The nitrogen(N2)-to-ammonia(NH3)fixation driven by renewable energy has an attractive prospect to relieve the global warming and reduce the consumption of fossil fuels.Ideally,photocatalytic,electrochemical,and photoe...The nitrogen(N2)-to-ammonia(NH3)fixation driven by renewable energy has an attractive prospect to relieve the global warming and reduce the consumption of fossil fuels.Ideally,photocatalytic,electrochemical,and photoelectrochemical approaches are developed as the next-generation NH3 synthesis technologies to substitute the Haber–Bosch method.However,the NH3 yield rate of nitrogen reduction reaction(NRR)by green approaches is extremely low,resulting in the current dilemma of NRR and contamination issues.Thus,in this mini review,the past advances on the sustainable NRR are briefly summarized in the three aspects as follows:the selectivity and adjustment of various catalysts,the type of electrolyte/solvent system,and the investigation of reaction conditions.Subsequently,the recent critical activities in the area of sustainable NH3 synthesis are analyzed and discussed deeply,and a perspective for rational and healthy development of this area is provided positively。展开更多
Electrochemical hydrogenation(ECH)of biomass-derived platform molecules is a burgeoning route for the sustainable utilization of hydrogen.However,the noble-metal-catalyzed ECH of phenolic compounds suffers from intens...Electrochemical hydrogenation(ECH)of biomass-derived platform molecules is a burgeoning route for the sustainable utilization of hydrogen.However,the noble-metal-catalyzed ECH of phenolic compounds suffers from intense competition with hydrogen evolution reaction.We prepared Pt Rh bimetallic nanoparticles dispersed on highly ordered mesoporous carbon nanospheres,which improves the utilization efficiency of adsorbed hydrogen(H_(ad))to ECH in H-UPD region(>0 V vs.RHE).Further analysis reveals(i)the strong overlapping between the d-orbitals of Pt and Rh enhances specific adsorption of phenol;(ii)incorporation of Rh devotes an electronic effect on weakening the alloy-H_(ad)interaction to increase the FE of ECH.DFT calculations confirm the selectivity difference and the ECH parallel pathways:cyclohexanol and cyclohexanone are formed via hydrogenation/dehydrogenation of the intermediate ^(*)C_(6)H_(10) OH.These findings deepen our fundamental understanding of the ECH process,and cast new light on exploration of highly efficient electrocatalysts for biomass upgrading.展开更多
基金The authors are grateful to the National Natural Science Foundation of China(51402100,21573066,21825201,22075075,21805080,and U19A2017)the Provincial Natural Science Foundation of Hunan(2016JJ1006,2020JJ5044,and 2016TP1009)Australian Research Council(DP180100568 and DP180100731)for financial support of this research.
文摘The nitrogen(N2)-to-ammonia(NH3)fixation driven by renewable energy has an attractive prospect to relieve the global warming and reduce the consumption of fossil fuels.Ideally,photocatalytic,electrochemical,and photoelectrochemical approaches are developed as the next-generation NH3 synthesis technologies to substitute the Haber–Bosch method.However,the NH3 yield rate of nitrogen reduction reaction(NRR)by green approaches is extremely low,resulting in the current dilemma of NRR and contamination issues.Thus,in this mini review,the past advances on the sustainable NRR are briefly summarized in the three aspects as follows:the selectivity and adjustment of various catalysts,the type of electrolyte/solvent system,and the investigation of reaction conditions.Subsequently,the recent critical activities in the area of sustainable NH3 synthesis are analyzed and discussed deeply,and a perspective for rational and healthy development of this area is provided positively。
基金supported by the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(21902047,21825201,U19A2017,21972164)the Natural Science Foundation of Hunan Province(2020JJ5045)XAS measurements were performed on the XAS beamlines of Australian Synchrotron,Victoria,Australia,part of ANSTO(under project 21805080,22075075,2020JJ5044)。
文摘Electrochemical hydrogenation(ECH)of biomass-derived platform molecules is a burgeoning route for the sustainable utilization of hydrogen.However,the noble-metal-catalyzed ECH of phenolic compounds suffers from intense competition with hydrogen evolution reaction.We prepared Pt Rh bimetallic nanoparticles dispersed on highly ordered mesoporous carbon nanospheres,which improves the utilization efficiency of adsorbed hydrogen(H_(ad))to ECH in H-UPD region(>0 V vs.RHE).Further analysis reveals(i)the strong overlapping between the d-orbitals of Pt and Rh enhances specific adsorption of phenol;(ii)incorporation of Rh devotes an electronic effect on weakening the alloy-H_(ad)interaction to increase the FE of ECH.DFT calculations confirm the selectivity difference and the ECH parallel pathways:cyclohexanol and cyclohexanone are formed via hydrogenation/dehydrogenation of the intermediate ^(*)C_(6)H_(10) OH.These findings deepen our fundamental understanding of the ECH process,and cast new light on exploration of highly efficient electrocatalysts for biomass upgrading.
