF despite the larger molecular dimension of the protein relative to the access pore sizes. Mechanistic studies suggest that the Cyt c molecules must undergo a significant conformational change during translocation into the MOF interior through the relatively small nanopores.
Co-reporter:Xi-Sen Wang, Matthew Chrzanowski, Wen-Yang Gao, Lukasz Wojtas, Yu-Sheng Chen, Michael J. Zaworotko and Shengqian Ma
Chemical Science 2012 vol. 3(Issue 9) pp:2823-2827
Publication Date(Web):21 Jun 2012
DOI:10.1039/C2SC20330H
Metal–organic materials that are constructed from polyhedral supermolecular building blocks, SBBs, can offer exquisite control over structure and afford useful features such as multiple cage types and relatively narrow pores. This contribution describes how a custom-designed porphyrin, tdcpp, self-assembles with M(II) (M = Zn, Cd) cations to generate the first examples of SBBs that are uniform polyhedra based upon a porphyrin molecular building block, MBB. The faces of tdcpp moieties link triangular M2(CO2)3 or M(CO2)3 moieties to form small cubicuboctahedral SBBs that are in turn fused to adjacent SBBs at the opposite face of each tdcpp moiety. The resulting high symmetry augmented pcu topology networks, MMPF-4 (M = Zn) and MMPF-5 (M = Cd), exhibit two distinct polyhedral cages and are permanently microporous with selective CO2 uptake.
Co-reporter:Xi-Sen Wang, Matthew Chrzanowski, Chungsik Kim, Wen-Yang Gao, Lukasz Wojtas, Yu-Sheng Chen, X. Peter Zhang and Shengqian Ma
Chemical Communications 2012 vol. 48(Issue 57) pp:7173-7175
Publication Date(Web):24 May 2012
DOI:10.1039/C2CC33118G
A porous metal–metalloporphyrin framework, MMPF-2, has been constructed from a custom-designed octatopic porphyrin ligand, tetrakis(3,5-dicarboxyphenyl)porphine, that links a distorted cobalt trigonal prism secondary building unit. MMPF-2 possesses permanent microporosity with the highest surface area of 2037 m2 g−1 among reported porphyrin-based MOFs, and demonstrates a high uptake capacity of 170 cm3 g−1 CO2 at 273 K and 1 bar.
Co-reporter:Wen-Yang Gao, Wuming Yan, Rong Cai, Kia Williams, Andrea Salas, Lukasz Wojtas, Xiaodong Shi and Shengqian Ma
Chemical Communications 2012 vol. 48(Issue 71) pp:8898-8900
Publication Date(Web):23 Jul 2012
DOI:10.1039/C2CC34380K
The replacement of the pillar ligand, 4,4′-bipyridine, in the prototypal pillared MOF, MOF-508, with the custom-designed ligand, 4,4′-(2H-1,2,3-triazole-2,4-diyl)dipyridine, affords a porous metal–triazolate framework, MTAF-3, which demonstrates remarkable enhancement of CO2 uptake capacity by a factor of ∼3 compared to the parent MOF-508.
Co-reporter:Yao Chen, Tran Hoang, and Shengqian Ma
Inorganic Chemistry 2012 Volume 51(Issue 23) pp:12600-12602
Publication Date(Web):November 20, 2012
DOI:10.1021/ic301923x
A porous metal–metalloporphyrin framework, MMPF-6, based upon an iron(III)-metalated porphyrin ligand and a secondary binding unit of a zirconium oxide cluster was constructed; MMPF-6 demonstrated interesting peroxidase activity comparable to that of the heme protein myoglobin as well as exhibited solvent adaptability of retaining the peroxidase activity in an organic solvent.
Co-reporter:Yao Chen ; Vasiliki Lykourinou ; Tran Hoang ; Li-June Ming
Inorganic Chemistry 2012 Volume 51(Issue 17) pp:9156-9158
Publication Date(Web):August 10, 2012
DOI:10.1021/ic301280n
The protein myoglobin has been successfully immobilized into a mesoporous metal–organic framework with hierarchical pore sizes, which demonstrates interesting size-selective biocatalysis as well as superior catalytic activities toward small substrate oxidation compared to its mesoporous silica material counterpart.
Co-reporter:Chi-Kai Lin, Dan Zhao, Wen-Yang Gao, Zhenzhen Yang, Jingyun Ye, Tao Xu, Qingfeng Ge, Shengqian Ma, and Di-Jia Liu
Inorganic Chemistry 2012 Volume 51(Issue 16) pp:9039-9044
Publication Date(Web):July 27, 2012
DOI:10.1021/ic301189m
The tunability of the band gaps in Zn-based metal–organic frameworks (MOFs) has been experimentally demonstrated via two different approaches: changing the cluster size of the secondary building unit (SBU) or alternating the conjugation of the organic linker.
Co-reporter:Wen-Yang Gao ; Wuming Yan ; Rong Cai ; Le Meng ; Andrea Salas ; Xi-Sen Wang ; Lukasz Wojtas ; Xiaodong Shi
Inorganic Chemistry 2012 Volume 51(Issue 8) pp:4423-4425
Publication Date(Web):March 26, 2012
DOI:10.1021/ic3002256
The self-assembly of a custom-designed bifunctional ligand featuring both 1,2,3-triazolate and carboxylate donor groups with a pentanuclear zinc cluster generated in situ affords a double-walled metal triazolate framework (MTAF) material, MTAF-1 (Zn5(μ3-O)2(C9N3H5O2)5(H+)4(H2O)17(C3H7NO)10), which exhibits a surface area of 2300 m2/g and demonstrates interesting selective CO2 uptake performances.
Co-reporter:Wen-Yang Gao, Youhong Niu, Yao Chen, Lukasz Wojtas, Jianfeng Cai, Yu-Sheng Chen and Shengqian Ma
CrystEngComm 2012 vol. 14(Issue 19) pp:6115-6117
Publication Date(Web):26 Apr 2012
DOI:10.1039/C2CE25484K
A two-fold interpenetrating microporous metal–organic framework, MMCF-1, has been constructed via the self-assembly of a custom-designed macrocyclic tetracarboxylate ligand and Cd(II), and it exhibits interesting selective uptake of CO2 over N2.
Co-reporter:Le Meng;Qigan Cheng;Chungsik Kim;Wen-Yang Gao;Lukasz Wojtas;Yu-Sheng Chen; Michael J. Zaworotko; X. Peter Zhang; Shengqian Ma
Angewandte Chemie International Edition 2012 Volume 51( Issue 40) pp:10082-10085
Publication Date(Web):
DOI:10.1002/anie.201205603
Co-reporter:Vasiliki Lykourinou ; Yao Chen ; Xi-Sen Wang ; Le Meng ; Tran Hoang ; Li-June Ming ; Ronald L. Musselman
Journal of the American Chemical Society 2011 Volume 133(Issue 27) pp:10382-10385
Publication Date(Web):June 17, 2011
DOI:10.1021/ja2038003
Microperoxidase-11 has for the first time been successfully immobilized into a mesoporous metal–organic framework (MOF) consisting of nanoscopic cages and it demonstrates superior enzymatic catalysis performances compared to its mesoporous silica counterpart.
Co-reporter:Xi-Sen Wang ; Le Meng ; Qigan Cheng ; Chungsik Kim ; Lukasz Wojtas ; Matthew Chrzanowski ; Yu-Sheng Chen ; X. Peter Zhang
Journal of the American Chemical Society 2011 Volume 133(Issue 41) pp:16322-16325
Publication Date(Web):September 28, 2011
DOI:10.1021/ja204339e
An unprecedented nanoscopic polyhedral cage-containing metal–metalloporphyrin framework, MMPF-1, has been constructed from a custom-designed porphyrin ligand, 5,15-bis(3,5-dicarboxyphenyl)porphine, that links Cu2(carboxylate)4 moieties. A high density of 16 open copper sites confined within a nanoscopic polyhedral cage has been achieved, and the packing of the porphyrin cages via an “ABAB” pattern affords MMPF-1 ultramicropores which render it selective toward adsorption of H2 and O2 over N2, and CO2 over CH4.
Co-reporter:Yao Chen and Shengqian Ma
Dalton Transactions 2016 - vol. 45(Issue 24) pp:NaN9753-9753
Publication Date(Web):2016/03/15
DOI:10.1039/C6DT00325G
Metal–organic frameworks (MOFs) have attracted great attention as a new type of prospective material with various merits and functionalities. MOFs can either act as biomimetic catalysts to mimic enzymatic activities or serve as hosts to encapsulate bio-active species for biomimetic catalysis. However, in comparison with the dramatic development of MOFs in other catalytic fields, MOF-based biomimetic catalysis is still in its infancy and is yet to be systematically and comprehensively explored. Herein, the principles and strategies for the design and synthesis of MOF-based biomimetic catalysts, especially the structural features of representative MOFs that are related to biomimetic catalysis, are summarized and reviewed. In addition, recent advances in biomimetic catalysis of MOFs and the relationships between their catalytic performances and the structural specificities are discussed in detail as well.
Co-reporter:Kia Williams, Le Meng, Sinhye Lee, Lacey Lux, Wenyang Gao and Shengqian Ma
Inorganic Chemistry Frontiers 2016 - vol. 3(Issue 3) pp:NaN396-396
Publication Date(Web):2016/01/06
DOI:10.1039/C5QI00229J
In this work, we demonstrate the impartment of Brønsted acidity into a zeolitic imidazole framework, ZIF-90, via post-synthetically oxidizing the aldehyde group into carboxylate group to afford ZIF-90-COOH. The preservation crystallinity and porosity after post-synthetic oxidation was confirmed by powder X-ray diffraction studies and N2 gas adsorption analysis respectively. The successful conversion of the aldehyde group into carboxylate group was verified by FT-IR studies, which resulted in remarkable enhancement of methylene blue uptake in the resultant ZIF-90-COOH due to the strong electrostatic interactions between cationic methylene blue and the anionic carboxylate group.
Co-reporter:Baiyan Li, Youssef Belmabkhout, Yiming Zhang, Prashant M. Bhatt, Hongming He, Daliang Zhang, Yu Han, Mohamed Eddaoudi, Jason A. Perman and Shengqian Ma
Chemical Communications 2016 - vol. 52(Issue 96) pp:NaN13900-13900
Publication Date(Web):2016/11/04
DOI:10.1039/C6CC08008A
We unveil a unique kinetic driven separation material for selectively removing linear paraffins from iso-paraffins via a molecular sieving mechanism. Subsequent carbonization and thermal treatment of CD-MOF-2, the cyclodextrin metal–organic framework, afforded a carbon molecular sieve with a uniform and reduced pore size of ca. 5.0 Å, and it exhibited highly selective kinetic separation of n-butane and n-pentane from iso-butane and iso-pentane, respectively.
Co-reporter:Yang Wang, Lu Wang, Wei Huang, Ting Zhang, Xiaoya Hu, Jason A. Perman and Shengqian Ma
Journal of Materials Chemistry A 2017 - vol. 5(Issue 18) pp:NaN8393-8393
Publication Date(Web):2017/04/05
DOI:10.1039/C7TA01066D
In this work, a conductive electrochemical sensor, UiO-66-NH2@PANI, was successfully prepared by polymerizing the conductive polyaniline (PANI) polymer around the metal–organic framework UiO-66-NH2. Fourier transform infrared spectra, X-ray diffraction patterns, and X-ray photoelectron spectral data support the formation of UiO-66-NH2@PANI. Additionally, scanning and transmission electron microscopy investigations confirm that PANI uniformly coated the surface of UiO-66-NH2. The resultant material was applied to construct a novel electrochemical sensor for the reliable detection of cadmium ions due to the chelation mechanism between metal cations and amine groups. Under optimized conditions, a linear detection of Cd2+ concentration range of 0.5–600 μg L−1 was repeatable with a 0.3 μg L−1 lowest level detection limit. Little to no interference effects from other co-existing ions allow the sensor to work in varying environments for practical application. This method of coating metal–organic frameworks may show utility for constructing highly sensitive electrochemical sensors for the detection of heavy metal ions and more.
Co-reporter:Hongming He, Fuxing Sun, Briana Aguila, Jason A. Perman, Shengqian Ma and Guangshan Zhu
Journal of Materials Chemistry A 2016 - vol. 4(Issue 39) pp:NaN15246-15246
Publication Date(Web):2016/09/12
DOI:10.1039/C6TA05098K
A bifunctional MOF (JUC-199) featuring dual functionality, open metal sites (Zn2+) and Lewis basic sites (–NH2), has been successfully synthesized using a custom-designed ligand. JUC-199 demonstrated good selective gas sorption behaviours with IAST selectivity values of 9, 30, 37 and 64 at 298 K and 101 kPa for CO2/CH4, CO2/N2, C2H6/CH4 and C2H4/CH4 respectively; surpassing those of most MOFs reported thus far. Moreover, JUC-199 can serve as a heterogeneous cascade catalyst to efficiently catalyse the tandem one-pot deacatalization-Knoevenagel condensation reaction.
Co-reporter:Qi Sun, Shengqian Ma, Zhifeng Dai, Xiangju Meng and Feng-Shou Xiao
Journal of Materials Chemistry A 2015 - vol. 3(Issue 47) pp:NaN23875-23875
Publication Date(Web):2015/10/21
DOI:10.1039/C5TA07267K
In this work we demonstrate for the first time the construction of a hierarchical porous ionic organic polymer via the polymerization of the vinyl-functionalized quaternary phosphonium salt monomer under solvothermal conditions. The resultant polymerized quaternary phosphonium (PQP) salt features a hierarchical porous structure and excellent amphiphilicity. After anion-exchange with peroxotungstate, the afforded W2O11/PQP demonstrates excellent performances as a heterogeneous phase-transfer catalyst in the context of epoxidation of olefin and oxidation of dibenzothiophene when using the environmentally benign H2O2 as the oxidant, superior to the homogeneous counterparts and other types of phase-transfer catalysts. Our work thereby paves a way to advance hierarchical porous ionic organic polymers as a new type of platform for heterogeneous phase transfer catalysis.
Co-reporter:Baiyan Li, Yiming Zhang, Dingxuan Ma, Zhenyu Xing, Tianliang Ma, Zhan Shi, Xiulei Ji and Shengqian Ma
Chemical Science (2010-Present) 2016 - vol. 7(Issue 3) pp:NaN2144-2144
Publication Date(Web):2015/12/14
DOI:10.1039/C5SC04507J
Ion-exchange materials, currently dominated by resins, are widely used in a plethora of areas. However, the drawbacks of conventional resins necessitate the creation of a new model of ion exchange materials that feature controllable swelling, easily accessible ion exchange sites, high ion exchange capacity, fast ion exchange kinetics, and high chemical stability as illustrated herein in the context of functionalizing a porous organic polymer (POP) with ion exchange groups. The advantages of POP-based ion exchange materials in comparison with conventional resins and other types of ion exchange materials have been highlighted through an evaluation of their performances in scavenging precious metals at trace concentrations, removal of nuclear waste model ions, and size-selective ion capture. Our work thereby provides a new perspective to develop ion functionalized POPs as a versatile type of ion exchange materials for various applications.
Co-reporter:Xi-Sen Wang, Matthew Chrzanowski, Wen-Yang Gao, Lukasz Wojtas, Yu-Sheng Chen, Michael J. Zaworotko and Shengqian Ma
Chemical Science (2010-Present) 2012 - vol. 3(Issue 9) pp:NaN2827-2827
Publication Date(Web):2012/06/21
DOI:10.1039/C2SC20330H
Metal–organic materials that are constructed from polyhedral supermolecular building blocks, SBBs, can offer exquisite control over structure and afford useful features such as multiple cage types and relatively narrow pores. This contribution describes how a custom-designed porphyrin, tdcpp, self-assembles with M(II) (M = Zn, Cd) cations to generate the first examples of SBBs that are uniform polyhedra based upon a porphyrin molecular building block, MBB. The faces of tdcpp moieties link triangular M2(CO2)3 or M(CO2)3 moieties to form small cubicuboctahedral SBBs that are in turn fused to adjacent SBBs at the opposite face of each tdcpp moiety. The resulting high symmetry augmented pcu topology networks, MMPF-4 (M = Zn) and MMPF-5 (M = Cd), exhibit two distinct polyhedral cages and are permanently microporous with selective CO2 uptake.
Co-reporter:Yang Wang, Guiqin Ye, Huanhuan Chen, Xiaoya Hu, Zheng Niu and Shengqian Ma
Journal of Materials Chemistry A 2015 - vol. 3(Issue 29) pp:NaN15298-15298
Publication Date(Web):2015/06/26
DOI:10.1039/C5TA03201F
In this work, we illustrate how to anchor –SO3H functional groups onto the pore surface of MOF for cadmium removal from aqueous solution via the approach of sequential post-synthetic modification and oxidation as exemplified in the context of functionalizing the MOF, Cu3(BTC)2 with sulfonic acid. The resultant sulfonic acid functionalized MOF, Cu3(BTC)2–SO3H demonstrates a high cadmium uptake capacity of 88.7 mg g−1, surpassing that of the benchmark adsorbents. In addition, it exhibits a fast kinetics with the kinetic rate constant k2 of 0.6818 g mg−1 min, which is 1–3 orders of magnitude higher than existing adsorbent materials for adsorbing cadmium ions from aqueous solution. Moreover, it demonstrates high selectivity of cadmium ions in the presents of other background metal ions, and can be readily regenerated and recycled without significant loss of cadmium uptake capacity. Our work thus paves a way for developing functionalized MOFs as a new type of platform for removing cadmium from wastewater.
Co-reporter:Xi-Sen Wang, Matthew Chrzanowski, Chungsik Kim, Wen-Yang Gao, Lukasz Wojtas, Yu-Sheng Chen, X. Peter Zhang and Shengqian Ma
Chemical Communications 2012 - vol. 48(Issue 57) pp:NaN7175-7175
Publication Date(Web):2012/05/24
DOI:10.1039/C2CC33118G
A porous metal–metalloporphyrin framework, MMPF-2, has been constructed from a custom-designed octatopic porphyrin ligand, tetrakis(3,5-dicarboxyphenyl)porphine, that links a distorted cobalt trigonal prism secondary building unit. MMPF-2 possesses permanent microporosity with the highest surface area of 2037 m2 g−1 among reported porphyrin-based MOFs, and demonstrates a high uptake capacity of 170 cm3 g−1 CO2 at 273 K and 1 bar.
Co-reporter:Xi-Sen Wang, Jian Liu, Jean M. Bonefont, Da-Qiang Yuan, Praveen K. Thallapally and Shengqian Ma
Chemical Communications 2013 - vol. 49(Issue 15) pp:NaN1535-1535
Publication Date(Web):2013/01/04
DOI:10.1039/C2CC38067F
A highly porous porphyrin-based organic polymer, PCPF-1, was constructed via homo-coupling reaction of the custom-designed porphyrin ligand, 5,10,15,20-tetrakis(4-bromophenyl)porphyrin. PCPF-1 possesses a large BET surface area of over 1300 m2 g−1 (Langmuir surface area of over 2400 m2 g−1) and exhibits strong hydrophobicity with a water contact angle of 135°, and these features afford it the highest adsorptive capacities for saturated hydrocarbons and gasoline among sorbent materials reported thus far, as well as render it the capability to remove oil from water.
Co-reporter:Wen-Yang Gao, Lukasz Wojtas and Shengqian Ma
Chemical Communications 2014 - vol. 50(Issue 40) pp:NaN5318-5318
Publication Date(Web):2013/11/27
DOI:10.1039/C3CC47542E
Self-assembly of the custom-designed octatopic porphyrin ligand of tetrakis(3,5-dicarboxybiphenyl)porphine with the in situ generated Cu2(CO2)4 paddlewheel moieties afforded a porous metal–metalloporphyrin framework, MMPF-9, which features a high density of Cu(II) sites confined within nanoscopic channels and demonstrates excellent performances as a heterogeneous Lewis-acid catalyst for chemical fixation of CO2 to form carbonates at room temperature under 1 atm pressure.
Co-reporter:Yiming Zhang, Baiyan Li and Shengqian Ma
Chemical Communications 2014 - vol. 50(Issue 62) pp:NaN8510-8510
Publication Date(Web):2014/06/11
DOI:10.1039/C4CC04012K
Dual functionalization of porous aromatic frameworks (PAFs) has been illustrated in the context of incorporating two antagonistic sites of strong acid and strong base into the highly porous and highly robust PAF-1 via stepwise post-synthetic modification. The resulting bifunctionalized PAF-1 exhibits excellent performances in catalyzing a series of cascade reactions and demonstrates superior chemical stability compared to the counterparts of mesoporous silica and MOFs, thereby opening the door for dual functionalization of PAFs as a new platform for heterogeneous cascade catalysis.
Co-reporter:Yiming Zhang, Baiyan Li, Rajamani Krishna, Zili Wu, Dingxuan Ma, Zhan Shi, Tony Pham, Katherine Forrest, Brian Space and Shengqian Ma
Chemical Communications 2015 - vol. 51(Issue 13) pp:NaN2717-2717
Publication Date(Web):2015/01/09
DOI:10.1039/C4CC09774B
The introduction of the combination of open metal site (OMS) and π-complexation into MOF has led to very high ethylene–ethane adsorption selectivity at 318 K, as illustrated in the context of MIL-101–Cr–SO3Ag. The interactions with ethylene from both OMS and π-complexation in MIL-101–Cr–SO3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest that π-complexation contributes dominantly to the high ethylene–ethane adsorption selectivity.
Co-reporter:Wen-Yang Gao, Kunyue Leng, Lindsay Cash, Matthew Chrzanowski, Chavis A. Stackhouse, Yinyong Sun and Shengqian Ma
Chemical Communications 2015 - vol. 51(Issue 23) pp:NaN4829-4829
Publication Date(Web):2015/02/10
DOI:10.1039/C4CC09410G
A series of prototypal metal–organic frameworks (MOFs) consisting of polyhedral cages with accessible Lewis-acid sites, have been systematically investigated for Friedländer annulation reaction, a straightforward approach to synthesizing quinoline and its derivatives. Amongst them MMCF-2 demonstrates significantly enhanced catalytic activity compared with the benchmark MOFs, HKUST-1 and MOF-505, as a result of a high-density of accessible Cu(II) Lewis acid sites and large window size in the cuboctahedral cage-based nanoreactor of MMCF-2.
Co-reporter:Yiming Zhang, Baiyan Li, Kia Williams, Wen-Yang Gao and Shengqian Ma
Chemical Communications 2013 - vol. 49(Issue 87) pp:NaN10271-10271
Publication Date(Web):2013/09/10
DOI:10.1039/C3CC45252B
Pre-introducing an extra carbon source into the porous aromatic framework of PAF-1 followed by thermolysis affords a new microporous carbon material, which demonstrates a CO2 uptake capacity of 93 cm3 g−1 (equivalent to 4.1 mmol g−1 or 18.2 wt%) at 295 K and 1 bar.
Co-reporter:Wen-Yang Gao, Tony Pham, Katherine A. Forrest, Brian Space, Lukasz Wojtas, Yu-Sheng Chen and Shengqian Ma
Chemical Communications 2015 - vol. 51(Issue 47) pp:NaN9639-9639
Publication Date(Web):2015/05/07
DOI:10.1039/C5CC02573G
Two rht-type metal–organic frameworks (MOFs) based upon the tetrazolate moiety and pyrazolate moiety, respectively, have been investigated for carbon dioxide (CO2) adsorption and selective adsorption of CO2 over CH4, which shows that the rht-MOF featuring the pyrazolate moiety demonstrates superior performances compared to the rht-MOF based on the tetrazolate moiety. In spite of more exposed nitrogen atoms in the tetrazolate-based rht-MOF, the counter-intuitive observations of CO2 capture in the two rht-MOFs were interpreted by computational studies, which reveal that the local electric field favours more than the richness of exposed nitrogen atoms for the interactions with CO2 molecules.
Co-reporter:Xiuli Wang, Wen-Yang Gao, Jian Luan, Lukasz Wojtas and Shengqian Ma
Chemical Communications 2016 - vol. 52(Issue 9) pp:NaN1974-1974
Publication Date(Web):2015/12/10
DOI:10.1039/C5CC09432A
Framework fragility upon the removal of guest solvent molecules has remained an issue for a substantial amount of metal–organic frameworks (MOFs). To address this issue, in this work we illustrate a strategy for the introduction of size-matching ligands as braces that are deliberately anchored onto the open metal sites to support and segment the pores thereby boosting the framework robustness. This is exemplified by employing 4,4′-bipyridine as a brace to bridge two trigonal prismatic clusters of Co3(μ3-O)(COO)6, generating a robust MOF that exhibits permanent porosity and selective gas adsorption behaviors.
Co-reporter:Baiyan Li, Yiming Zhang, Dingxuan Ma, Liangkui Zhu, Daliang Zhang, Matthew Chrzanowski, Zhan Shi and Shengqian Ma
Chemical Communications 2015 - vol. 51(Issue 41) pp:NaN8686-8686
Publication Date(Web):2015/04/16
DOI:10.1039/C5CC01828E
In this work, we illustrate a template strategy to create extra pores in microporous carbon for enhancing ambient-pressure CO2 uptake, as exemplified in the context of carbonizing the silicon-containing POP, PPN-4, followed by removal of the silicon template. The resultant PPN-4/C600 demonstrates a remarkable enhancement of CO2 uptake capacity at 295 K and 1 bar by a factor of 2.3 compared to the parent PPN-4.
Co-reporter:Wen-Yang Gao, Rong Cai, Le Meng, Lukasz Wojtas, Wei Zhou, Taner Yildirim, Xiaodong Shi and Shengqian Ma
Chemical Communications 2013 - vol. 49(Issue 89) pp:NaN10518-10518
Publication Date(Web):2013/09/18
DOI:10.1039/C3CC45986A
A strategy for building highly connected robust MOFs from linear ligands is exemplified by the construction of MTAF-4, a rare (6,9)-connected MOF, based on the custom-designed bifunctional linear ligand, 4-(1,2,3-triazol-4-yl)-benzoate, that connects two types of highly connected zinc cluster moieties generated in situ. MTAF-4 is robust and permanently microporous and is capable of adsorbing CO2, H2 and CH4 under high pressures.
Co-reporter:Wen-Yang Gao, Matthew Chrzanowski and Shengqian Ma
Chemical Society Reviews 2014 - vol. 43(Issue 16) pp:NaN5866-5866
Publication Date(Web):2014/03/28
DOI:10.1039/C4CS00001C
This review presents comprehensively recent progress in metal–metalloporphyrin frameworks (MMPFs) with an emphasis on versatile functionalities. Following a brief introduction of basic concepts and the potential virtues of MMPFs, we give a snapshot of the historical perspective of MMPFs since 1991. We then summarize four effective strategies implemented frequently to construct prototypal MMPFs. MMPFs represent a resurging class of promising functional materials, highlighted with diverse applications including guest-molecule adsorption and separation, catalysis, nano-thin films and light-harvesting.
Co-reporter:Wen-Yang Gao, Wuming Yan, Rong Cai, Kia Williams, Andrea Salas, Lukasz Wojtas, Xiaodong Shi and Shengqian Ma
Chemical Communications 2012 - vol. 48(Issue 71) pp:NaN8900-8900
Publication Date(Web):2012/07/23
DOI:10.1039/C2CC34380K
The replacement of the pillar ligand, 4,4′-bipyridine, in the prototypal pillared MOF, MOF-508, with the custom-designed ligand, 4,4′-(2H-1,2,3-triazole-2,4-diyl)dipyridine, affords a porous metal–triazolate framework, MTAF-3, which demonstrates remarkable enhancement of CO2 uptake capacity by a factor of ∼3 compared to the parent MOF-508.
Co-reporter:Qi Sun, Briana Aguila and Shengqian Ma
Inorganic Chemistry Frontiers 2017 - vol. 1(Issue 7) pp:NaN1316-1316
Publication Date(Web):2017/01/23
DOI:10.1039/C6QM00363J
A bifunctional covalent organic framework (COF) has been illustrated in the context of partial metalation of a highly porous and chemically robust pyridine containing COF (COF-TpPa-Py) with Pd species and by taking advantage of the base catalytic behavior of pyridine. The resultant bifunctionalized COF exhibits excellent performance in catalyzing one-pot cascade aerobic oxidation–Knoevenagel condensation reactions, outperforming the corresponding homogeneous and porous organic polymer based catalytic systems, thereby opening a new avenue for multifunctional COFs as a promising platform for heterogeneous cascade catalysis.
Co-reporter:Weijie Zhang, Briana Aguila and Shengqian Ma
Journal of Materials Chemistry A 2017 - vol. 5(Issue 19) pp:NaN8824-8824
Publication Date(Web):2017/03/28
DOI:10.1039/C6TA11168H
Porous materials are important in established processes, such as catalysis and molecular separations, and in emerging technologies for energy and health. Porous organic polymers (POPs), a class of highly crosslinked, amorphous polymers possessing nanopores, have recently emerged as a versatile platform for potential applications. As an emerging material, POPs offer high flexibility for the molecular design and post-synthetic modification of their conjugated skeletons and nanopores. They have shown great potential for challenging energy and environmental issues, as exemplified by their excellent performance in gas storage/separation, catalysis, environmental remediation, and sensing. This review article summarizes the recent frontiers of functional exploration and potential applications of porous organic polymers.
Co-reporter:Wen-Yang Gao, Sathvik Palakurty, Lukasz Wojtas, Yu-Sheng Chen and Shengqian Ma
Inorganic Chemistry Frontiers 2015 - vol. 2(Issue 4) pp:NaN372-372
Publication Date(Web):2015/01/26
DOI:10.1039/C4QI00240G
Open metal sites are devised to dangle on cobalt trigonal prismatic secondary building units (SBUs) of a porous MOF, when a rigid octacarboxylate ligand, 1,3,6,8-tetra(3,5-dicarboxylphenyl)pyrene, assembled with Co(NO3)2 under solvothermal conditions. The functional role of dangled open metal sites is exploited for CO2 capture studies.
