Co-reporter:Fulin Yang, Yongting Chen, Gongzhen Cheng, Shengli Chen, and Wei Luo
ACS Catalysis June 2, 2017 Volume 7(Issue 6) pp:3824-3824
Publication Date(Web):April 24, 2017
DOI:10.1021/acscatal.7b00587
Searching for non-noble-metal-based electrocatalysts with high efficiency and durability toward the hydrogen evolution reaction (HER) is vitally necessary for the upcoming clean and renewable energy systems. Here we report the synthesis of CoP nanoparticles encapsulated in ultrathin nitrogen-doped porous carbon (CoP@NC) through a metal–organic framework (MOF) route. This hybrid exhibits remarkable electrocatalytic activity toward the HER in both acidic and alkaline media, with good stability. Experiments and theoretical calculations reveal that the carbon atoms adjacent to N dopants on the shells of CoP@NC are active sites for hydrogen evolution and that CoP and N dopants synergistically optimize the binding free energy of H* on the active sites, which results in a higher electrocatalytic activity in comparison to its counterparts without nitrogen doping and/or CoP encapsulation.Keywords: catalytically active site; cobalt phosphide; DFT; hydrogen evolution; ultrathin nitrogen-doped carbon layer;
Co-reporter:Cheng Du, Lan Yang, Fulin Yang, Gongzhen Cheng, and Wei Luo
ACS Catalysis June 2, 2017 Volume 7(Issue 6) pp:4131-4131
Publication Date(Web):May 10, 2017
DOI:10.1021/acscatal.7b00662
The investigation of high-efficiency nonprecious electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of great significance for renewable energy technologies. Here, we provide a successive hydrothermal, oxidation, and phosphidation method to fabricate a 3D nest-like ternary NiCoP/carbon cloth (CC) electrocatalyst with superior catalytic activity and stability toward HER/OER. Nest-like NiCoP/CC requires overpotentials of 44 and 62 mV to reach the current density of 10 mA cm–2 in acidic and alkaline media, respectively, toward HER. For OER, the NiCoP/CC exhibits high active and durable performance with an overpotential of 242 mV at current density of 10 mA cm–2 in alkaline solutions. Furthermore, the practical application of NiCoP/CC as a bifunctional catalyst for overall water splitting reaction yields current densities of 10 and 100 mA cm–2 at 1.52 and 1.77 V, respectively.Keywords: HER; nest-like; NiCoP; OER; TMP; water splitting;
Co-reporter:Yeshuang Du;Gongzhen Cheng
Catalysis Science & Technology (2011-Present) 2017 vol. 7(Issue 20) pp:4604-4608
Publication Date(Web):2017/10/16
DOI:10.1039/C7CY01496A
We report the colloidal synthesis of a NiSe2/FeSe2 catalyst with branched nanodendrite architecture. The Ni0.5Fe0.5Se2 catalyst exhibits superior catalytic activity towards OER with an overpotential of 235 mV at a current density of 10 mA cm−2 in an alkaline electrolyte owing to its unique 3D structure and the synergistic effect between NiSe2 and FeSe2.
Co-reporter:Quan Zuo;Gongzhen Cheng
Dalton Transactions 2017 vol. 46(Issue 29) pp:9344-9348
Publication Date(Web):2017/07/25
DOI:10.1039/C7DT01694H
A reduced graphene oxide/covalent cobalt porphyrin framework has been synthesized by using pyridine-functionalized reduced graphene oxide (G-dye) as the building block. Due to the unique 3-dimensional architecture and good electronic properties of graphene, as well as the electron accepting ability of the nitrogen atoms in the G-dye, the as-synthesized CoCOF-Py-0.05rGO catalyst exhibits excellent oxygen reduction reaction (ORR) activity with superior long-term stability and methanol tolerance.
Co-reporter:Fulin Yang;Luhong Fu;Gongzhen Cheng;Shengli Chen
Journal of Materials Chemistry A 2017 vol. 5(Issue 44) pp:22959-22963
Publication Date(Web):2017/11/14
DOI:10.1039/C7TA07635E
In this study, we report successful synthesis of ultrafine worm-like Ir-oriented nanocrystalline assemblies (ONAs) and their further use as efficient electrocatalysts towards the HOR/HER in an alkaline medium. Due to the fast mass/charge transfer rate as well as the appearance of the long segments of low-index crystalline planes, the as-synthesized Ir ONAs exhibit a remarkable performance for the HOR/HER in an alkaline electrolyte.
Co-reporter:Jiahao Yu;Gongzhen Cheng
Journal of Materials Chemistry A 2017 vol. 5(Issue 30) pp:15838-15844
Publication Date(Web):2017/08/01
DOI:10.1039/C7TA04438K
The development of low-cost, highly efficient, and stable electrocatalysts toward overall water splitting (both the anodic oxygen evolution reaction (OER) and the cathodic hydrogen evolution reaction (HER)) is essential for future energy supply. In this report, 3D ternary nickel iron sulfide microflowers with a hierarchically porous structure directly grown on Ni foam via a convenient two-step method have been fabricated, and further used as an efficient electrocatalyst for both the HER and the OER. Thanks to the unique 3D morphology and strong electron interactions between Fe, Ni and S, the as-synthesized Ni0.7Fe0.3S2 delivers an overpotential of 198 mV at a current density of 10 mA cm−2 toward the OER in alkaline media, which is, to the best of our knowledge, the best among the reported non-noble metal based electrocatalysts. Furthermore, when used as both the anode and cathode, a low cell voltage of 1.625 V is needed to obtain 10 mA cm−2 for the overall water splitting.
Co-reporter:Luhong Fu;Gongzhen Cheng
Journal of Materials Chemistry A 2017 vol. 5(Issue 47) pp:24836-24841
Publication Date(Web):2017/12/05
DOI:10.1039/C7TA08982A
The search for high-performance bifunctional electrocatalysts for overall water splitting under acidic conditions is highly desirable for the development of polymer electrolyte membrane (PEM) electrolyzers, whereas, there are still many challenges to fabricate satisfactory electrocatalysts that could exhibit excellent activity with long-term stability. Herein, we report the colloidal synthesis of monodisperse trimetallic IrNiFe nanoparticles (NPs) with an average diameter of 2.2 nm. By taking advantage of ultrasmall monodisperse NPs with narrow size distribution and the strong synergistic electronic effect between Ir, Ni and Fe, the resultant IrNi0.57Fe0.82 NPs exhibit good activity and excellent durability for both the HER and OER in acidic electrolyte. To reach a current density of 10 mA cm−2, the overpotential of the HER and OER in 0.5 M HClO4 is 24 and 284 mV, respectively. Furthermore, the practical application of IrNi0.57Fe0.82 as a bifunctional catalyst for acidic overall water splitting yields a current density of 10 mA cm−2 at 1.64 V with long-term stability.
Co-reporter:Jiahao Yu;Gongzhen Cheng
Journal of Materials Chemistry A 2017 vol. 5(Issue 22) pp:11229-11235
Publication Date(Web):2017/06/06
DOI:10.1039/C7TA02968C
Developing low-cost, highly efficient, and superior stable electrocatalysts for the oxygen evolution reaction (OER) is essential for upcoming renewable and clean energy systems. Here, 3D ternary nickel iron phosphide microflowers with a hierarchically porous morphology directly grown on Ni foam via a successive hydrothermal and phosphidation method are synthesized. Benefitting from their unique 3D hierarchical microflower-like structure and the strong electron interactions between Fe, Ni and P, the as-synthesized (NixFe1−x)2P catalysts can effectively catalyze the OER with an overpotential of 219 mV at a current density of 20 mA cm−2 in alkaline media, which is, to the best of our knowledge, the best among the reported non-noble metal-based catalysts.
Co-reporter:Yeshuang Du;Gongzhen Cheng
Nanoscale (2009-Present) 2017 vol. 9(Issue 20) pp:6821-6825
Publication Date(Web):2017/05/25
DOI:10.1039/C7NR01413A
The search for highly efficient non-precious metal electrocatalysts toward the oxygen evolution reaction (OER) is extremely essential for renewable energy systems. Here, we report the colloidal synthesis of Fe doped NiSe2, which functions as a high-performance electrocatalyst for the OER in alkaline solution. The NiFeSe catalysts are composed of urchin-like dendrites with a high number of active sites, which could provide fast transportation of electrons and electrolytes, and facile release of the evolved O2 bubbles during the OER catalysis. Benefitting from this unique urchin-like structure and strong electron interaction between Fe, Ni, and Se, the Ni1.12Fe0.49Se2 catalyst exhibits excellent electrocatalytic activity and high durability toward the OER in alkaline solution, with an overpotential of 227 mV at a current density of 10 mA cm−2, which is, to the best of our knowledge, higher than most of the reported selenide-based electrocatalysts.
Co-reporter:Luhong Fu;Ping Cai;Gongzhen Cheng
Sustainable Energy & Fuels (2017-Present) 2017 vol. 1(Issue 5) pp:1199-1203
Publication Date(Web):2017/06/27
DOI:10.1039/C7SE00113D
The design of high-performance electrocatalysts for oxygen evolution reactions (OER) in acidic condition is highly desirable for the development of the proton exchange membrane (PEM)-based water electrolyzer. Herein, we report the colloidal synthesis of iridium-iron alloy nanoparticles with an average diameter of 2.4 nm. The as-synthesized IrFe alloy produces a current density of 10 mA cm−2 in acidic and alkaline conditions at overpotentials of 278 and 286 mV, respectively.
Co-reporter:Yana Men, Xiaoqiong Du, Gongzhen Cheng, Wei Luo
International Journal of Hydrogen Energy 2017 Volume 42, Issue 44(Volume 42, Issue 44) pp:
Publication Date(Web):2 November 2017
DOI:10.1016/j.ijhydene.2017.08.214
•Facile synthesis of CeOx modified NiFe catalysts grown on rGO.•The NiFe-CeOx/rGO catalysts exhibit a branched nanodendrit architecture.•NiFe-CeOx/rGO exhibits superior catalytic activity dehydrogenation of hydrazine.CeOx-modified NiFe catalysts with branched nanodendritic architectures have been successfully deposited on reduced graphene oxide (rGO) through a simple co-reduction method. Thanks to the synergistic electronic effect between Ni, Fe, and Ce, as well as dendritic morphology with a high number of active sites, the resulted Ni3Fe-(CeOx)0.15/rGO exhibited superior catalytic activity toward dehydrogenation of hydrous hydrazine in alkaline condition, with turnover frequency (TOF) values of 56.8 h−1, and 126.2 h−1 at 328, and 343 K, respectively.
Co-reporter:Xiaoqiong Du, Chenlu Yang, Xiang Zeng, Tong Wu, ... Wei Luo
International Journal of Hydrogen Energy 2017 Volume 42, Issue 20(Volume 42, Issue 20) pp:
Publication Date(Web):18 May 2017
DOI:10.1016/j.ijhydene.2017.04.052
•Facile one-pot wet-chemical approach to prepare P-doped Ni nanoparticles.•Transition metal phosphide is used as efficient catalysts for NH3BH3 hydrolysis.•NiP/rGO exhibits superior catalytic activity and stability toward NH3BH3 hydrolysis.Transition metal phosphide based amorphous NiP/rGO hybrids have been successfully synthesized through a facile one-pot co-reduction method. The prepared NiP/rGO hybrids are characterized by powder X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM) and energy dispersive X-ray detector (EDX) techniques. Compared with Ni/rGO, the resulted Ni91P9/rGO hybrid exhibits superior catalytic activity toward hydrogen generation from hydrolysis of ammonia borane (NH3BH3), with turnover frequency (TOF) value of 13.3 min−1. The activation energy (Ea) of Ni91P9/rGO for this reaction is calculated to be 34.7 kJ mol−1, which is much lower than those of the other reported catalysts. This superior catalytic performance may be due to the good dispersibility of Ni91P9 nanoparticles and the synergistic electronic interactions between nickel and phosphorus.
Co-reporter:Xiaoqiong Du, Ping Cai, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2017 Volume 42, Issue 9(Volume 42, Issue 9) pp:
Publication Date(Web):2 March 2017
DOI:10.1016/j.ijhydene.2016.12.049
•A facile one-pot wet-chemical approach to prepare P-doped Rh NPs.•TMPs were first used for catalytic dehydrogenation of hydrazine.•RhP/rGO hybrids exhibit high catalytic activity and hydrogen selectivity toward dehydrogenation of hydrazine.RhP nanoparticles supported on reduced graphene oxide (RhP/rGO) synthesized by using a simple one-step wet-chemical approach have been investigated as superior catalysts toward dehydrogenation of hydrous hydrazine for chemical hydrogen storage. These RhP/rGO catalysts with different contents of P doping were characterized by ICP-AES, XRD, XPS, TEM, and STEM-HAADF. Thanks to the synergistic effect of phosphorous-doping, the obtained Rh92.6P7.4/rGO hybrid exhibits 100% H2 selectivity, superior stability, and excellent catalytic performance with turnover frequency value (TOF) of 843.9 h−1 toward hydrogen generation from alkaline solution of hydrazine at 323 K.Download high-res image (176KB)Download full-size image
Co-reporter:Xiaoqiong Du;Chao Liu;Cheng Du;Ping Cai;Gongzhen Cheng
Nano Research 2017 Volume 10( Issue 8) pp:2856-2865
Publication Date(Web):06 May 2017
DOI:10.1007/s12274-017-1494-6
The safe and efficient storage and release of hydrogen is one of the key technological challenges for the fuel cell-based hydrogen economy. Hydrazine monohydrate has attracted considerable attention as a safe and convent chemical hydrogen-storage material. Herein, we report the facile synthesis of NiPt-CeOx nanocomposites supported by three-dimensional nitrogen-doped graphene hydrogels (NGHs) via a simple one-step co-reduction synthesis method. These catalysts were composition-dependent for hydrogen generation from an alkaline solution of hydrazine. (Ni5Pt5)1-(CeOx)0.3/NGH exhibited the highest catalytic activity, with 100% hydrogen selectivity and turnover frequencies of 408 h–1 at 298 K and 3,064 h–1 at 323 K. These superior catalytic performances are attributed to the electronic structure of the NiPt centers, which was modified by the electron interaction between NiPt and CeOx and the strong metal–support interaction between NiPt-CeOx and the NGH.
Co-reporter:Quan Zuo, Pingping Zhao, Wei Luo and Gongzhen Cheng
Nanoscale 2016 vol. 8(Issue 29) pp:14271-14277
Publication Date(Web):23 Jun 2016
DOI:10.1039/C6NR03273G
Developing high-performance non-precious catalysts to replace platinum as oxygen reduction reaction (ORR) catalysts is still a big scientific and technological challenge. Herein, we report a simple method for the synthesis of a FeNC catalyst with a 3D hierarchically micro/meso/macro porous network and high surface area through a simple carbonization method by taking the advantages of a high specific surface area and diverse pore dimensions in 3D porous covalent-organic material. The resulting FeNC-900 electrocatalyst with improved reactant/electrolyte transport and sufficient active site exposure, exhibits outstanding ORR activity with a half-wave potential of 0.878 V, ca. 40 mV more positive than Pt/C for ORR in alkaline solution, and a half-wave potential of 0.72 V, which is comparable to that of Pt/C in acidic solution. In particular, the resulting FeNC-900 exhibits a much higher stability and methanol tolerance than those of Pt/C, which makes it among the best non-precious catalysts ever reported for ORR.
Co-reporter:Bingquan Xia, Teng Liu, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2016 vol. 4(Issue 15) pp:5616-5622
Publication Date(Web):10 Mar 2016
DOI:10.1039/C6TA00766J
Safe and efficient storage of hydrogen is the key issue for the hydrogen economy. Hydrazine monohydrate is regarded as a potential hydrogen carrier. Herein, we report a facile synthesis of NiPt–MnOx supported on nitrogen-doped porous carbon (NPC) derived from annealing metal–organic frameworks (MOFs) at different temperatures in Ar. Interestingly, the obtained (Ni3Pt7)0.5–(MnOx)0.5/NPC-900 exhibits superior catalytic activity toward dehydrogenation of an alkaline solution of hydrazine, with initial turnover frequency values of 706 and 120 h−1 at 323 K and room temperature, respectively. This excellent catalytic performance may have resulted from the synergistic electronic effect of NiPt and MnOx, the small size and high dispersion of NiPt–MnOx nanocatalysts, NPC as an excellent support with large pore volume, high surface area, high nitrogen content, electrical conductance, and also the high density of the metal-N active sites between NiPt–MnOx and NPC.
Co-reporter:Teng Liu, Pingping Zhao, Xing Hua, Wei Luo, Shengli Chen and Gongzhen Cheng
Journal of Materials Chemistry A 2016 vol. 4(Issue 29) pp:11357-11364
Publication Date(Web):21 Jun 2016
DOI:10.1039/C6TA03265F
A simple Zn/Fe bimetallic zeolitic–imidazolite framework (ZIF) carbonization method is developed to synthesize an Fe–N–C hybrid with hierarchical nitrogen-doped porous carbons crossed by carbon nanotubes. Both the specific ratios of Zn/Fe in the bimetallic metal–organic framework (MOF) precursors and the selected annealing temperature are essential for the formation of this unique hybrid structure with good conductivity and exposure of more active sites. The resulting FeNC-20-1000 hybrid electrocatalyst exhibits excellent oxygen reduction reaction (ORR) activity, with a half-wave potential of 0.770 V comparable to that of the commercial Pt/C catalysts in acidic media, and a half-wave potential of 0.880 V, ca. 50 mV more positive than that of Pt/C for ORR in alkaline solution. More importantly, the as-prepared Fe–N–C hybrid exhibits much more stability for the ORR in both acidic and alkaline solutions than Pt/C, which makes it among the best non-noble-metal catalysts ever reported for ORR under acidic and alkaline conditions.
Co-reporter:Pingping Zhao, Xing Hua, Wei Xu, Wei Luo, Shengli Chen and Gongzhen Cheng
Catalysis Science & Technology 2016 vol. 6(Issue 16) pp:6365-6371
Publication Date(Web):01 Jun 2016
DOI:10.1039/C6CY01031H
Active and stable electrocatalysts based on earth-abundant elements for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucially important for the utilization of renewable energy. Herein, we reported the synthesis of Fe3C nanorod encapsulated, N-doped carbon nanotubes grown on N-doped porous carbon sheets (Fe3C@NCNT/NPC) by simply annealing a Fe-based MOF (MIL-88B) loaded with melamine at 800 °C in N2. Thanks to the synergistic effect of the high density of Fe–N active sites and electric conductance offered by the unique hybrid structure, the as-prepared Fe3C@NCNT/NPC hybrid exhibited a half-wave potential ca. 60 mV more positive and a durability performance much better than that of Pt/C for ORR, and an overpotential ca. 20 mV lower and a Tafel slope much smaller than that of IrO2 for OER, which make it one of the best reported nonprecious metal bifunctional electrocatalysts for oxygen electrode reactions.
Co-reporter:Lan Yang, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2016 Volume 41(Issue 1) pp:439-446
Publication Date(Web):5 January 2016
DOI:10.1016/j.ijhydene.2015.10.074
•Facile synthesis of 2.8 nm monodisperse CoAgPd NPs supported on graphene.•The catalysts exhibit 100% hydrogen selectivity toward dehydrogenation of FA.•The catalysts exhibit high catalytic activity with TOF value of 110 h−1 at room temperature.Monodisperse trimetallic CoAgPd alloy nanoparticles (NPs) were synthesized by a controlled co-reduction of cobalt (II) acetylacetonate, silver nitrate and palladium acetylacetonate in oleylamine at 90 °C using 2-methylpyridine borane as the reducing agents. This is the first time using amine borane as the reducing agent to synthesize non-noble metal contained monodisperse trimetallic alloy NPs at relatively low temperature. The 2.8 nm monodisperse CoAgPd NPs were further assembled on graphene by a simple solution-phase self-assembly method, and tested for catalytic dehydrogenation of formic acid at room temperature. Unexpectedly, the introducing of small amount of cobalt can significantly enhance the catalytic activity and selectivity.
Co-reporter:Xiaoqiong Du;Cheng Du; Ping Cai; Wei Luo; Gongzhen Cheng
ChemCatChem 2016 Volume 8( Issue 7) pp:1410-1416
Publication Date(Web):
DOI:10.1002/cctc.201501405
Abstract
Boron and nitrogen co-doped graphene (BNG) with negligible covalent boron–nitride (BN) bonding, and high boron and pyridinic nitrogen contents has been synthesized by a two-step method using boron–carbon–nitride (BCN) as the boron and nitrogen sources. The use of the BCN precursor is the key for preparing BNG, while annealing reduced graphene oxide, urea, and boric acid in a one-step method results in separated domains of larger amounts of covalent BN in the graphene networks (s-BNG). The resulting BNGs are further used to anchor NiPt nanoparticles (NPs) with good dispersion. Consequently, Ni3Pt7/BNG-1000 exhibits the highest catalytic activity toward hydrazine dehydrogenation at room temperature, with the turnover frequency of 199.4 h−1. Furthermore, as evidence of its multifunctionality, Ni3Pt7/BNG-1000 is further employed for electrocatalytic methanol oxidation.
Co-reporter:Pingping Zhao
The Journal of Physical Chemistry C 2016 Volume 120(Issue 20) pp:11006-11013
Publication Date(Web):May 6, 2016
DOI:10.1021/acs.jpcc.6b03070
A facile one-step synthesis of the hybrid of hierarchical nitrogen-doped porous carbon and Fe3C nanoparticles encapsulated a nitrogen-doped carbon nanotube through simply annealing the mixture of FeCl3, o-phthalic anhydride, and melamine at 800 °C in Ar was proposed. Both the specific ratio of these precursors and the selected annealing temperature are key factors for the formation of the unique hybrid structure, while any subtle modulation will result in different morphologies. Thanks to the good conductivity and hierarchical porous diversity, Fe–N–C material obtained at 800 °C exhibits a half-wave potential of 0.880 V, ca. 50 mV more positive than Pt/C, for oxygen reduction reaction (ORR) and an overpotential of 0.41 V, ca. 36 mV lower than IrO2 black, at the current of 10 mA cm–2 for oxygen evolution reaction (OER).
Co-reporter:Pingping Zhao, Nan Cao, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2015 vol. 3(Issue 23) pp:12468-12475
Publication Date(Web):06 May 2015
DOI:10.1039/C5TA02201K
Nanoscale MIL-101 has been controlled, synthesized by a seeding method, and further used as the support for immobilizing RhNi nanoparticles (NPs) as efficient catalysts toward hydrogen generation from hydrous hydrazine in alkaline solution. Compared with other commercial materials and bulk MIL-101, RhNi NPs supported on nanoscale MIL-101 exhibit the highest catalytic activity and 100% hydrogen selectivity.
Co-reporter:Yeshuang Du, Jun Su, Wei Luo, and Gongzhen Cheng
ACS Applied Materials & Interfaces 2015 Volume 7(Issue 2) pp:1031
Publication Date(Web):January 6, 2015
DOI:10.1021/am5068436
Ultrafine monodisperse bimetallic NiPt nanoparticles with different compositions have been successfully synthesized by coreduction of nickel acetylacetonate and platinum acetylacetonate with borane-tert-butylamine in oleylamine. Among all the catalysts tested, Ni84Pt16/graphene exhibited 100% hydrogen selectivity, and marked high catalytic activity, with TOF values of 415 h–1 at 50 °C, and 133 h–1 at 25 °C for hydrogen generation from alkaline solution of hydrazine.Keywords: hydrazine; hydrogen storage; monodisperse; Ni; Pt
Co-reporter:Pingping Zhao, Nan Cao, Jun Su, Wei Luo, and Gongzhen Cheng
ACS Sustainable Chemistry & Engineering 2015 Volume 3(Issue 6) pp:1086
Publication Date(Web):April 29, 2015
DOI:10.1021/acssuschemeng.5b00009
Highly dispersed ultrafine NiIr nanoparticles with different compositions were successfully encapsulated into the cavities of MIL-101 and applied to catalyze the dehydrogenation of hydrazine monohydrate. The catalytic activities relied on the composition of metals, support materials, alkaline, as well as the temperature strongly. Among all the catalysts tested, Ni85Ir15@MIL-101 exhibited the highest catalytic performance in the presence of NaOH at 50 °C. Even at 25 °C, the Ni85Ir15@MIL-101 exhibited the complete dehydrogenation of hydrazine with a turnover frequency value of 24 h–1.Keywords: Hydrazine; Hydrogen storage; Ir; MIL-101; Ni;
Co-reporter:Lan Wen, Xiaoqiong Du, Jun Su, Wei Luo, Ping Cai and Gongzhen Cheng
Dalton Transactions 2015 vol. 44(Issue 13) pp:6212-6218
Publication Date(Web):19 Feb 2015
DOI:10.1039/C5DT00493D
Well-dispersed bimetallic Ni–Pt nanoparticles (NPs) with different compositions have been successfully grown on the MIL-96 by a simple liquid impregnation method using NaBH4 as the reducing agent. Powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, N2 adsorption–desorption, and inductively coupled plasma-atomic emission spectroscopy measurements were employed to characterize the NiPt/MIL-96. Catalytic activity of NiPt/MIL-96 catalysts was tested in the hydrogen generation from the aqueous alkaline solution of hydrazine at room temperature. These catalysts are composition dependent on their catalytic activity, while Ni64Pt36/MIL-96 exhibits the highest catalytic activity among all the catalysts tested, with a turnover frequency value of 114.3 h−1 and 100% hydrogen selectivity. This excellent catalytic performance might be due to the synergistic effect of the MIL-96 support and NiPt NPs, while NiPt NPs supported on other conventional supports, such as SiO2, carbon black, γ-Al2O3, poly(N-vinyl-2-pyrrolidone) (PVP), and the physical mixture of NiPt and MIL-96, all of them exhibit inferior catalytic activity compared to that of NiPt/MIL-96.
Co-reporter:Junfeng Shen, Lan Yang, Kai Hu, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2015 Volume 40(Issue 2) pp:1062-1070
Publication Date(Web):12 January 2015
DOI:10.1016/j.ijhydene.2014.11.031
•One-step synthesis of graphene supported Rh NPs.•The catalysts exhibit excellent catalytic activity.•The catalysts show good durable stability.Well dispersed 2.4 nm Rh nanoparticles (NPs) supported on graphene have been synthesized via a one-step in situ procedure by using methylamine borane (MeAB) as the reducing agent. Compared with other conventional supports, such as carbon black, SiO2, γ-Al2O3, and the physical mixture of Rh and graphene, the as-prepared Rh NPs supported on graphene exhibit superior catalytic activity towards the hydrolysis of ammonia borane. Kinetic studies of catalytic hydrolysis of amine boranes indicate that the as-synthesized Rh/graphene is first order with respect to Rh concentration. Among all the reported Rh-based catalysts, the Rh/graphene exhibits the highest turnover frequency (TOF) values of 325 and 146 min−1, the lowest activation energy (Ea) values of 19.7 and 16.4 kJ/mol, toward hydrolysis of ammonia borane (AB) and MeAB, respectively.
Co-reporter:Cheng Du, Qiang Ao, Nan Cao, Lan Yang, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2015 Volume 40(Issue 18) pp:6180-6187
Publication Date(Web):18 May 2015
DOI:10.1016/j.ijhydene.2015.03.070
•Facile synthesis of graphene supported monodisperse Ru NPs.•The catalysts exhibit excellent catalytic activity.•The catalysts show good durable stability.Monodisperse ruthenium (Ru) nanoparticles (NPs) supported on graphene have been synthesized by co-reduction of RuCl3 and graphite oxide in ethylene glycol using ascorbic acid as reducing agents. Thanks to the narrow size distribution of Ru NPs and the synergistic effect with graphene, the as-synthesized Ru/graphene exerts exceedingly high catalytic activity toward hydrogen generation from hydrolysis of ammonia borane, with the turnover frequency (TOF) value of 600 mol H2 min−1 (mol Ru)−1, which is among the highest value ever reported.
Co-reporter:Bingquan Xia, Chang Liu, Han Wu, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2015 Volume 40(Issue 46) pp:16391-16397
Publication Date(Web):14 December 2015
DOI:10.1016/j.ijhydene.2015.10.038
•Facile synthesis of ZIF-8 supported bimetallic RhNi NPs.•The catalysts exhibit the high TOF toward hydrolysis of ammonia borane.•The catalysts exhibit good selectivity and recycle ability.Highly dispersed bimetallic Rh–Ni nanoparticles with an average diameter of 1.1 ± 0.2 nm have been successfully anchored on the metal-organic frameworks (ZIF-8) by using a simple liquid impregnation method. The RhNi@ZIF-8 nanocatalysts are isolated from the solution and well characterized by using powder XRD, TEM, EDX, XPS, ICP-AES, and N2 adsorption-desorption. Among all the tested catalysts with different compositions, Rh15Ni85@ZIF-8 exhibits the highest catalytic activity toward hydrolysis of ammonia borane, with the turnover frequency value of 58.8 mol H2·min−1·(mol catalyst)−1, and 100% hydrogen selectivity at room temperature.
Co-reporter:Lan Wen, Zhong Zheng, Wei Luo, Ping Cai, Gong-Zhen Cheng
Chinese Chemical Letters 2015 Volume 26(Issue 11) pp:1345-1350
Publication Date(Web):November 2015
DOI:10.1016/j.cclet.2015.06.019
Ultrafine Ru nanoparticles are successfully deposited on MCM-41 by using a simple liquid impregnation-reduction method, and further investigated for catalytic hydrolysis of ammonia borane and methylamine borane. Among all the catalysts tested, 1.12 wt% Ru/MCM-41 exhibits the highest catalytic activity, with turnover frequency value of 288 min−1.Ultrafine Ru nanoparticles have been successfully deposited on MCM-41 by using a simple liquid impregnation method. The 1.12 wt% Ru/MCM-41 exhibit the highest catalytic activity, with the turnover frequency value of 288 min−1 toward catalytic hydrolysis of ammonia borane.
Co-reporter:Bingquan Xia;Kang Chen;Gongzhen Cheng
Nano Research 2015 Volume 8( Issue 11) pp:3472-3479
Publication Date(Web):2015 November
DOI:10.1007/s12274-015-0845-4
Well-dispersed bimetallic NiRh nanoparticles (NPs) with different compositions supported on nitrogen-doped porous carbon (NPC) derived from metal–organic frameworks (ZIF-8) were synthesized through a co-reduction method. The NPC-900 supported NiRh catalyst exhibits the highest catalytic activity and 100% hydrogen selectivity toward hydrogen generation from hydrazine. These properties might be attributed to the high surface area and high graphitization of the NPC. This strategy may open up a new avenue for designing high-performance catalysts by utilizing NPC as a support to anchor active metal NPs for additional applications.
Co-reporter:Hongmei Dai, Nan Cao, Lan Yang, Jun Su, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2014 vol. 2(Issue 29) pp:11060-11064
Publication Date(Web):21 May 2014
DOI:10.1039/C4TA02066A
Bimetallic AgPd nanoparticles were successfully immobilized into the metal–organic frameworks (MIL-101), and tested for their catalytic dehydrogenation of formic acid. These catalysts were composition dependent for the catalytic activity. Among all the AgPd@MIL-101 catalysts tested, the Ag20Pd80@MIL-101 catalyst exhibits the highest catalytic activity for the conversion of formic acid to high-quality hydrogen at 80 °C with a TOF value of 848 h−1, which is among the highest values reported at 80 °C.
Co-reporter:Nan Cao, Lan Yang, Cheng Du, Jun Su, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2014 vol. 2(Issue 35) pp:14344-14347
Publication Date(Web):15 Jul 2014
DOI:10.1039/C4TA02964J
Flower-like Ni–Pt nanoclusters assembled on graphene have been facilely synthesized by a co-reduction route. Thanks to the unique structure and strong interaction with graphene, the as-synthesized Ni3Pt7/graphene nanoclusters exhibit 100% hydrogen selectivity and exceedingly high activity toward hydrogen generation from alkaline solution of hydrazine at room temperature.
Co-reporter:Cheng Du, Yuxiang Liao, Xing Hua, Wei Luo, Shengli Chen and Gongzhen Cheng
Chemical Communications 2014 vol. 50(Issue 85) pp:12843-12846
Publication Date(Web):05 Sep 2014
DOI:10.1039/C4CC05019C
Wavy palladium (Pd) nanorods were obtained by controlled synthesis by using amine–boranes as the reducing agents. Thanks to the unique structure and strong interaction with graphene, the as-synthesized Pd nanorods supported on graphene exhibit much enhanced electrocatalytic activity towards formic acid oxidation as compared with Pd nanoparticles.
Co-reporter:Nan Cao, Lan Yang, Hongmei Dai, Teng Liu, Jun Su, Xiaojun Wu, Wei Luo, and Gongzhen Cheng
Inorganic Chemistry 2014 Volume 53(Issue 19) pp:10122-10128
Publication Date(Web):September 8, 2014
DOI:10.1021/ic5010352
We report a facile liquid impregnation approach for immobilization of ultrafine bimetallic Ni–Pt nanoparticles (NPs) inside the pores of MIL-101. The methods of powder X-ray diffraction, N2 physisorption, X-ray photoelectron spectroscopy, transmission electron microscopy, and inductively coupled plasma-atomic emission spectroscopy were employed to characterize the NiPt@MIL-101 catalysts and further indicated the as-synthesized Ni–Pt NPs were confined in the pores of MIL-101. These as-synthesized bimetallic NiPt@MIL-101 NPs exhibit exceedingly high catalytic activity, selectivity, and durability toward hydrogen generation from alkaline solution of hydrazine.
Co-reporter:Nan Cao, Jun Su, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2014 Volume 39(Issue 1) pp:426-435
Publication Date(Web):2 January 2014
DOI:10.1016/j.ijhydene.2013.10.059
•One-step in situ synthesizes Ru@Ni core–shell NPs supported on graphene.•High activity toward the hydrolysis of AB with the TOF value of 340 mol H2.•Efficient and reusable catalyst for hydrolysis of MeAB.Ru@Ni core–shell nanoparticles (NPs) supported on graphene have been synthesized by one-step in situ co-reduction of aqueous solution of ruthenium (III) chloride, nickel (II) chloride, and graphene oxide (GO) with ammonia borane (AB) as the reducing agent under ambient condition. The as-synthesized NPs exhibit much higher catalytic activity for hydrolytic dehydrogenation of AB than the monometallic, bimetallic alloy (RuNi/graphene), and graphene-free core–shell (Ru@Ni) counterparts. Additionally, the Ru@Ni/graphene NPs facilitate the hydrolysis of AB, with the turnover frequency (TOF) value of 340 mol H2 min−1 (mol Ru)−1, which is among the highest value reported on Ru-based NPs so far, and even higher than the reversed Ni@Ru NPs. Furthermore, the as-prepared NPs exert satisfied durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB and methylamine borane (MeAB). Moreover, this simple synthetic method can be extended to other Ru-based bimetallic core–shell systems for more applications.
Co-reporter:Lan Yang, Jun Su, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2014 Volume 39(Issue 7) pp:3360-3370
Publication Date(Web):25 February 2014
DOI:10.1016/j.ijhydene.2013.12.089
•Facile synthesize trimetallic Ag@CoFe and Ag@NiFe core–shell NPs.•The catalysts exhibit excellent catalytic activity toward hydrolysis of AB and MeAB.•The catalysts supported on graphene exhibit the highest activity.We reported the synthesis and characterization of two trimetallic (Ag@CoFe, and Ag@NiFe) core–shell nanoparticles (NPs), and their catalytic activity toward hydrolytic dehydrogenation of ammonia borane (AB) and methylamine borane (MeAB). The as-synthesized trimetallic core–shell NPs were obtained via a facile one-step in situ procedure using methylamine borane as a reducing agent and graphene as the support under ambient condition. The as-synthesized NPs are well dispersed on graphene, and exhibit higher catalytic activity than the catalysts with other conventional supports, such as the SiO2, carbon black, and γ-Al2O3. Additionally, compared with NaBH4 and AB, the as-synthesized Ag@CoFe/graphene NPs reduced by MeAB exhibit the highest catalytic activity, with the turnover frequency (TOF) value of 82.9 (mol H2 min−1 (mol Ag)−1), and the activation energy (Ea) value of 32.79 kJ/mol. Furthermore, the as-prepared NPs exert good durable and magnetically recyclability for the hydrolytic dehydrogenation of AB and MeAB. Moreover, this simple strategic synthesis method can be easily extended to the facile preparation of other graphene supported multi-metal core–shell NPs.
Co-reporter:Wenqi Feng, Lan Yang, Nan Cao, Cheng Du, Hongmei Dai, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2014 Volume 39(Issue 7) pp:3371-3380
Publication Date(Web):25 February 2014
DOI:10.1016/j.ijhydene.2013.12.113
•One-step synthesis of graphene supported CoNi NPs by the mixture of NaBH4/AB.•The TOF is 16.4 mol H2 min−1 (mol catalyst)−1 for hydrolysis of AB.•The second lowest activation energy of 13.49 kJ/mol for hydrolysis of AB.•The catalysts show good durable stability and magnetically recyclability.Well dispersed magnetically recyclable bimetallic CoxNi1−x (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) nanoparticles (NPs) supported on graphene have been synthesized via a facile in situ one-step procedure, using the mixture of sodium borohydride (NaBH4) and methylamine borane (MeAB) as the reducing agent under ambient condition. These NPs were composition dependent for catalytic hydrolysis of amine boranes. Among all the CoNi/graphene catalysts tested, the Co0.9Ni0.1/graphene NPs exhibit the highest catalytic activity toward hydrolysis of AB with the turnover frequency (TOF) value of 16.4 (mol H2 min−1 (mol catalyst)−1), being higher than that of most reported non-noble metal-based NPs, and even many noble metal-based NPs. Moreover, the activation energy (Ea) value is 13.49 kJ/mol, which is the second lowest value ever reported for catalytic hydrolytic dehydrogenation of ammonia borane, indicating the superior catalytic performance of the as-synthesized Co0.9Ni0.1/graphene catalysts. Additionally, Compared with other reducing agents, such as NaBH4, AB, MeAB, and the mixture of NaBH4 and AB, the as-synthesized Co0.9Ni0.1/graphene catalysts reduced by the mixture of NaBH4 and MeAB exert the highest catalytic activity. The Co0.9Ni0.1 NPs supported on graphene exhibit higher catalytic activity than catalysts with other conventional supports, such as SiO2, carbon black, and γ-Al2O3. Furthermore, the as-synthesized Co0.9Ni0.1/graphene NPs show good recyclability and magnetically reusability for the hydrolytic dehydrogenation of amine boranes, which make the practical reusing application of the catalysts more convenient.
Co-reporter:Hongmei Dai, Jun Su, Kai Hu, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2014 Volume 39(Issue 10) pp:4947-4953
Publication Date(Web):26 March 2014
DOI:10.1016/j.ijhydene.2014.01.068
•Ultrafine Pd NPs have been immobilized in the framework of MIL-101.•Pd@MIL-101 exhibit the highest catalytic activity among Pd-based catalysts.•The Pd@MIL-101 shows good durable stability.Well dispersed ultrafine Pd NPs have been immobilized in the framework of MIL-101, and tested for the catalytic hydrolysis of ammonia borane. The powder XRD, N2 adsorption–desorption, TEM, and ICP-AES were employed to characterize the Pd@MIL-101 catalyst. The as-synthesized Pd@MIL-101 exhibit the highest catalytic activity toward hydrolysis of AB among the Pd-based nano-catalysts ever reported, with the TOF value of 45 mol H2 min−1 (mol Pd)−1.
Co-reporter:Nan Cao, Jun Su, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2014 Volume 39(Issue 18) pp:9726-9734
Publication Date(Web):15 June 2014
DOI:10.1016/j.ijhydene.2014.04.075
•Facile synthesis of MIL-101 supported bimetallic Ni–Pt NPs.•The catalysts exhibit the highest TOF toward hydrolysis of hydrazine.•The catalysts exhibit good selectivity and recycle ability.Highly dispersed bimetallic Ni–Pt nanoparticles with different compositions supported on MIL-101 have been successfully synthesized by a simple liquid impregnation method. The as-synthesized NPs in an average of 1.9 ± 0.4 nm could be isolated by certification and characterized by using PXRD, TEM, EDX, XPS, BET, and ICP-AES. Catalytic activity of the Ni–Pt@MIL-101 was tested in the hydrogen generation from aqueous alkaline solution of hydrazine. These catalysts were composition dependent for the catalytic activity. Among all the Ni–Pt@MIL-101 catalysts tested, the Ni88Pt12@MIL-101 exhibited the highest catalytic activity, with the turnover frequency (TOF) value of 350 molH2molmetal−1h−1 at 50 °C, which is the highest among all the previously reported catalysts.
Co-reporter:Lan Wen, Jun Su, Xiaojun Wu, Ping Cai, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2014 Volume 39(Issue 30) pp:17129-17135
Publication Date(Web):13 October 2014
DOI:10.1016/j.ijhydene.2014.07.179
•Ultrafine Ru NPs have been successfully deposited on MIL-96.•Ru/MIL-96 exhibit exceedingly high catalytic activity with TOF value of 231 min−1.•Ru supported on MIL-96 exhibit enhanced activity compared with other supports.For the first time, ultrafine Ru nanoparticles with mean diameter of 2 nm are successfully deposited on MIL-96 by using a simple liquid impregnation strategy, and tested for catalytic hydrolysis of ammonia borane. The powder X-ray diffraction, N2 physical adsorption, transmission electron microscopy, energy-dispersive X-ray spectroscopy and inductively coupled plasma-atomic emission spectroscopy measurements are employed to characterized the Ru/MIL-96 catalysts. Thanks to the unique 3D structure of MIL-96, Ru NPs supported on MIL-96 exhibit much enhanced catalytic activity compared with other commercial supported materials and graphene, with the TOF value of 231 mol H2 min−1 (mol Ru)−1, which is among the highest value ever reported. Moreover, this simple method can be extended to facile synthesis of other MOFs supported monometallic and polymetallic NPs for more application.
Co-reporter:Nan Cao, Teng Liu, Jun Su, Xiaojun Wu, Wei Luo and Gongzhen Cheng
New Journal of Chemistry 2014 vol. 38(Issue 9) pp:4032-4035
Publication Date(Web):25 Jun 2014
DOI:10.1039/C4NJ00739E
Ultrafine Ru nanoparticles were successfully immobilized inside the pores of MIL-101 by using a simple liquid impregnation method. The turnover frequency (TOF) value of the as-synthesized 2.80 wt% Ru@MIL-101 toward catalytic hydrolysis of ammonia borane is 178 mol H2 min−1 (mol Ru)−1, which is among the highest values ever reported.
Co-reporter:Xiangyu Meng, Shuangshi Li, Bingquan Xia, Lan Yang, Nan Cao, Jun Su, Man He, Wei Luo and Gongzhen Cheng
RSC Advances 2014 vol. 4(Issue 62) pp:32817-32825
Publication Date(Web):21 Jul 2014
DOI:10.1039/C4RA04894F
Magnetic tetrametallic core–shell Cu@FeCoNi nanoparticles (NPs) supported on graphene have been synthesized through a simple one-step in situ procedure using methylamine borane (MeAB) as a reducing agent. The use of MeAB is the key for making the well-defined tetrametallic core–shell NPs, as sodium borohydride (NaBH4) resulting in tetrametallic alloy NPs, and ammonia borane (AB) resulting in a mixture of monometallic Cu and Cu@FeCoNi NPs. Thanks to the core–shell structure, the Cu@FeCoNi/graphene NPs exhibit much higher catalytic performance toward hydrolysis of AB than their counterparts reduced by NaBH4 and AB. Among all the catalysts studied, Cu12.6@Fe9.8Co38.8Ni38.8/graphene displays the highest catalytic performance toward hydrolysis of AB, with a turnover frequency (TOF) value of 20.93 mol H2 per min per mol per catalyst, which is higher than that of most reported non-noble metal-based catalysts, and even some noble-metal based catalysts. Furthermore, the as-prepared NPs exhibit good durability and magnetic recyclability toward hydrolysis of AB and MeAB, which makes the practical recycling application of the NPs more convenient.
Co-reporter:Lan Yang, Nan Cao, Cheng Du, Hongmei Dai, Kai Hu, Wei Luo, Gongzhen Cheng
Materials Letters 2014 Volume 115() pp:113-116
Publication Date(Web):15 January 2014
DOI:10.1016/j.matlet.2013.10.039
•One-step synthesis of graphene supported Co NPs.•The catalysts exhibit excellent catalytic activity toward hydrolysis of AB.•The catalysts show good durable stability and magnetically recyclability.Cobalt(0) nanoparticles supported on graphene have been synthesized via a one-step in situ procedure, using the mixture of ammonia borane (AB) and sodium borohydride (NaBH4) as the reducing agents under ambient temperature. Compared with NaBH4, the as-prepared Co/graphene NPs which reduced by the mixture of NaBH4/AB exhibit superior catalytic activity towards the hydrolytic dehydrogenation of AB. A kinetic study shows that the catalytic hydrolysis of AB is first order with respect to the concentration of the as as-synthesized NPs. The turnover frequency (TOF) is 13.8 mol H2 min−1 (mol Co)−1, which is higher than most of the non-noble metal catalysts, and even noble-metal based NPs. The activation energy has been measured to be 32.75 kJ mol−1, which is lower than many reported values for the catalytic hydrolytic dehydrogenation of ammonia borane.
Co-reporter:Cheng Du, Jun Su, Wei Luo, Gongzhen Cheng
Journal of Molecular Catalysis A: Chemical 2014 Volumes 383–384() pp:38-45
Publication Date(Web):March 2014
DOI:10.1016/j.molcata.2013.11.018
•Facile synthesize graphene supported Ag@Co core–shell NPs.•The catalysts exhibit excellent catalytic activity toward hydrolysis of AB and MeAB.•The catalysts show good durable stability and magnetically recyclability.Well-dispersed Ag@Co core–shell nanoparticles (NPs) supported on graphene with controlled compositions were synthesized by the reduction of silver nitrate, cobalt(II) acetate, and graphene oxide (GO) in the presence of hydrazine and ethylene glycol. These NPs were composition dependent catalysts for hydrogen generation from the hydrolysis of ammonia borane. Among all Ag@Co catalysts tested, the Ag0.5@Co0.5/graphene NPs exhibited the highest catalytic activity, with the turnover frequency (TOF) value of 10.5 mol H2 min−1 (mol catalyst)−1, and activation energy value of 39.33 kJ/mol. Kinetic studies reveal that the catalytic hydrolysis of AB and MeAB are both first order with respect to the catalyst concentrations. Furthermore, the Ag0.5@Co0.5/graphene NPs show good durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB and MeAB, which makes the practical recycling application of the catalyst more convenient.
Co-reporter:Xiangyu Meng;Lan Yang;Nan Cao;Cheng Du;Dr. Kai Hu;Dr. Jun Su;Dr. Wei Luo;Dr. Gongzhen Cheng
ChemPlusChem 2014 Volume 79( Issue 2) pp:325-332
Publication Date(Web):
DOI:10.1002/cplu.201300336
Abstract
Trimetallic core–shell Cu@CoNi nanoparticles (NPs) supported on graphene with different compositions are synthesized through a one-step in situ reduction process by using methylamine borane (MeAB) as a reducing agent. The as-synthesized Cu-core/CoNi-shell NPs are well dispersed on graphene. Among the catalysts studied, Cu0.1@Co0.45Ni0.45/graphene displays the highest catalytic performance toward the hydrolysis of ammonia borane (AB), with a turnover frequency (TOF) value of 15.46 mol H2 min−1(mol catalyst)−1, which is higher than those of most reported non-noble-metal-based NPs, and even higher than many noble-metal-based NPs. Additionally, the as-synthesized Cu0.1@Co0.45Ni0.45/graphene NPs reduced by MeAB exhibit a higher catalytic activity than those reduced by NaBH4 and AB. Furthermore, the as-prepared NPs have good durability and magnetic recyclability for the hydrolytic dehydrogenation of AB and MeAB.
Co-reporter:Bingquan Xia;Nan Cao;Hongmei Dai;Dr. Jun Su;Dr. Xiaojun Wu; Wei Luo; Gongzhen Cheng
ChemCatChem 2014 Volume 6( Issue 9) pp:2549-2552
Publication Date(Web):
DOI:10.1002/cctc.201402353
Abstract
Highly dispersed bimetallic Ni–Rh nanoparticles with an average diameter of (1.2±0.2) nm were successfully deposited on the metal–organic framework (MOF) ZIF-8 by using a simple liquid impregnation method. These catalysts were composition dependent toward the dehydrogenation of hydrazine in alkaline solution, whereas Ni66Rh34@ZIF-8 exhibited the highest catalytic activity among all the catalysts tested with a turnover frequency value of 140 h−1 and 100 % hydrogen selectivity at 50 °C. The excellent catalytic performance may be caused by the synergistic molecular-scale alloying effect of the bimetallic Ni–Rh nanoparticles on ZIF-8 and the promotion effect of ZIF-8. The development of high-performance catalysts by utilizing MOFs as a novel porous catalyst support to control the limited growth of metal nanoparticles may promote the application of hydrous hydrazine as a promising chemical hydrogen-storage material and open up new opportunities to use MOF-supported metal nanoparticles for more applications.
Co-reporter:Lan Yang;Dr. Jun Su;Dr. Wei Luo;Dr. Gongzhen Cheng
ChemCatChem 2014 Volume 6( Issue 6) pp:1617-1625
Publication Date(Web):
DOI:10.1002/cctc.201400042
Abstract
Tetrametallic core–shell Ag@CoNiFe nanoparticles (NPs) supported on graphene have been synthesized by a facile one-step in situ procedure for the first time. We tuned the reducing ability of the reductants to control the structure and particle size of the as-synthesized NPs. The use of weaker reducing agents, such as ammonia borane (AB) and methylamine borane (MeAB), result in the core–shell structure, whereas the stronger reducing agent NaBH4 results in alloy NPs. The as-synthesized core–shell NPs reduced by MeAB possess a smaller particle size and exhibit a superior catalytic activity compared to the core–shell NPs reduced by AB and alloy NPs reduced by NaBH4 for the hydrolytic dehydrogenation of AB. Moreover, the turnover frequency of the as-synthesized tetrametallic core–shell NPs is 118.5 mol min−1 molAg−1, which is higher than that of Ag-based trimetallic, bimetallic core–shell, and alloy counterparts and even higher than that of most reported noble-metal-based NPs. Kinetic studies indicate that the catalytic hydrolysis of AB and MeAB by the Ag@CoNiFe/graphene NPs is a first-order reaction. Furthermore, the as-prepared NPs exert good catalytic activities and recycle stabilities towards the hydrolysis of AB. Additionally, the as-prepared NPs display magnetic recyclability, which makes the practical recycling of the NPs more convenient.
Co-reporter:Nan Cao;Dr. Jun Su;Xinlin Hong; Wei Luo; Gongzhen Cheng
Chemistry – An Asian Journal 2014 Volume 9( Issue 2) pp:562-571
Publication Date(Web):
DOI:10.1002/asia.201301171
Abstract
Well-dispersed core–shell Ru@M (M=Co, Ni, Fe) nanoparticles (NPs) supported on carbon black have been synthesized via a facile in situ one-step procedure under ambient condition. Core-shell Ru@Co NPs were synthesized and characterized for the first time. The as-synthesized Ru@Co and Ru@Ni NPs exhibit superior catalytic activity in the hydrolysis of ammonia borane compared with their monometallic and alloy counterparts. The Ru@Co/C NPs are the most reactive, with a turnover frequency (TOF) value of 320 (mol min−1) molRu−1 and activation energy (Ea) of 21.16 kJ mol−1. Ru@Ni/C NPs are the next most active, whereas Ru@Fe/C NPs are almost inactive. Additionally, the as-synthesized NPs supported on carbon black exhibit higher catalytic activity than catalysts on other conventional supports, such as SiO2 and γ-Al2O3.
Co-reporter:Lan Yang, Jun Su, Xiangyu Meng, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2013 vol. 1(Issue 34) pp:10016-10023
Publication Date(Web):24 Jun 2013
DOI:10.1039/C3TA11835E
Well dispersed magnetically recyclable trimetallic core–shell Ag@CoNi nanoparticles (NPs) supported on graphene have been synthesized via a facile one-step in situ procedure using methylamine borane (MeAB) as the reducing agent. The as-synthesized NPs exhibit much higher catalytic activities for hydrolytic dehydrogenation of ammonia borane (AB) than the monometallic, bimetallic, trimetallic alloy (AgCoNi/graphene), and graphene free (Ag@CoNi) counterparts. Moreover, compared with NaBH4 and AB, the weaker reducing agent MeAB has much better control during the synthesis of the graphene supported Ag@CoNi NPs, which resulted in the highest catalytic activity. Kinetic studies indicate that the catalytic hydrolysis of AB by the Ag@CoNi/graphene NPs is first order, with the activation energy measured to be 36.15 kJ mol−1. Furthermore, the as-prepared NPs exert good catalytic activities and recycle stabilities towards the hydrolysis of AB and MeAB. Hence, this general method indicates that MeAB can be used as both a potential hydrogen storage material and an efficient reducing agent, and can be easily extended to facile preparation of other graphene supported multi-metal NPs.
Co-reporter:Lan Yang, Wei Luo, and Gongzhen Cheng
ACS Applied Materials & Interfaces 2013 Volume 5(Issue 16) pp:8231
Publication Date(Web):July 26, 2013
DOI:10.1021/am402373p
Well-dispersed magnetically recyclable core–shell Ag@M (M = Co, Ni, Fe) nanoparticles (NPs) supported on graphene have been synthesized via a facile in situ one-step procedure, using methylamine borane (MeAB) as a reducing agent under ambient condition. Their catalytic activity toward hydrolysis of ammonia borane (AB) were studied. Although the Ag@Fe/graphene NPs are almost inactive, the as-prepared Ag@Co/graphene NPs are the most reactive catalysts, followed by Ag@Ni/graphene NPs. Compared with AB and NaBH4, the as-synthesized Ag@Co/graphene catalysts which reduced by MeAB exert the highest catalytic activity. Additionally, the Ag@Co NPs supported on graphene exhibit higher catalytic activity than the catalysts with other conventional supports, such as the SiO2, carbon black, and γ-Al2O3. The as-synthesized Ag@Co/graphene NPs exert satisfied catalytic activity, with the turnover frequency (TOF) value of 102.4 (mol H2 min–1 (mol Ag)−1), and the activation energy Ea value of 20.03 kJ/mol. Furthermore, the as-synthesized Ag@Co/graphene NPs show good recyclability and magnetically reusability for the hydrolytic dehydrogenation of AB and MeAB, which make the practical reusing application of the catalysts more convenient. Moreover, this simple synthetic method indicates that MeAB could be used as not only a potential hydrogen storage material but also an efficient reducing agent. It can be easily extended to facile preparation of other graphene supported metal NPs.Keywords: ammonia borane; core−shell NPs; graphene; hydrogen storage; methylamine borane;
Co-reporter:Yeshuang Du, Nan Cao, Lan Yang, Wei Luo and Gongzhen Cheng
New Journal of Chemistry 2013 vol. 37(Issue 10) pp:3035-3042
Publication Date(Web):15 Jul 2013
DOI:10.1039/C3NJ00552F
In this study, well dispersed Cu@Co core–shell nanoparticles (NPs) on rGO surfaces were successfully synthesized via a one-step in situ procedure using methylamine borane (MeAB) as reductant under ambient conditions. The Cu@Co/rGO NPs exhibit superior catalytic activity than their alloy (CuCo/rGO) and graphene-free (Cu@Co) counterparts toward the hydrolytic dehydrogenation of ammonia borane (AB). Additionally, compared with the NPs reduced by AB, the as-synthesized Cu@Co/rGO NPs generated by the weaker reducing agent MeAB exhibit higher catalytic activities. Furthermore, the as-synthesized NPs exerted satisfactory catalytic activities and recycle stabilities for the hydrolysis of MeAB. Moreover, this general method indicates that MeAB can be used as both a potential hydrogen storage material and an efficient reductant which can be easily extended to the facile preparation of other rGO-supported metal NPs.
Co-reporter:Nan Cao, Wei Luo, Gongzhen Cheng
International Journal of Hydrogen Energy 2013 Volume 38(Issue 27) pp:11964-11972
Publication Date(Web):10 September 2013
DOI:10.1016/j.ijhydene.2013.06.125
•One-step synthesize Ru NPs supported on graphene.•Using methylamine borane as reducing agent get the best catalytic activity.•Lowest activation energy value ever reported for catalytic hydrolysis of AB.Ru nanoparticles supported on graphene have been synthesized via a one-step procedure using methylamine borane as reducing agent. Compared with NaBH4 and ammonia borane, the as-prepared Ru/graphene NPs reduced by methylamine borane exhibit superior catalytic activity towards the hydrolytic dehydrogenation of ammonia borane. Additionally, the Ru/graphene NPs exhibit higher catalytic activity than its graphene free counterparts, and retain 72% of their initial catalytic activity after 4 reaction cycles. A kinetic study shows that the catalytic hydrolysis of ammonia borane is first order with respect to Ru concentration, the turnover frequency is 100 mol H2 min−1 (mol Ru)−1. The activation energy for the hydrolysis of ammonia borane in the presence of Ru/graphene NPs has been measured to be 11.7 kJ/mol, which is the lowest value ever reported for the catalytic hydrolytic dehydrogenation of ammonia borane.
Co-reporter:Lan Yang;Gong-Zhen Cheng
Catalysis Letters 2013 Volume 143( Issue 9) pp:873-880
Publication Date(Web):2013 September
DOI:10.1007/s10562-013-1038-y
Amorphous nickel catalysts derived from nickel halides (NiF2, NiCl2, NiBr2, NiI2) were in situ synthesized in an aqueous solution of NaBH4/NH3BH3. The halide anions have effects on the formation of Ni(0) catalysts, which can further affect the catalytic activities and activation energies of the catalysts for the hydrolysis of ammonia borane. The PVP stabilized catalysts have higher hydrogen evolution rates and durabilities than bare Ni catalysts for the hydrolysis of ammonia borane. The catalysts derived from NiBr2 stabilized by PVP present the highest catalytic activity and the lowest activation energy, which has been measured to be 25.58 kJ/mol. This value is lower than most of reported Ni-based catalysts and even noble-metal containing catalysts. The results of mercury poisoning experiment reveal that Ni(0) catalysts derived from NiBr2 are heterogeneous catalysts in the hydrolysis of ammonia borane.
Co-reporter:Jiahao Yu, Gongzhen Cheng and Wei Luo
Journal of Materials Chemistry A 2017 - vol. 5(Issue 30) pp:NaN15844-15844
Publication Date(Web):2017/07/11
DOI:10.1039/C7TA04438K
The development of low-cost, highly efficient, and stable electrocatalysts toward overall water splitting (both the anodic oxygen evolution reaction (OER) and the cathodic hydrogen evolution reaction (HER)) is essential for future energy supply. In this report, 3D ternary nickel iron sulfide microflowers with a hierarchically porous structure directly grown on Ni foam via a convenient two-step method have been fabricated, and further used as an efficient electrocatalyst for both the HER and the OER. Thanks to the unique 3D morphology and strong electron interactions between Fe, Ni and S, the as-synthesized Ni0.7Fe0.3S2 delivers an overpotential of 198 mV at a current density of 10 mA cm−2 toward the OER in alkaline media, which is, to the best of our knowledge, the best among the reported non-noble metal based electrocatalysts. Furthermore, when used as both the anode and cathode, a low cell voltage of 1.625 V is needed to obtain 10 mA cm−2 for the overall water splitting.
Co-reporter:Jiahao Yu, Gongzhen Cheng and Wei Luo
Journal of Materials Chemistry A 2017 - vol. 5(Issue 22) pp:NaN11235-11235
Publication Date(Web):2017/05/09
DOI:10.1039/C7TA02968C
Developing low-cost, highly efficient, and superior stable electrocatalysts for the oxygen evolution reaction (OER) is essential for upcoming renewable and clean energy systems. Here, 3D ternary nickel iron phosphide microflowers with a hierarchically porous morphology directly grown on Ni foam via a successive hydrothermal and phosphidation method are synthesized. Benefitting from their unique 3D hierarchical microflower-like structure and the strong electron interactions between Fe, Ni and P, the as-synthesized (NixFe1−x)2P catalysts can effectively catalyze the OER with an overpotential of 219 mV at a current density of 20 mA cm−2 in alkaline media, which is, to the best of our knowledge, the best among the reported non-noble metal-based catalysts.
Co-reporter:Xiaoqiong Du, Shiyi Tan, Ping Cai, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2016 - vol. 4(Issue 38) pp:NaN14576-14576
Publication Date(Web):2016/08/31
DOI:10.1039/C6TA05917A
Transition metal phosphide based hybrids (RhNiP/rGO) with different phosphorus contents have been successfully synthesized via a facile one-pot co-reduction route. Thanks to the synergistic electronic effect between Rh, Ni, and P, the as-synthesized RhNiP/rGO hybrid exhibits superior catalytic activity toward hydrogen generation from an alkaline solution of hydrazine.
Co-reporter:Quan Zuo, Gongzhen Cheng and Wei Luo
Dalton Transactions 2017 - vol. 46(Issue 29) pp:NaN9348-9348
Publication Date(Web):2017/06/15
DOI:10.1039/C7DT01694H
A reduced graphene oxide/covalent cobalt porphyrin framework has been synthesized by using pyridine-functionalized reduced graphene oxide (G-dye) as the building block. Due to the unique 3-dimensional architecture and good electronic properties of graphene, as well as the electron accepting ability of the nitrogen atoms in the G-dye, the as-synthesized CoCOF-Py-0.05rGO catalyst exhibits excellent oxygen reduction reaction (ORR) activity with superior long-term stability and methanol tolerance.
Co-reporter:Pingping Zhao, Xing Hua, Wei Xu, Wei Luo, Shengli Chen and Gongzhen Cheng
Catalysis Science & Technology (2011-Present) 2016 - vol. 6(Issue 16) pp:NaN6371-6371
Publication Date(Web):2016/06/01
DOI:10.1039/C6CY01031H
Active and stable electrocatalysts based on earth-abundant elements for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucially important for the utilization of renewable energy. Herein, we reported the synthesis of Fe3C nanorod encapsulated, N-doped carbon nanotubes grown on N-doped porous carbon sheets (Fe3C@NCNT/NPC) by simply annealing a Fe-based MOF (MIL-88B) loaded with melamine at 800 °C in N2. Thanks to the synergistic effect of the high density of Fe–N active sites and electric conductance offered by the unique hybrid structure, the as-prepared Fe3C@NCNT/NPC hybrid exhibited a half-wave potential ca. 60 mV more positive and a durability performance much better than that of Pt/C for ORR, and an overpotential ca. 20 mV lower and a Tafel slope much smaller than that of IrO2 for OER, which make it one of the best reported nonprecious metal bifunctional electrocatalysts for oxygen electrode reactions.
Co-reporter:Cheng Du, Yuxiang Liao, Xing Hua, Wei Luo, Shengli Chen and Gongzhen Cheng
Chemical Communications 2014 - vol. 50(Issue 85) pp:NaN12846-12846
Publication Date(Web):2014/09/05
DOI:10.1039/C4CC05019C
Wavy palladium (Pd) nanorods were obtained by controlled synthesis by using amine–boranes as the reducing agents. Thanks to the unique structure and strong interaction with graphene, the as-synthesized Pd nanorods supported on graphene exhibit much enhanced electrocatalytic activity towards formic acid oxidation as compared with Pd nanoparticles.
Co-reporter:Lan Wen, Xiaoqiong Du, Jun Su, Wei Luo, Ping Cai and Gongzhen Cheng
Dalton Transactions 2015 - vol. 44(Issue 13) pp:NaN6218-6218
Publication Date(Web):2015/02/19
DOI:10.1039/C5DT00493D
Well-dispersed bimetallic Ni–Pt nanoparticles (NPs) with different compositions have been successfully grown on the MIL-96 by a simple liquid impregnation method using NaBH4 as the reducing agent. Powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, N2 adsorption–desorption, and inductively coupled plasma-atomic emission spectroscopy measurements were employed to characterize the NiPt/MIL-96. Catalytic activity of NiPt/MIL-96 catalysts was tested in the hydrogen generation from the aqueous alkaline solution of hydrazine at room temperature. These catalysts are composition dependent on their catalytic activity, while Ni64Pt36/MIL-96 exhibits the highest catalytic activity among all the catalysts tested, with a turnover frequency value of 114.3 h−1 and 100% hydrogen selectivity. This excellent catalytic performance might be due to the synergistic effect of the MIL-96 support and NiPt NPs, while NiPt NPs supported on other conventional supports, such as SiO2, carbon black, γ-Al2O3, poly(N-vinyl-2-pyrrolidone) (PVP), and the physical mixture of NiPt and MIL-96, all of them exhibit inferior catalytic activity compared to that of NiPt/MIL-96.
Co-reporter:Teng Liu, Pingping Zhao, Xing Hua, Wei Luo, Shengli Chen and Gongzhen Cheng
Journal of Materials Chemistry A 2016 - vol. 4(Issue 29) pp:NaN11364-11364
Publication Date(Web):2016/06/21
DOI:10.1039/C6TA03265F
A simple Zn/Fe bimetallic zeolitic–imidazolite framework (ZIF) carbonization method is developed to synthesize an Fe–N–C hybrid with hierarchical nitrogen-doped porous carbons crossed by carbon nanotubes. Both the specific ratios of Zn/Fe in the bimetallic metal–organic framework (MOF) precursors and the selected annealing temperature are essential for the formation of this unique hybrid structure with good conductivity and exposure of more active sites. The resulting FeNC-20-1000 hybrid electrocatalyst exhibits excellent oxygen reduction reaction (ORR) activity, with a half-wave potential of 0.770 V comparable to that of the commercial Pt/C catalysts in acidic media, and a half-wave potential of 0.880 V, ca. 50 mV more positive than that of Pt/C for ORR in alkaline solution. More importantly, the as-prepared Fe–N–C hybrid exhibits much more stability for the ORR in both acidic and alkaline solutions than Pt/C, which makes it among the best non-noble-metal catalysts ever reported for ORR under acidic and alkaline conditions.
Co-reporter:Bingquan Xia, Teng Liu, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2016 - vol. 4(Issue 15) pp:NaN5622-5622
Publication Date(Web):2016/03/10
DOI:10.1039/C6TA00766J
Safe and efficient storage of hydrogen is the key issue for the hydrogen economy. Hydrazine monohydrate is regarded as a potential hydrogen carrier. Herein, we report a facile synthesis of NiPt–MnOx supported on nitrogen-doped porous carbon (NPC) derived from annealing metal–organic frameworks (MOFs) at different temperatures in Ar. Interestingly, the obtained (Ni3Pt7)0.5–(MnOx)0.5/NPC-900 exhibits superior catalytic activity toward dehydrogenation of an alkaline solution of hydrazine, with initial turnover frequency values of 706 and 120 h−1 at 323 K and room temperature, respectively. This excellent catalytic performance may have resulted from the synergistic electronic effect of NiPt and MnOx, the small size and high dispersion of NiPt–MnOx nanocatalysts, NPC as an excellent support with large pore volume, high surface area, high nitrogen content, electrical conductance, and also the high density of the metal-N active sites between NiPt–MnOx and NPC.
Co-reporter:Pingping Zhao, Nan Cao, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2015 - vol. 3(Issue 23) pp:NaN12475-12475
Publication Date(Web):2015/05/06
DOI:10.1039/C5TA02201K
Nanoscale MIL-101 has been controlled, synthesized by a seeding method, and further used as the support for immobilizing RhNi nanoparticles (NPs) as efficient catalysts toward hydrogen generation from hydrous hydrazine in alkaline solution. Compared with other commercial materials and bulk MIL-101, RhNi NPs supported on nanoscale MIL-101 exhibit the highest catalytic activity and 100% hydrogen selectivity.
Co-reporter:Nan Cao, Lan Yang, Cheng Du, Jun Su, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2014 - vol. 2(Issue 35) pp:NaN14347-14347
Publication Date(Web):2014/07/15
DOI:10.1039/C4TA02964J
Flower-like Ni–Pt nanoclusters assembled on graphene have been facilely synthesized by a co-reduction route. Thanks to the unique structure and strong interaction with graphene, the as-synthesized Ni3Pt7/graphene nanoclusters exhibit 100% hydrogen selectivity and exceedingly high activity toward hydrogen generation from alkaline solution of hydrazine at room temperature.
Co-reporter:Hongmei Dai, Nan Cao, Lan Yang, Jun Su, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2014 - vol. 2(Issue 29) pp:NaN11064-11064
Publication Date(Web):2014/05/21
DOI:10.1039/C4TA02066A
Bimetallic AgPd nanoparticles were successfully immobilized into the metal–organic frameworks (MIL-101), and tested for their catalytic dehydrogenation of formic acid. These catalysts were composition dependent for the catalytic activity. Among all the AgPd@MIL-101 catalysts tested, the Ag20Pd80@MIL-101 catalyst exhibits the highest catalytic activity for the conversion of formic acid to high-quality hydrogen at 80 °C with a TOF value of 848 h−1, which is among the highest values reported at 80 °C.
Co-reporter:Lan Yang, Jun Su, Xiangyu Meng, Wei Luo and Gongzhen Cheng
Journal of Materials Chemistry A 2013 - vol. 1(Issue 34) pp:NaN10023-10023
Publication Date(Web):2013/06/24
DOI:10.1039/C3TA11835E
Well dispersed magnetically recyclable trimetallic core–shell Ag@CoNi nanoparticles (NPs) supported on graphene have been synthesized via a facile one-step in situ procedure using methylamine borane (MeAB) as the reducing agent. The as-synthesized NPs exhibit much higher catalytic activities for hydrolytic dehydrogenation of ammonia borane (AB) than the monometallic, bimetallic, trimetallic alloy (AgCoNi/graphene), and graphene free (Ag@CoNi) counterparts. Moreover, compared with NaBH4 and AB, the weaker reducing agent MeAB has much better control during the synthesis of the graphene supported Ag@CoNi NPs, which resulted in the highest catalytic activity. Kinetic studies indicate that the catalytic hydrolysis of AB by the Ag@CoNi/graphene NPs is first order, with the activation energy measured to be 36.15 kJ mol−1. Furthermore, the as-prepared NPs exert good catalytic activities and recycle stabilities towards the hydrolysis of AB and MeAB. Hence, this general method indicates that MeAB can be used as both a potential hydrogen storage material and an efficient reducing agent, and can be easily extended to facile preparation of other graphene supported multi-metal NPs.
