Cobalt carbide(Co2C)was considered as potential catalysts available for large-scale industrialization of transforming syngas(H2 and CO)to clean fuels.Herein,we successfully synthesized Co-based catalysts with MnO supp...Cobalt carbide(Co2C)was considered as potential catalysts available for large-scale industrialization of transforming syngas(H2 and CO)to clean fuels.Herein,we successfully synthesized Co-based catalysts with MnO supported,to comprehend the effects of Co2C for Fischer–Tropsch synthesis(FTS)under ambient conditions.The huge variety of product selectivity which was contained by different active sites(Co and Co2C)has been found.Furthermore,density functional theory(DFT)shows that Co2C is efficacious of CO adsorption,whereas is weaker for H adsorption than Co.Combining the advantages of Co and Co2C,the catalyst herein can not only obtain more C5+products but also suppress methane selectivity.It can be a commendable guide for the design of industrial application products in FTS.展开更多
Cobalt carbide has recently been reported to catalyse the FTO con version of syngas with high selectivity for the production of lower olefins (C2-C4). Clarifying the formation process and atomic structure of cobalt ca...Cobalt carbide has recently been reported to catalyse the FTO con version of syngas with high selectivity for the production of lower olefins (C2-C4). Clarifying the formation process and atomic structure of cobalt carbide will help understand the catalytic mechanism of FTO. Herein, hydrogenati on of carb on monoxide was investigated for cobalt carbide synthesized from CoMn catalyst, followed by X-ray diffraction, transmission electron microscopy, temperature programmed reaction and in situ X-ray absorption spectroscopy. By monitoring the evolution of cobalt carbide during syngas conversion, the wavelet transform results give evidenee for the formation of the cobalt carbide and clearly demonstrate that the active site of catalysis was cobalt carbide.展开更多
Metal–organic frameworks have garnered attention as highly efficient pre-electrocatalysts for the oxygen evolution reaction(OER).Current structure–activity relationships primarily rely on the assumption that the comp...Metal–organic frameworks have garnered attention as highly efficient pre-electrocatalysts for the oxygen evolution reaction(OER).Current structure–activity relationships primarily rely on the assumption that the complete dissolution of organic ligands occurs during electrocatalysis.Herein,modeling based on NiFe Prussian blue analogs(NiFe-PBAs)show that cyanide ligands leach from the matrix and subsequently oxidize to corresponding inorganic ions(ammonium and carbonate)that re-adsorb onto the surface of NiFe OOH during the OER process.Interestingly,the surface-adsorbed inorganic ions induce the OER reaction of NiFe OOH to switch from the adsorbate evolution to the lattice-oxygen–mediated mechanism,thus contributing to the high activity.In addition,this reconstructed inorganic ion layer acting as a versatile protective layer can prevent the dissolution of metal sites to maintain contact between catalytic sites and reactive ions,thus breaking the activity–stability trade-off.Consequently,our constructed NiFePBAs exhibit excellent durability for 1250 h with an ultralow overpotential of 253 mV at 100 mA cm2.The scale-up NiFe-PBAs operated with a low energy consumption of4.18 kWh m3 H2 in industrial water electrolysis equipment.The economic analysis of the entire life cycle demonstrates that this green hydrogen production is priced at US$2.59 kg^(-1)H_(2),meeting global targets(<US$2.5 kg^(-1)H_(2)).展开更多
Cu-based electrocatalysts with favorable facets and Cu^(+)can boost CO_(2) reduction to valuable multicarbon products.However,the inevitable Cu^(+)reduction and the phase evolution usually result in poor performance.H...Cu-based electrocatalysts with favorable facets and Cu^(+)can boost CO_(2) reduction to valuable multicarbon products.However,the inevitable Cu^(+)reduction and the phase evolution usually result in poor performance.Herein,we fabricate CuI nanodots with favorable(220)facets and a stable Cu^(+)state,accomplished by operando reconstruction of Cu(OH)_(2) under CO_(2)-and I--containing electrolytes for enhanced CO_(2)-to-C_(2)H_(4) conversion.Synchrotron X-ray absorption spectroscopy(XAS),in-situ Raman spectroscopy and thermodynamic potential analysis reveal the preferred formation of CuI.Vacuum gas electroresponse and density functional theory(DFT)calculations reveal that CO_(2)-related species induce the exposure of the(220)plane of Cu I.Moreover,the small size of nanodots enables the adequate contact with I^(-),which guarantees the rapid formation of Cu I instead of the electroreduction to Cu^(0).As a result,the resulting catalysts exhibit a high C2H4 Faradaic efficiency of 72.4%at a large current density of 800 m A cm^(-2) and robust stability for 12 h in a flow cell.Combined in-situ ATR-SEIRS spectroscopic characterizations and DFT calculations indicate that the(220)facets and stable Cu^(+) in CuI nanodots synergistically facilitate CO_(2)/*CO adsorption and*CO dimerization.展开更多
基金supported from the National Natural Science Foundation of China,Grant/Award Number:U1732267,21503218.
文摘Cobalt carbide(Co2C)was considered as potential catalysts available for large-scale industrialization of transforming syngas(H2 and CO)to clean fuels.Herein,we successfully synthesized Co-based catalysts with MnO supported,to comprehend the effects of Co2C for Fischer–Tropsch synthesis(FTS)under ambient conditions.The huge variety of product selectivity which was contained by different active sites(Co and Co2C)has been found.Furthermore,density functional theory(DFT)shows that Co2C is efficacious of CO adsorption,whereas is weaker for H adsorption than Co.Combining the advantages of Co and Co2C,the catalyst herein can not only obtain more C5+products but also suppress methane selectivity.It can be a commendable guide for the design of industrial application products in FTS.
基金the financial support from Joint Fund U1732267 of the National Natural Science Foundation of Chinathe Strategic Priority Research Program of Chinese Academy of Sciences(XDB17000000)+2 种基金the National Key R&D Program of China(2017YFB0602500)the National Natural Science Foundation of China(Grant no.21503218)DICP DMTO201306(Grant no.DICP DMTO201306)
文摘Cobalt carbide has recently been reported to catalyse the FTO con version of syngas with high selectivity for the production of lower olefins (C2-C4). Clarifying the formation process and atomic structure of cobalt carbide will help understand the catalytic mechanism of FTO. Herein, hydrogenati on of carb on monoxide was investigated for cobalt carbide synthesized from CoMn catalyst, followed by X-ray diffraction, transmission electron microscopy, temperature programmed reaction and in situ X-ray absorption spectroscopy. By monitoring the evolution of cobalt carbide during syngas conversion, the wavelet transform results give evidenee for the formation of the cobalt carbide and clearly demonstrate that the active site of catalysis was cobalt carbide.
基金supported by the Foundation of Basic and Applied Basic Research of Guangdong Province(2023B1515120043)the National Natural Science Foundation of China(22071069 and 22275060)+3 种基金the Yangfan Project of Maoming City(MMGCIRI2022YFJH-Y-014)Guangdong Basic and Applied Basic Research Foundation(2019A1515011512,2021A1515010172,and 2023A1515030274)the Foundation of the Smart Medical Innovation Technology Center in Guangdong University of Technology(ZYZX24-031)support from Analysis and Testing Center of Guangdong University of Technology。
文摘Metal–organic frameworks have garnered attention as highly efficient pre-electrocatalysts for the oxygen evolution reaction(OER).Current structure–activity relationships primarily rely on the assumption that the complete dissolution of organic ligands occurs during electrocatalysis.Herein,modeling based on NiFe Prussian blue analogs(NiFe-PBAs)show that cyanide ligands leach from the matrix and subsequently oxidize to corresponding inorganic ions(ammonium and carbonate)that re-adsorb onto the surface of NiFe OOH during the OER process.Interestingly,the surface-adsorbed inorganic ions induce the OER reaction of NiFe OOH to switch from the adsorbate evolution to the lattice-oxygen–mediated mechanism,thus contributing to the high activity.In addition,this reconstructed inorganic ion layer acting as a versatile protective layer can prevent the dissolution of metal sites to maintain contact between catalytic sites and reactive ions,thus breaking the activity–stability trade-off.Consequently,our constructed NiFePBAs exhibit excellent durability for 1250 h with an ultralow overpotential of 253 mV at 100 mA cm2.The scale-up NiFe-PBAs operated with a low energy consumption of4.18 kWh m3 H2 in industrial water electrolysis equipment.The economic analysis of the entire life cycle demonstrates that this green hydrogen production is priced at US$2.59 kg^(-1)H_(2),meeting global targets(<US$2.5 kg^(-1)H_(2)).
基金financially supported by The National Key Research and Development Program of China(2021YFA1600800)the Start-up Funding of the Huazhong University of Science and Technology(HUST)+2 种基金the Program for HUST Academic Frontier Youth Teamthe National Natural Science Foundation of China(22075092)the National 1000 Young Talents Program of China and The Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)。
文摘Cu-based electrocatalysts with favorable facets and Cu^(+)can boost CO_(2) reduction to valuable multicarbon products.However,the inevitable Cu^(+)reduction and the phase evolution usually result in poor performance.Herein,we fabricate CuI nanodots with favorable(220)facets and a stable Cu^(+)state,accomplished by operando reconstruction of Cu(OH)_(2) under CO_(2)-and I--containing electrolytes for enhanced CO_(2)-to-C_(2)H_(4) conversion.Synchrotron X-ray absorption spectroscopy(XAS),in-situ Raman spectroscopy and thermodynamic potential analysis reveal the preferred formation of CuI.Vacuum gas electroresponse and density functional theory(DFT)calculations reveal that CO_(2)-related species induce the exposure of the(220)plane of Cu I.Moreover,the small size of nanodots enables the adequate contact with I^(-),which guarantees the rapid formation of Cu I instead of the electroreduction to Cu^(0).As a result,the resulting catalysts exhibit a high C2H4 Faradaic efficiency of 72.4%at a large current density of 800 m A cm^(-2) and robust stability for 12 h in a flow cell.Combined in-situ ATR-SEIRS spectroscopic characterizations and DFT calculations indicate that the(220)facets and stable Cu^(+) in CuI nanodots synergistically facilitate CO_(2)/*CO adsorption and*CO dimerization.
