Co-reporter:Jian Shen, Wei Chai, Kaixuan Wang, and Fang Zhang
ACS Applied Materials & Interfaces July 12, 2017 Volume 9(Issue 27) pp:22440-22440
Publication Date(Web):June 14, 2017
DOI:10.1021/acsami.7b04325
A urea-functionalized ordered mesoporous polymeric nanoparticle for removing the perrhenate anion ReO4– as the surrogate of the particularly intractable anion radioactive pollutant TcO4– was demonstrated in the present study. This nanomaterial (denoted as urea-MPN) was produced for the first time by a surfactant-directed urea-phenol-formaldehyde resol oligomers self-assembly protocol under hydrothermal condition. The obtained urea-MPN possessed the uniform nanosized spherical morphology with a 3D interconnected ordered cubic mesoporous structure. Also, the urea functional groups were succefully embedded in the polymer framework without the alteration of the molecular configuration. Meanwhile, it exhibited excellent β radiation resistance up to 200 kGy dose. We employed the perrhenate anion ReO4– to test its potential for the removal of anionic radioactive pollutant TcO4– from water. Interestingly, the optimized urea-MPN nanocomposite achieved the high removal efficiency at a low concentration of 0.25 mM within a short contact time of 30 min. The control experimental results revealed that the short nanoscale pore channels and the hydrophobic mesopore surface facilitated the hydrogen-bonding interaction between the charge-diffuse ReO4– tetrahedral oxoanion and the urea moieties in the framework of urea-MPN, accounting for the rapid and effective removal performance in pure water. Importantly, it can selectively capture ReO4– in the presence of different competitive anions including NO3–, CO32–, SO42–, and PO43–. This attractive capability of this unique nanosized mesoporous polymeric sorbent will pave the way for the diverse applications in the decontamination of nuclear wastes in a more economical and sustainable manner.Keywords: adsorbent; mesoporous polymeric nanoparticle; nuclear waste; TcO4−; urea-functionalization;
Co-reporter:Kaixuan Wang;Liping Yang;Weiliang Zhao;Linqing Cao;Zhenliang Sun
Green Chemistry (1999-Present) 2017 vol. 19(Issue 8) pp:1949-1957
Publication Date(Web):2017/04/20
DOI:10.1039/C7GC00219J
A novel mesoporous phenol-formaldehyde resin-supported copper nanoparticles catalyst was prepared using a two-step protocol involving the melt infiltration of copper nitrate hydrates and the subsequent template pyrolysis-induced in situ reduction of Cu(II) ions. Notably, this synthetic process effectively saved time and reduced waste because it did not use any solvents, capping reagents, or reducing reagents. The obtained Cu NPs@MP catalysts had large surface areas and narrow pore size distributions. In addition, most of the Cu nanoparticles, with sizes around 3 to 5 nm, were highly dispersed in the pore channels of the mesoporous polymer. In solvent-free Sonogashira reactions for the synthesis of ynones from acyl chlorides and terminal alkynes, this catalyst exhibited much higher catalytic reactivity than commercial Cu powder and mesoporous silica SBA-15-supported Cu nanoparticles. The excellent catalytic performance can be attributed to the synergistic advantages of mesoporous structure, monodispersed Cu nanoparticles and surface hydrophobicity, which stabilized and concentrated the reactants and increased the accessibility of the active sites while decreasing the mass transfer resistance. Meanwhile, the catalyst could be easily recycled and reused at least ten times, showing good stability under solvent-free reaction conditions.
Co-reporter:Xiaoyan Li, Zhongkai Hao, Fang Zhang, and Hexing Li
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 19) pp:12141
Publication Date(Web):April 22, 2016
DOI:10.1021/acsami.6b01100
A sodium benzenesulfonate (PhSO3Na)-functionalized reduced graphene oxide was synthesized via a two-step aryl diazonium coupling and subsequent NaCl ion-exchange procedure, which was used as a support to immobilize tris(bipyridine)ruthenium(II) complex (Ru(bpy)3Cl2) by coordination reaction. This elaborated Ru(bpy)3-rGO catalyst exhibited excellent catalytic efficiency in visible-light-driven reductive dehalogenation reactions under mild conditions, even for ary chloride. Meanwhile, it showed the comparable reactivity with the corresponding homogeneous Ru(bpy)3Cl2 catalyst. This high catalytic performance could be attributed to the unique two-dimensional sheet-like structure of Ru(bpy)3-rGO, which efficiently diminished diffusion resistance of the reactants. Meanwhile, the nonconjugated PhSO3Na-linkage between Ru(II) complex and the support and the very low electrical conductivity of the catalyst inhibited energy/electron transfer from Ru(II) complex to rGO support, resulting in the decreased support-induced quenching effect. Furthermore, it could be easily recycled at least five times without significant loss of catalytic reactivity.Keywords: diazonium coupling; reduced graphene oxide; reductive dehalogenation reaction; Ru(bpy)3Cl2; visible-light photocatalysis
Co-reporter:Yongyi Wei, Zhongkai Hao, Fang Zhang and Hexing Li
Journal of Materials Chemistry A 2015 vol. 3(Issue 28) pp:14779-14785
Publication Date(Web):10 Jun 2015
DOI:10.1039/C5TA03008K
We report a facile coordination-induced growth approach to fabricate a SO3H-functionalized graphene oxide and nanosized zeolitic imidazolate framework composite (ZIF-8@SO3H-GO) under mild conditions. The interactions between the functional groups on the sheets of GO with Zn(II) ions of the ZIF-8 precursor initiated the nucleation and growth of ZIF-8 on the GO and meanwhile nanosized ZIF-8 particles were well dispersed on the sheets of GO. Owing to the co-existing basic imidazole moieties from ZIF-8 and the SO3− and CO2−-functional groups on the sheets and Zn2+ ions from ZIF-8 in this Lewis acid rich composite, it exhibited high catalytic reactivity and selectivity in [3 + 3] formal cycloaddition reactions that consist of two-step Knoevenagel-type condensation and electrocyclic ring-closure to give various synthetically valuable pyranyl heterocycles. Interestingly, it was especially advantageous for the large sized reactants. The results indicated that it displayed 2 times higher reactivity compared to ZIF-8 nanoparticles due to the newly formed mesopores in the junctions between GO sheets and ZIF-8 nanoparticles. More importantly, it could be conveniently recovered and recycled 10 times without the loss of activity.
Co-reporter:Fang Zhang, Huangyong Jiang, Xiaotao Wu, Zhan Mao, and Hexing Li
ACS Applied Materials & Interfaces 2015 Volume 7(Issue 3) pp:1669
Publication Date(Web):January 2, 2015
DOI:10.1021/am507221a
In this work, we reported the synthesis of bifunctional carbocatalyst with acid–base dual-activation mechanism by introducing organoamines on the basal planes of graphene oxide (GO). Interestingly, GO-supported primary amine (AP-GO) exclusively promoted one-pot Henry-Michael reactions with excellent activity to give synthetically valuable multifunctionalized nitroalkanes. Notably, it also exhibited significantly higher activity than those using propylamine, activated carbon-supported primary amine, and mesoporous silica-supported primary amine as the catalysts. This superior catalytic performance originated from the unique properties of AP-GO, which provided the acid–base cooperative effect by the appropriate positioning of primary amines on their basal planes and carboxyl acids along their edges and the decreased diffusion resistance of the reactants and the intermediates during the multistep catalytic cycles because of its open two-dimensional sheet-like structure. Moreover, it could be readily recycled by simple filtration and subsequently reused without significant loss of its catalytic activity in a six times run test.Keywords: acid−base dual activation; bifunctional catalyst; carbocatalyst; one-pot multistep reaction; organoamine-functionalized graphene oxide
Co-reporter:Fang Zhang, Huangyong Jiang, Xiaoyan Li, Xiaotao Wu, and Hexing Li
ACS Catalysis 2014 Volume 4(Issue 2) pp:394
Publication Date(Web):December 20, 2013
DOI:10.1021/cs400761r
The amine-functionalized graphene oxide was prepared by a facile one-step silylation approach and used as an acid–base bifunctional catalyst in one-pot cascade reactions containing successive acetal hydrolysis and Knoevenagel condensation owing to the separate coexistence of original carboxylic acid on the edge of the GO sheet and the postgrafted amine groups on the GO basal surface. This catalyst exhibited much higher activity than either amine-functionalized active carbon, amine-functionalized SBA-15, or amine-functionalized Al2O3 due to the enriched surface acid sites and the diminished diffusion limitation as well as high catalyst dispersion in liquid solution due to the unique two-dimensional structure. More importantly, this catalyst could be easily recycled and used repetitively, showing potential application in industry.Keywords: acetal hydrolysis; acid−base bifunctional catalyst; amine-functionalized graphene oxide; Knoevenagel condensation; one-pot cascade reactions
Co-reporter:Fang Zhang, Xiaotao Wu, Chao Liang, Xiaoyan Li, Zhen Wang and Hexing Li
Green Chemistry 2014 vol. 16(Issue 8) pp:3768-3777
Publication Date(Web):27 Mar 2014
DOI:10.1039/C4GC00178H
A novel magnetic mesoporous Lewis acid catalyst was prepared through immobilizing Yb(OTf)3 on a sodium propylsulphonate and phenyl group co-functionalized magnetic core–mesoporous silica shell composite. The obtained Yb(OTf)2-SO3Na&Ph-MCMSS catalyst had a typical core–shell structure with a Fe3O4 magnetic core, a middle amorphous silica layer and a multifunctional mesoporous silica shell with radial pore channels. In water medium Mukaiyama–Aldol reactions, it exhibited a higher catalytic reactivity than that of the homogeneous catalyst Yb(OTf)3, and control catalysts Yb(OTf)2-SO3Na-MCMSS without phenyl groups inside the mesoporous channels, Yb(OTf)2-SO3Na&Ph-MCSS without a mesoporous structure, mesoporous Yb(OTf)2-SO3Na&Ph-MCM-41 with an irregular morphology and nonporous Yb(OTf)2-SO3Na-Amberlyst-15 ion-exchange resin. The systematic analysis demonstrated that this excellent catalytic performance could be attributed to the synergetic effect resulting from its radial mesoporous channels and the pore surface hydrophobicity, leading to the increased accessibility of actives sites and the decreased diffusion limitation of reactants. More importantly, this catalyst was stable in water and could be easily separated with a simple magnet and reused at least six times without loss of catalytic activity.
Co-reporter:Mingzhen Chen, Chao Liang, Fang Zhang, and Hexing Li
ACS Sustainable Chemistry & Engineering 2014 Volume 2(Issue 3) pp:486
Publication Date(Web):December 2, 2013
DOI:10.1021/sc400391r
Phenyl-bridged periodic mesoporous organosilica modified with sodium benzenesulfonate groups (NaSO3Ph-PMO) was frabicated by template-assembled co-condensation and subsequent ion-exchange processes. This functionalized support efficiently anchored scandium triflate to generate a mesoporous Lewis acid catalyst (Sc(OTf)2-SO3Ph-PMO). It exhibited superior catalytic reactivity compared to those of the homogeneous catalyst scandium triflate and Sc(OTf)2-SO3Ph-SBA-15, without the phenyl groups inside the mesoporous wall of the water medium Barbier–Grignard and Mukaiyama–Aldol reactions. The physico–chemical characterizations demonstrated that its excellent catalytic performance was due to its ordered mesoporous channel and hydrophobicity microenvironment, which could stabilize and concentrate the substances as well as decrease intrinsic mass transfer resistance. Furthermore, the Sc(OTf)2-SO3Ph-PMO catalyst retained high catalytic reactivity even after 10 reuses, confirming its excellent catalytic stability.Keywords: Lewis acid; Periodic mesoporous silica; Scandium triflate; Water medium organic synthesis
Co-reporter:Dr. Fang Zhang;Chao Liang;Xiaotao Wu ;Dr. Hexing Li
Angewandte Chemie 2014 Volume 126( Issue 32) pp:8638-8642
Publication Date(Web):
DOI:10.1002/ange.201404353
Abstract
The design of robust solid catalysts which can selectively synthesize highly functionalized carbohydrate derivatives from unprotected and unactivated simple sugars in water is an outstanding challenge. Herein we describe the preparation of a novel nanospherical ordered mesoporous Lewis acid polymer (Sc(OTf)2-NSMP) by functionalizing the mesoporous phenol-formaldehyde polymer framework with scandium triflate groups. In the C-glycosylation reaction between D-glucose and dimedone with the Sc(OTf)2-NSMP catalyst, the conversion was 99 % and the yield of xanthone-C-glucoside reached 92 % after 2 days, which exceeded the previous best results. It was shown that other xanthone glycosides can be obtained from various sugars with moderate to good yields. Furthermore, the catalyst can be easily recovered and reused at least seven times without loss of catalytic activity.
Co-reporter:Chenguang Yu;Aiguo Song;Dr. Fang Zhang;Dr. Wei Wang
ChemCatChem 2014 Volume 6( Issue 7) pp:1863-1865
Publication Date(Web):
DOI:10.1002/cctc.201402121
Co-reporter:Dr. Fang Zhang;Chao Liang;Xiaotao Wu ;Dr. Hexing Li
Angewandte Chemie International Edition 2014 Volume 53( Issue 32) pp:8498-8502
Publication Date(Web):
DOI:10.1002/anie.201404353
Abstract
The design of robust solid catalysts which can selectively synthesize highly functionalized carbohydrate derivatives from unprotected and unactivated simple sugars in water is an outstanding challenge. Herein we describe the preparation of a novel nanospherical ordered mesoporous Lewis acid polymer (Sc(OTf)2-NSMP) by functionalizing the mesoporous phenol-formaldehyde polymer framework with scandium triflate groups. In the C-glycosylation reaction between D-glucose and dimedone with the Sc(OTf)2-NSMP catalyst, the conversion was 99 % and the yield of xanthone-C-glucoside reached 92 % after 2 days, which exceeded the previous best results. It was shown that other xanthone glycosides can be obtained from various sugars with moderate to good yields. Furthermore, the catalyst can be easily recovered and reused at least seven times without loss of catalytic activity.
Co-reporter:Fang Zhang, Chao Liang, Mingzheng Chen, Haibing Guo, Huangyong Jiang and Hexing Li
Green Chemistry 2013 vol. 15(Issue 10) pp:2865-2871
Publication Date(Web):16 Jul 2013
DOI:10.1039/C3GC41020J
A periodic mesoporous Lewis acid catalyst ((OTf)2Sc-SO3-Ph-PMO) was synthesized through chelating scandium triflate (Sc(OTf)3) with sodium benzenesulfonate-functionalized periodic mesoporous silica (PhSO3Na-Ph-PMO). Compared with homogeneous catalyst Sc(OTf)3 and mesoporous SBA-15-supported scandium triflate catalyst ((OTf)2Sc-SO3-Ph-SBA-15), it exhibited superior catalytic activity and selectivity in water-medium Mukaiyama-aldol reaction. Hydrophobicity tests and substrate adsorption experiments demonstrated that its unique catalytic performance was related to the combined advantage of mesoporosity and hydrophobic microenvironment, which effectively stabilized and concentrated the substances as well as decreased intrinsic mass transfer resistance. Noted that the periodically arranged Lewis acids in the mesoporous silica framework inhibited the active sites leaching, leading to its high catalytic recyclability with almost unchanged catalytic efficiency for more than 10 times in water media.
Co-reporter:Fang Zhang, Xushi Yang, Lei Jiang, Chao Liang, Ruixing Zhu and Hexing Li
Green Chemistry 2013 vol. 15(Issue 6) pp:1665-1672
Publication Date(Web):08 Apr 2013
DOI:10.1039/C3GC40215K
A piperazine-functionalized mesoporous polymer (PP-MPs) was synthesized through a one-step surfactant-directed phenol–formaldehyde–piperazinecarbaldehyde oligomer self-assembly approach. This novel PP-MP catalyst exhibited highly catalytic reactivity and selectivity for water-medium Knoevenagel reaction, water-medium [3 + 3] cycloaddition reaction and intermolecular cross-conjugated addition reaction. The excellent performance could be attributed to its high dispersion of piperazine active sites and ordered mesoporous structure, which effectively diminished the steric hindrance and diffusion limitation. Moreover, its pure organic framework could enhance surface hydrophobicity, which promoted organic reactant molecule adsorption, especially in water. Meanwhile, piperazine functional groups embedded in the polymeric framework could inhibit the leaching of active species and thus resulted in the excellent durability without significant loss of activity for recovery and recycling at least four times.
Co-reporter:Jiewei Yin;Wei Chai;Hexing Li
Applied Organometallic Chemistry 2013 Volume 27( Issue 9) pp:512-518
Publication Date(Web):
DOI:10.1002/aoc.3017
Phenyl-bridged periodic mesoporous organosilicas (PMOs) functionalized with diphenylphosphino (PPh2-) ligands were synthesized via a surfactant-directed self-assembly approach, and were used as a support to immobilize Ni(II) organometallic complex by coordination interaction. In comparison with Ni-PPh2-SBA-15 and Ni-PPh2-PMOs(Et) catalysts, the as-prepared Ni-PPh2-PMOs(Ph) exhibited superior catalytic reactivity and selectivity in water-medium Sonogashira reaction. A control experiment demonstrated that its high activity could be attributed to the high dispersion of Ni(II) active sites and ordered mesopore channels, which effectively diminished diffusion limitation. Meanwhile, the phenyl organic groups in the support wall enhanced surface hydrophobicity, which promoted the adsorption for organic reactant molecules. Moreover, it displayed almost the same catalytic efficiency with the corresponding homogeneous Ni(PPh3)2Cl2 catalyst and could be used repetitively, which was considered as a more environmentally friendly catalytic process since it simultaneously avoided the use of noble metal active species and toxic organic solvents. Copyright © 2013 John Wiley & Sons, Ltd.
Co-reporter:Yuhan Lin, Fang Zhang and Daocheng Pan
Journal of Materials Chemistry A 2012 vol. 22(Issue 42) pp:22619-22623
Publication Date(Web):07 Sep 2012
DOI:10.1039/C2JM35166H
A series of (ZnS)x(CuInS2)1−x hierarchical micro/nano-structured solid solutions with precisely controlled chemical composition were synthesized via a facile one-pot solvothermal method. ZnO, Cu2O, and In(OH)3 are used as the starting materials and dissolved in ethanol dithiocarbamic acid which is formed from CS2 and ethanolamine in situ. The ethanol dithiocarbamic acid not only serves as a thermally-degradable ligand, but also acts as sulfur source during synthesis, and can be completely removed by a simple calcination process. As-prepared (ZnS)x(CuInS2)1−x microspheres have a hierarchical micro/nano structure composed of around 7 nm nanoparticles. These samples show excellent photocatalytic H2 evolution activity under visible-light irradiation without any noble metal loading owing to their high surface area (as high as 101.6 m2 g−1) and unique hierarchical structure.
Co-reporter:Jianlin Huang, Jiewei Yin, Wei Chai, Chao Liang, Jian Shen and Fang Zhang
New Journal of Chemistry 2012 vol. 36(Issue 6) pp:1378-1384
Publication Date(Web):30 Mar 2012
DOI:10.1039/C2NJ21073H
Multifunctional mesoporous material (NH2&Ph-SBA-15) was synthesized by co-condensation of tetraethyl orthosilicate, amine-silane and phenyl-silane in the presence of triblock copolymer P123. The Pd nanoparticles immobilized on the NH2&Ph-SBA-15 support were fabricated by the impregnation and subsequent reduction method. The XRD, TEM, N2 sorption, IR and solid NMR measurements revealed that this novel mesoporous Pd catalyst (Pd/NH2&Ph-SBA-15) not only maintained ordered hexagonal mesopores, but also possessed characteristics of the two organic functional groups on the mesopore surface. Compared with Pd nanoparticles supported on the parent SBA-15 or monofunctionalized mesoporous materials, it displayed much higher catalytic reactivity and selectivity in the water-medium Ullmann reaction. This could be attributed to the synergic promoting effect derived from binary organic functional groups since the NH2-groups led to the uniform dispersion of Pd nanoparticles inside the pore channels while the Ph-groups decreased the diffusion limitation of organic molecules in water. Furthermore, it could be conveniently recovered and recycled six times without significant loss of activity and selectivity.
Co-reporter:Ruixing Zhu, Jian Shen, Yongyi Wei and Fang Zhang
New Journal of Chemistry 2011 vol. 35(Issue 9) pp:1861-1866
Publication Date(Web):06 Jul 2011
DOI:10.1039/C1NJ20030E
Urea-functionalized mesoporous polymers (urea-MPs) were synthesized through the surfactant-directed urea-phenol-formaldehyde oligomers self-assembly approach. The as-prepared urea-MPs material exhibited superior catalytic activity than parent urea in water-medium Knoevenagel condensation reactions and could be used repetitively for seven times. The excellent activity could be attributed to the synergic effect derived from the secondary amine with the surface phenolic groups in the mesoporous support, which generated the acid–base cooperative catalytic behavior. Meanwhile, the urea functional groups embedded in the mesopore wall could inhibit the leaching of active species and thus resulted in the relatively good durability.
Co-reporter:Jianlin Huang
Applied Organometallic Chemistry 2010 Volume 24( Issue 11) pp:767-773
Publication Date(Web):
DOI:10.1002/aoc.1696
Abstract
Water-medium organic reactions were studied over periodic mesoporous silica (PMO) containing Pd(II) organometallic complex. This heterogeneous catalyst was achieved by Pd(II) compound coordinated with the PPh2-ligand onto the pore surface of phenylene-bridged PMO support. This catalyst displayed ordered mesoporous channels, which ensured the high dispersion of Pd(II) active sites and the convenient diffusion of reactant molecules into the pore channels. Meanwhile, the phenyl group in the pore wall of PMO could enhance the surface hydrophobicity which promoted the adsorption of organic reactant molecules on the catalyst in aqueous environment. As a result, this elaborated catalyst exhibited comparable activity and selectivity with the corresponding PdCl2(PPh3)2 homogeneous catalyst in the water-medium organic reactions, and could be used repeatedly, showing a good potential in industrial applications. Copyright © 2010 John Wiley & Sons, Ltd.
Co-reporter:Chunmei Kang, Jianlin Huang, Wenhan He, Fang Zhang
Journal of Organometallic Chemistry 2010 695(1) pp: 120-127
Publication Date(Web):
DOI:10.1016/j.jorganchem.2009.09.036
Co-reporter:Yongyi Wei, Zhongkai Hao, Fang Zhang and Hexing Li
Journal of Materials Chemistry A 2015 - vol. 3(Issue 28) pp:NaN14785-14785
Publication Date(Web):2015/06/10
DOI:10.1039/C5TA03008K
We report a facile coordination-induced growth approach to fabricate a SO3H-functionalized graphene oxide and nanosized zeolitic imidazolate framework composite (ZIF-8@SO3H-GO) under mild conditions. The interactions between the functional groups on the sheets of GO with Zn(II) ions of the ZIF-8 precursor initiated the nucleation and growth of ZIF-8 on the GO and meanwhile nanosized ZIF-8 particles were well dispersed on the sheets of GO. Owing to the co-existing basic imidazole moieties from ZIF-8 and the SO3− and CO2−-functional groups on the sheets and Zn2+ ions from ZIF-8 in this Lewis acid rich composite, it exhibited high catalytic reactivity and selectivity in [3 + 3] formal cycloaddition reactions that consist of two-step Knoevenagel-type condensation and electrocyclic ring-closure to give various synthetically valuable pyranyl heterocycles. Interestingly, it was especially advantageous for the large sized reactants. The results indicated that it displayed 2 times higher reactivity compared to ZIF-8 nanoparticles due to the newly formed mesopores in the junctions between GO sheets and ZIF-8 nanoparticles. More importantly, it could be conveniently recovered and recycled 10 times without the loss of activity.
Co-reporter:Yuhan Lin, Fang Zhang and Daocheng Pan
Journal of Materials Chemistry A 2012 - vol. 22(Issue 42) pp:NaN22623-22623
Publication Date(Web):2012/09/07
DOI:10.1039/C2JM35166H
A series of (ZnS)x(CuInS2)1−x hierarchical micro/nano-structured solid solutions with precisely controlled chemical composition were synthesized via a facile one-pot solvothermal method. ZnO, Cu2O, and In(OH)3 are used as the starting materials and dissolved in ethanol dithiocarbamic acid which is formed from CS2 and ethanolamine in situ. The ethanol dithiocarbamic acid not only serves as a thermally-degradable ligand, but also acts as sulfur source during synthesis, and can be completely removed by a simple calcination process. As-prepared (ZnS)x(CuInS2)1−x microspheres have a hierarchical micro/nano structure composed of around 7 nm nanoparticles. These samples show excellent photocatalytic H2 evolution activity under visible-light irradiation without any noble metal loading owing to their high surface area (as high as 101.6 m2 g−1) and unique hierarchical structure.