The electronic modification effect of various metal oxides over Pt-Al;O;catalyst andthe relationships between the polarizing force of cations（PFC）and the electrophiliccharacter（EC）and catalytic performances（CP）o...The electronic modification effect of various metal oxides over Pt-Al;O;catalyst andthe relationships between the polarizing force of cations（PFC）and the electrophiliccharacter（EC）and catalytic performances（CP）of promoted Pt catalyst have been studiecby competitive hydrogenation reaction method（CHRM）and test reaction,i.e.hydrogena-tion of benzene and hydrogenolysis of cyclopentane.展开更多
The steep reduction in costs and systematic optimization of renewable electricity has ignited an intensifying interest in harnessing electroreduction of carbon dioxide(CO_(2)RR)for the generation of chemicals and fuel...The steep reduction in costs and systematic optimization of renewable electricity has ignited an intensifying interest in harnessing electroreduction of carbon dioxide(CO_(2)RR)for the generation of chemicals and fuels.The focus of research over the past few decades has been on the optimization of the electrode and the electrolyte environment.Notably,cation species in the latter have recently been found to dramatically alter the selectivity of CO_(2)RR and even their catalytic activity by multiple orders of magnitude.As a result,the selection of cations is a critical factor in designing catalytic interfaces with high selectivity and efficiency for targeted products.Informed decision-making regarding cation selection relies on a comprehensive understanding of prevailing electrolyte effect models that have been used to elucidate observed experimental trends.In this perspective,we review the hypotheses that explain how electrolyte cations influence CO_(2)RR by mechanisms such as through tuning of the interfacial electric field,buffering of the local pH,stabilization of the key intermediates and regulation of the interfacial water.Our endeavor is to elucidate the molecular mechanisms underpinning cation effects,thus fostering the evolution of more holistic and universally applicable predictive models.In this regard,we highlight the current challenges in this area of research,while also identifying potential avenues for future investigations.展开更多
Cation vacancy engineering is considered to be one of the effective methods to solve the issues of shuttling and sluggish redox kinetics of Li PSs owing to the intrinsic tunability of electronic structure.However,cati...Cation vacancy engineering is considered to be one of the effective methods to solve the issues of shuttling and sluggish redox kinetics of Li PSs owing to the intrinsic tunability of electronic structure.However,cation vacancies are few studied in the Li-S realm due to their complex and rigid preparation methods.In this work,one-step pyrolysis is reported to in situ introduce Fe-vacancies into iron sulfide(Fe_(0.96)S)as a sulfur host.For this host structure,Fe_(0.96)S is first employed as an adsorbent and catalyst in Li-S system.During the carbonization process,a tight contact structure of Fe_(0.96)S crystal and carbon network(Fe_(0.96)S@C)is in situ constructed,and the carbon layer as a conductor provides smooth electrons transfer pathways for redox reactions.Meanwhile,due to the introduction of Fe-vacancies in Fe S crystal,the adsorption capability and catalytic effect for Li PSs have been substantially enhanced.Moreover,the presence of Fe_(0.96)S crystal favors the mobility of electron and diffusion of Li+,which is revealed by the experiments and theoretical calculations.Through synergy respective advantages effect of Fe_(0.96)S and carbon,the Fe_(0.96)S@C-S cathode delivers high-rate capability at 5.0 C and stable long-life performance.Even under a high sulfur loading of 3.5 mg/cm^(2),the durable cyclic stability is still exhibited with the capacity retention of 93%over 400 cycles at 1.0 C,and the coulombic efficiency is≥98%.Noting that this strategy greatly simplifies the synthetic process of currently known cation-vacancy materials and furnishes a universal mentality for designing both divinable and astonishing new cation-vacancy materials.展开更多
文摘The electronic modification effect of various metal oxides over Pt-Al;O;catalyst andthe relationships between the polarizing force of cations（PFC）and the electrophiliccharacter（EC）and catalytic performances（CP）of promoted Pt catalyst have been studiecby competitive hydrogenation reaction method（CHRM）and test reaction,i.e.hydrogena-tion of benzene and hydrogenolysis of cyclopentane.
基金Financial support from National Natural Science Foundation of China(Nos.22109099 and 22072101)“Chen Guang”Project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(No.21CGA66)+1 种基金Natural Science Foundation of Jiangsu Province(No.BK20211306)Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions。
文摘The steep reduction in costs and systematic optimization of renewable electricity has ignited an intensifying interest in harnessing electroreduction of carbon dioxide(CO_(2)RR)for the generation of chemicals and fuels.The focus of research over the past few decades has been on the optimization of the electrode and the electrolyte environment.Notably,cation species in the latter have recently been found to dramatically alter the selectivity of CO_(2)RR and even their catalytic activity by multiple orders of magnitude.As a result,the selection of cations is a critical factor in designing catalytic interfaces with high selectivity and efficiency for targeted products.Informed decision-making regarding cation selection relies on a comprehensive understanding of prevailing electrolyte effect models that have been used to elucidate observed experimental trends.In this perspective,we review the hypotheses that explain how electrolyte cations influence CO_(2)RR by mechanisms such as through tuning of the interfacial electric field,buffering of the local pH,stabilization of the key intermediates and regulation of the interfacial water.Our endeavor is to elucidate the molecular mechanisms underpinning cation effects,thus fostering the evolution of more holistic and universally applicable predictive models.In this regard,we highlight the current challenges in this area of research,while also identifying potential avenues for future investigations.
基金supported by the National Natural Science Foundation of China(52173274 and 52172202)the Natural Science Foundation of Guangdong Province 2022A1515010049+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA16021101)the China Postdoctoral Science Foundation(2021M691228)。
文摘Cation vacancy engineering is considered to be one of the effective methods to solve the issues of shuttling and sluggish redox kinetics of Li PSs owing to the intrinsic tunability of electronic structure.However,cation vacancies are few studied in the Li-S realm due to their complex and rigid preparation methods.In this work,one-step pyrolysis is reported to in situ introduce Fe-vacancies into iron sulfide(Fe_(0.96)S)as a sulfur host.For this host structure,Fe_(0.96)S is first employed as an adsorbent and catalyst in Li-S system.During the carbonization process,a tight contact structure of Fe_(0.96)S crystal and carbon network(Fe_(0.96)S@C)is in situ constructed,and the carbon layer as a conductor provides smooth electrons transfer pathways for redox reactions.Meanwhile,due to the introduction of Fe-vacancies in Fe S crystal,the adsorption capability and catalytic effect for Li PSs have been substantially enhanced.Moreover,the presence of Fe_(0.96)S crystal favors the mobility of electron and diffusion of Li+,which is revealed by the experiments and theoretical calculations.Through synergy respective advantages effect of Fe_(0.96)S and carbon,the Fe_(0.96)S@C-S cathode delivers high-rate capability at 5.0 C and stable long-life performance.Even under a high sulfur loading of 3.5 mg/cm^(2),the durable cyclic stability is still exhibited with the capacity retention of 93%over 400 cycles at 1.0 C,and the coulombic efficiency is≥98%.Noting that this strategy greatly simplifies the synthetic process of currently known cation-vacancy materials and furnishes a universal mentality for designing both divinable and astonishing new cation-vacancy materials.
