Developing low-cost,high-performance electrocatalysts for the hydrogen evolution reaction(HER)is essential for producing hydrogen from renewable energy sources.Herein,we report phosphated IrMo bimetallic clusters supp...Developing low-cost,high-performance electrocatalysts for the hydrogen evolution reaction(HER)is essential for producing hydrogen from renewable energy sources.Herein,we report phosphated IrMo bimetallic clusters supported by macroporous nitrogen-doped carbon(IrMoP/MNC)as a highly efficient alkaline HER catalyst.The experimental and theoretical results demonstrate that P and Mo synergistically tune the electronic structure of atomically dispersed Ir to improve adsorption of the reactant H_(2)O and desorption of the product OH^(-).P itself serves as an active site and cooperates with the nearby Ir atom to significantly enhance the HER kinetics.Even with only 2.6 wt%Ir in the catalyst,IrMoP/MNC exhibits an ultralow overpotential of 14 mV at 10 mA cm^(-2),as well as an unprecedented high mass activity of 18.58 A mg Ir^(-1) at an overpotential of 100 mV,superior to commercial Pt/C and overwhelmingly better than other Ir-based electrocatalysts.This study demonstrates a multi-level design strategy to effectively improve the atom efficiency of a noble metal,involving spatial geometry,local electronic structure,and dual-atom synergy.展开更多
Two-dimensional transition metal hydroxides with abundant reserves and low prices have played an indispensable role in energy catalytic applications.Recent reports indicated that the incorporation of Fe species into C...Two-dimensional transition metal hydroxides with abundant reserves and low prices have played an indispensable role in energy catalytic applications.Recent reports indicated that the incorporation of Fe species into Co-based catalysts can synergistically enhance oxygen evolution reaction(OER)activity.Constructing a heterointerface on the surface of Co-based catalysts can provide a platform to investigate the role of heterointerface in reaction kinetics.Herein,we constructed a Fe-O-Co heterointerface without electronic effect by depositing FeO_(x)clusters on the oxygen vacancies of CoOOH surface.FeO_(x)/CoOOH exhibited excellent OER intrinsic activity,which can deliver the turnover frequency(TOF)of 4.56 s^(-1)at the overpotentials of 300 mV and the Tafel slope of 33 mV·dec^(-1).In-situ electrochemical impedance spectroscopy(EIS)and density functional theory(DFT)calculations demonstrated that the synergistic effect between Fe sites and Co sites confined at the Fe-O-Co heterointerface accelerated the charge transfer during OER and optimized the adsorption of oxygen intermediates,consequently enhancing OER.展开更多
Ru has recently been regarded as a promising catalyst for hydrogen oxidation reaction(HOR) and hydrogen evolution reaction(HER) due to its similar binding energy towards *H but lower price compared to Pt.Nevertheless,...Ru has recently been regarded as a promising catalyst for hydrogen oxidation reaction(HOR) and hydrogen evolution reaction(HER) due to its similar binding energy towards *H but lower price compared to Pt.Nevertheless, the quest of high-efficiency Ru-based catalysts for HOR and HER is driven by the current disadvantages including low activity and unsatisfactory stability. Herein, we have fabricated and engineered two-dimensional(2D) Ru-based snow-like nanosheets with Ru/Ru O2interface(Ru/Ru O2SNSs)via a post-annealing treatment. Detailed characterizations and theoretical calculations indicate that the interfacial synergy, which is dependent on the temperature for annealing, can alter the hydrogen binding energy(HBE) and hydroxide binding energy(OHBE), as a result of the enhanced HOR and HER performance. Impressively, the optimal Ru/RuO_(2) SNSs display a mass activity of 9.13 A mgRu^(–1) at an overpotential of 50 m V in 0.1 mol L^(–1) KOH for HOR, which is 65, 304, and 21 times higher than those of Ru SNSs(0.14 A mg_(Ru)^(–1)), RuO_(2) SNSs(0.03 A mg_(Ru)^(–1)), and commercial Pt/C(0.43 A mg_(Ru)^(–1)), respectively.Moreover, Ru/RuO_(2) SNSs display improved HER activity with a low overpotential of 20.2 m V for achieving10 m A cm^(-2)in 1 mol L^(–1)KOH. This work not only provides an efficient catalyst for HOR and HER, but also promotes fundamental research on the fabrication and modification of catalysts in heterogeneous catalysis.展开更多
Alkaline hydrogen evolution reaction(HER)is suppressed by the water dissociation,leading to more sluggish kinetics than acidic HER.Developing multifunction catalysts via constructing heterogeneous interfaces is a feas...Alkaline hydrogen evolution reaction(HER)is suppressed by the water dissociation,leading to more sluggish kinetics than acidic HER.Developing multifunction catalysts via constructing heterogeneous interfaces is a feasible tactic to accelerate the alkaline HER.Herein,NiO coupled with Ni and MoxN(NMN)nanorods were prepared via a hydro-thermal synthesis combined with a thermal decomposition under ammonia atmosphere.The low crystalline NMN nanorods are rich in heterointerfaces,and have sufficient high active sites for HER.The synergistic effect between NiO and Ni-MoxN promotes the water dissociation the hydrogen adsorption,and the charge transfer,contributing to excellent alkaline HER activity.The overpotential on NMN is only 36 and 150 mV for the current density of 10 and 300 mA cm^(-2),respectively,and the Tafel slope is 48 mV/dec,demonstrating a superior performance for alkaline HER,which is even comparable to the commercial electrocatalysts.展开更多
基金supported by Natural Science Foundation of Beijing Municipality(Z200012)National Key Research and Development Program of China(2021YFB4000601)National Natural Science Foundation of China(21975010,U21A20328).
文摘Developing low-cost,high-performance electrocatalysts for the hydrogen evolution reaction(HER)is essential for producing hydrogen from renewable energy sources.Herein,we report phosphated IrMo bimetallic clusters supported by macroporous nitrogen-doped carbon(IrMoP/MNC)as a highly efficient alkaline HER catalyst.The experimental and theoretical results demonstrate that P and Mo synergistically tune the electronic structure of atomically dispersed Ir to improve adsorption of the reactant H_(2)O and desorption of the product OH^(-).P itself serves as an active site and cooperates with the nearby Ir atom to significantly enhance the HER kinetics.Even with only 2.6 wt%Ir in the catalyst,IrMoP/MNC exhibits an ultralow overpotential of 14 mV at 10 mA cm^(-2),as well as an unprecedented high mass activity of 18.58 A mg Ir^(-1) at an overpotential of 100 mV,superior to commercial Pt/C and overwhelmingly better than other Ir-based electrocatalysts.This study demonstrates a multi-level design strategy to effectively improve the atom efficiency of a noble metal,involving spatial geometry,local electronic structure,and dual-atom synergy.
基金This work was supported by the National Key Research and Development Program of China(Nos.2017YFA0403402,2019YFA0405600,2019YFA0405602,and 2021YFA1500500)National Natural Science Foundation of China(NSFC,Nos.21972132,21673214,22202192,U19A2015,92045301,U1732149,and U1732272)+8 种基金National Science Fund for Distinguished Young Scholars(No.21925204)Fundamental Research Funds for the Central Universities(No.20720220010)Provincial Key Research and Development Program of Anhui(No.202004a05020074)K.C.Wong Education(No.GJTD-2020-15)the DNL Cooperation Fund,Chinese Academy of Sciences(CAS,No.DNL202003)Users with Excellence Program of Hefei Science Center CAS(No.2020HSC-UE001)USTC Research Funds of the Double First-Class Initiative(No.YD2340002002)Anhui Natural Science Foundation for Young Scholars(Nos.2208085QB52 and 2208085QB41)CAS Project for Young Scientists in Basic Research(No.YSBR-051).
文摘Two-dimensional transition metal hydroxides with abundant reserves and low prices have played an indispensable role in energy catalytic applications.Recent reports indicated that the incorporation of Fe species into Co-based catalysts can synergistically enhance oxygen evolution reaction(OER)activity.Constructing a heterointerface on the surface of Co-based catalysts can provide a platform to investigate the role of heterointerface in reaction kinetics.Herein,we constructed a Fe-O-Co heterointerface without electronic effect by depositing FeO_(x)clusters on the oxygen vacancies of CoOOH surface.FeO_(x)/CoOOH exhibited excellent OER intrinsic activity,which can deliver the turnover frequency(TOF)of 4.56 s^(-1)at the overpotentials of 300 mV and the Tafel slope of 33 mV·dec^(-1).In-situ electrochemical impedance spectroscopy(EIS)and density functional theory(DFT)calculations demonstrated that the synergistic effect between Fe sites and Co sites confined at the Fe-O-Co heterointerface accelerated the charge transfer during OER and optimized the adsorption of oxygen intermediates,consequently enhancing OER.
基金supported by the National Key R&D Program of China(2020YFB1505802)the Ministry of Science and Technology of China(2017YFA0208200,2016YFA0204100)+4 种基金the National Natural Science Foundation of China(22025108,U21A20327,and22121001)China Postdoctoral Science Foundation(2020M682083)Guangdong Provincial Natural Science Fund for Distinguished Young Scholars(2021B1515020081)Start-up Support from Xiamen University and the Guangzhou Key Laboratory of Low Dimensional Materials and Energy Storage Devices(20195010002)。
文摘Ru has recently been regarded as a promising catalyst for hydrogen oxidation reaction(HOR) and hydrogen evolution reaction(HER) due to its similar binding energy towards *H but lower price compared to Pt.Nevertheless, the quest of high-efficiency Ru-based catalysts for HOR and HER is driven by the current disadvantages including low activity and unsatisfactory stability. Herein, we have fabricated and engineered two-dimensional(2D) Ru-based snow-like nanosheets with Ru/Ru O2interface(Ru/Ru O2SNSs)via a post-annealing treatment. Detailed characterizations and theoretical calculations indicate that the interfacial synergy, which is dependent on the temperature for annealing, can alter the hydrogen binding energy(HBE) and hydroxide binding energy(OHBE), as a result of the enhanced HOR and HER performance. Impressively, the optimal Ru/RuO_(2) SNSs display a mass activity of 9.13 A mgRu^(–1) at an overpotential of 50 m V in 0.1 mol L^(–1) KOH for HOR, which is 65, 304, and 21 times higher than those of Ru SNSs(0.14 A mg_(Ru)^(–1)), RuO_(2) SNSs(0.03 A mg_(Ru)^(–1)), and commercial Pt/C(0.43 A mg_(Ru)^(–1)), respectively.Moreover, Ru/RuO_(2) SNSs display improved HER activity with a low overpotential of 20.2 m V for achieving10 m A cm^(-2)in 1 mol L^(–1)KOH. This work not only provides an efficient catalyst for HOR and HER, but also promotes fundamental research on the fabrication and modification of catalysts in heterogeneous catalysis.
基金financially supported by National Key R&D Program of China(2022YFF0705104)National Natural Science Foundation of China(51402199,U21A20316)+2 种基金Liaoning Revitalization Talents Program(XLYC2007193)Natural Science Foundation of Liaoning Province(2022-MS-289,2021NLTS1210)Scientific Research Foundation of Education Department of Liaoning Province(LJKZ0457).
文摘Alkaline hydrogen evolution reaction(HER)is suppressed by the water dissociation,leading to more sluggish kinetics than acidic HER.Developing multifunction catalysts via constructing heterogeneous interfaces is a feasible tactic to accelerate the alkaline HER.Herein,NiO coupled with Ni and MoxN(NMN)nanorods were prepared via a hydro-thermal synthesis combined with a thermal decomposition under ammonia atmosphere.The low crystalline NMN nanorods are rich in heterointerfaces,and have sufficient high active sites for HER.The synergistic effect between NiO and Ni-MoxN promotes the water dissociation the hydrogen adsorption,and the charge transfer,contributing to excellent alkaline HER activity.The overpotential on NMN is only 36 and 150 mV for the current density of 10 and 300 mA cm^(-2),respectively,and the Tafel slope is 48 mV/dec,demonstrating a superior performance for alkaline HER,which is even comparable to the commercial electrocatalysts.
