CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the ...CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the alkali metals on the physicochemical properties of the CoCu/TiO_2 catalysts and the catalytic performance for CO_2 hydrogenation to long-chain hydrocarbons（C_（5＋））were investigated in this work. According to the characterization of the catalysts based on X-ray photoelectron spectroscopy, X-ray diffraction, CO_2 temperature-programmed desorption（TPD）, and H_2-TPD, the introduction of alkali metals could increase the CO_2 adsorption and decrease the H_2 chemisorption, which could suppress the formation of CH_4, enhance the production of C_（5＋）, and decrease the hydrogenation activity. Among all the promoters, the Na-modified CoCu/TiO_2 catalyst provided the maximum C_（5＋） yield of 5.4%, with a CO_2 conversion of 18.4% and C_（5＋） selectivity of42.1%, because it showed the strongest basicity and a slight decrease in the amount of H_2 desorption;it also exhibited excellent catalytic stability of more than 200 h.展开更多
Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetalli...Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetallic alloy nanoparticles on N-doped carbon support(RuCoMn@NC)via the pyrolysis-adsorption-pyrolysis process using ZIF-67 as a precursor.The RuCoMn@NC catalyst exhibited excellent electrocatalytic performance for the hydrogen evolution reaction(HER)over a wide range of pH and glucose oxidation reaction in alkaline media.It showed exceptional HER activity in alkaline medium,superior to that of the commercial Pt/C catalyst(20 wt%),and good electrochemical stability.Further,a two-electrode alkaline electrolyzer pairing RuCoMn@NC as both cathode and anode was employed,and only a cell voltage of 1.63 V was required to attain a current density of 10 mA cm^(-2)in glucose electrolysis,which is about 270 mV lower than that in the overall water-splitting electrolyzer.This paper provides a promising method for developing efficiently bifunctional electrocatalysts driving redox electrocatalysis,and it would be beneficial to energy-saving electrolytic H_(2) production.展开更多
The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation...The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation of porous carbon-confined Ru-doped Cu nanoparticles(denoted as Ru-Cu@C)by direct pyrolysis of the Ru-exchanged Cu-BTC metal–organic framework.When served as the electrocatalyst for HER,strikingly,the obtained Ru-Cu@C catalyst exhibits an ultralow overpotential(only 20 mV at 10 mA cm^(-2))with a small Tafel slope of 37 m V dec^(-1)in alkaline electrolyte.The excellent performance is comparable or even superior to that of commercial Pt/C catalyst.Density functional theory(DFT)calculations confirm that introducing Ru atoms into Cu nanocrystals can significantly alter the desorption of H_(2) to achieve a close-to-zero hydrogen adsorption energy and thereby boost the HER process.This strategy gives a fresh impetus to explore low-cost and high-performance catalysts for HER in alkaline media.展开更多
基金supported by the National Natural Science Foundation of China(21133011,21373246)Hundred-Talent Programme of the Chinese Academy of SciencesLanzhou Institute of Chemical Physics,Chinese Academy of Sciences~~
基金The Scientific Research Foundation for the Returned Overseas Chinese Scholars of State Education Ministry(2004-527)the State Key Laboratory of Coal Conversion(06-603)
文摘CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the alkali metals on the physicochemical properties of the CoCu/TiO_2 catalysts and the catalytic performance for CO_2 hydrogenation to long-chain hydrocarbons（C_（5＋））were investigated in this work. According to the characterization of the catalysts based on X-ray photoelectron spectroscopy, X-ray diffraction, CO_2 temperature-programmed desorption（TPD）, and H_2-TPD, the introduction of alkali metals could increase the CO_2 adsorption and decrease the H_2 chemisorption, which could suppress the formation of CH_4, enhance the production of C_（5＋）, and decrease the hydrogenation activity. Among all the promoters, the Na-modified CoCu/TiO_2 catalyst provided the maximum C_（5＋） yield of 5.4%, with a CO_2 conversion of 18.4% and C_（5＋） selectivity of42.1%, because it showed the strongest basicity and a slight decrease in the amount of H_2 desorption;it also exhibited excellent catalytic stability of more than 200 h.
基金supported by the National Natural Science Foundation of China(52072035,51631001,21801015,51902023 and 51872030)the Fundamental Research Funds for the Central Universities(2017CX01003)+1 种基金Beijing Institute of Technology Research Fund Program for Young Scholarsthe Joint R&D Plan of Hong Kong,Macao,Taiwan,and Beijing(Z191100001619002).
文摘Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetallic alloy nanoparticles on N-doped carbon support(RuCoMn@NC)via the pyrolysis-adsorption-pyrolysis process using ZIF-67 as a precursor.The RuCoMn@NC catalyst exhibited excellent electrocatalytic performance for the hydrogen evolution reaction(HER)over a wide range of pH and glucose oxidation reaction in alkaline media.It showed exceptional HER activity in alkaline medium,superior to that of the commercial Pt/C catalyst(20 wt%),and good electrochemical stability.Further,a two-electrode alkaline electrolyzer pairing RuCoMn@NC as both cathode and anode was employed,and only a cell voltage of 1.63 V was required to attain a current density of 10 mA cm^(-2)in glucose electrolysis,which is about 270 mV lower than that in the overall water-splitting electrolyzer.This paper provides a promising method for developing efficiently bifunctional electrocatalysts driving redox electrocatalysis,and it would be beneficial to energy-saving electrolytic H_(2) production.
基金the National Key R&D Program of China(2018YFB0605700)the National Natural Science Foundation of China(51778570,51879230,21725101,21871244,21521001,and 21703145)+1 种基金China Postdoctoral Science Foundation(2019TQ0298,2019M660151)Fujian Institute of Innovation(CAS)。
文摘The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction(HER)is of great importance for water splitting.Herein,we develop a facile approach for preparation of porous carbon-confined Ru-doped Cu nanoparticles(denoted as Ru-Cu@C)by direct pyrolysis of the Ru-exchanged Cu-BTC metal–organic framework.When served as the electrocatalyst for HER,strikingly,the obtained Ru-Cu@C catalyst exhibits an ultralow overpotential(only 20 mV at 10 mA cm^(-2))with a small Tafel slope of 37 m V dec^(-1)in alkaline electrolyte.The excellent performance is comparable or even superior to that of commercial Pt/C catalyst.Density functional theory(DFT)calculations confirm that introducing Ru atoms into Cu nanocrystals can significantly alter the desorption of H_(2) to achieve a close-to-zero hydrogen adsorption energy and thereby boost the HER process.This strategy gives a fresh impetus to explore low-cost and high-performance catalysts for HER in alkaline media.
