The electrocatalytic nitrogen reduction reaction(NRR)is challenging but crucial for the sustainable development of both industry and agriculture.To enhance NRR performance,it is critically important to construct advan...The electrocatalytic nitrogen reduction reaction(NRR)is challenging but crucial for the sustainable development of both industry and agriculture.To enhance NRR performance,it is critically important to construct advanced electrocatalysts that offer satisfactory performance containing high activity and selectivity.However,the strong affinity of nitrogen-containing species on the Ru surface resulted in suboptimal NRR activity.Herein,we propose a dual-site catalyst,RuNi,to optimize the binding strength,which leads to superior electrocatalytic performance,achieving a high NH_(3)yield rate of 5.07μg h^(-1)cm^(-2)at-0.2 V vs.RHE and a Faradaic efficiency(FE)of 26.2%at-0.1 V vs.RHE in 0.1 mol/L Na_(2)SO_(4).Owing to the synergistic interaction between Ru and Ni,a remarkable performance is realized over the RuNi catalyst.In-situ characterization evidenced that hydrogen radicals(H^(*))on the Ni site of the RuNi catalyst participate in the dissociation of N_(2)adsorbed on the Ru site,and theoretical investigations indicated that RuNi reduces the adsorption strength of intermediates.This offers an effective approach to the synthesis of dual-site catalysts for electrocatalytic ammonia synthesis.展开更多
Recently,the plasma-driven air oxidation coupled with electrocatalytic NO_(x)reduction reaction(pAO-eNO_(x)RR)technology for sustained NH_(3)synthesis displays the promise in tackling the high energy-consumption and c...Recently,the plasma-driven air oxidation coupled with electrocatalytic NO_(x)reduction reaction(pAO-eNO_(x)RR)technology for sustained NH_(3)synthesis displays the promise in tackling the high energy-consumption and carbon-emission associated with the Haber-Bosch process.Here,a technical and economic assessment of pAO-eNO_(x)RR technology is comprehensively undertaken to determine its feasibility as a potential substitute for the Haber-Bosch process.The technical assessment suggests that,in terms of both environmental impact and energy efficiency,N_(2)-NO-NH_(3)and N_(2)-NO_(2)^(-)-NH_(3)are presently the most effective pathways.The deep analysis of the current state-of-the-art technological performance indicates that the pAO-eNO_(x)RR technology is competitive with commercial processes in achieving large-scale NH_(3)synthesis.However,lower energy efficiency of pAO-eNO_(x)RR technology leads to high electricity costs that surpass the current market price of NH_(3).Subsequently,we conducted a comprehensive analysis which reveals that,for the economic viability of NH_(3)synthesis,an energy efficiency in the range of 33.8–38.6%must be attained.The expenses associated with plasma equipment,electrolyzer,catalysts,and NH_(3)distillation also contribute significantly to the economic burden.The further development of pAO-eNO_(x)RR technology should be centered around advancements in plasma catalysts,electrocatalysts,reactors,as well as the exploration for energy-efficient cathode-anode synergistic catalytic systems.展开更多
Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consum...Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consumption and greenhouse gas emissions.Therefore,achieving ammonia synthesis under milder conditions has been a long-standing goal.In this study,we design and synthesize a series of CeO_(2)-modified Fe/carbon-based catalysts with varying amounts of CeO_(2)(Ce_(x)Fe_(y)/C).The catalyst Ce_(2)Fe_(5)/C demonstrates an ammonia yield rate of 3.5 mmol/(g·h),which is 44 times greater than that of Fe/C and 8 times greater than that of commercial Fe-based catalysts at 300℃and 1 MPa.Temperature-programmed desorption experiments show that Ce_(2)Fe_(5)/C has enhanced nitrogen adsorption capabilities.Multiple analyses confirm that the CeO_(2)in Ce_(2)Fe_(5)/C is rich in oxygen vacancies,which can provide electrons to Fe,facilitating nitrogen adsorption,dissociation,and activity in low-temperature ammonia synthesis.展开更多
基金supported by the National Natural Science Foundation of China(Nos.U22A20418,22075196)the Research Project Supported by Shanxi Scholarship Council of China(No.2022–050)。
文摘The electrocatalytic nitrogen reduction reaction(NRR)is challenging but crucial for the sustainable development of both industry and agriculture.To enhance NRR performance,it is critically important to construct advanced electrocatalysts that offer satisfactory performance containing high activity and selectivity.However,the strong affinity of nitrogen-containing species on the Ru surface resulted in suboptimal NRR activity.Herein,we propose a dual-site catalyst,RuNi,to optimize the binding strength,which leads to superior electrocatalytic performance,achieving a high NH_(3)yield rate of 5.07μg h^(-1)cm^(-2)at-0.2 V vs.RHE and a Faradaic efficiency(FE)of 26.2%at-0.1 V vs.RHE in 0.1 mol/L Na_(2)SO_(4).Owing to the synergistic interaction between Ru and Ni,a remarkable performance is realized over the RuNi catalyst.In-situ characterization evidenced that hydrogen radicals(H^(*))on the Ni site of the RuNi catalyst participate in the dissociation of N_(2)adsorbed on the Ru site,and theoretical investigations indicated that RuNi reduces the adsorption strength of intermediates.This offers an effective approach to the synthesis of dual-site catalysts for electrocatalytic ammonia synthesis.
基金supported by the National Key R&D Project of China(Grant No.2020YFA0710000)National Natural Science Foundation of China(Grant Nos.22225606,22176029)Science and Technology Project of Sichuan Province(2025NSFTD0003,2024YFHZ0222).
文摘Recently,the plasma-driven air oxidation coupled with electrocatalytic NO_(x)reduction reaction(pAO-eNO_(x)RR)technology for sustained NH_(3)synthesis displays the promise in tackling the high energy-consumption and carbon-emission associated with the Haber-Bosch process.Here,a technical and economic assessment of pAO-eNO_(x)RR technology is comprehensively undertaken to determine its feasibility as a potential substitute for the Haber-Bosch process.The technical assessment suggests that,in terms of both environmental impact and energy efficiency,N_(2)-NO-NH_(3)and N_(2)-NO_(2)^(-)-NH_(3)are presently the most effective pathways.The deep analysis of the current state-of-the-art technological performance indicates that the pAO-eNO_(x)RR technology is competitive with commercial processes in achieving large-scale NH_(3)synthesis.However,lower energy efficiency of pAO-eNO_(x)RR technology leads to high electricity costs that surpass the current market price of NH_(3).Subsequently,we conducted a comprehensive analysis which reveals that,for the economic viability of NH_(3)synthesis,an energy efficiency in the range of 33.8–38.6%must be attained.The expenses associated with plasma equipment,electrolyzer,catalysts,and NH_(3)distillation also contribute significantly to the economic burden.The further development of pAO-eNO_(x)RR technology should be centered around advancements in plasma catalysts,electrocatalysts,reactors,as well as the exploration for energy-efficient cathode-anode synergistic catalytic systems.
基金the Haihe Laboratory of Sus-tainable Chemical Transformations for financial support(No.24HHWCSS00009).
文摘Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consumption and greenhouse gas emissions.Therefore,achieving ammonia synthesis under milder conditions has been a long-standing goal.In this study,we design and synthesize a series of CeO_(2)-modified Fe/carbon-based catalysts with varying amounts of CeO_(2)(Ce_(x)Fe_(y)/C).The catalyst Ce_(2)Fe_(5)/C demonstrates an ammonia yield rate of 3.5 mmol/(g·h),which is 44 times greater than that of Fe/C and 8 times greater than that of commercial Fe-based catalysts at 300℃and 1 MPa.Temperature-programmed desorption experiments show that Ce_(2)Fe_(5)/C has enhanced nitrogen adsorption capabilities.Multiple analyses confirm that the CeO_(2)in Ce_(2)Fe_(5)/C is rich in oxygen vacancies,which can provide electrons to Fe,facilitating nitrogen adsorption,dissociation,and activity in low-temperature ammonia synthesis.
