High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic mat...High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic materials.This increased multiplicity stimulates a cocktail effect and a scaling-relation breaking effect,and results in improved activity.However,the multiplicity of active sites in HEAs also poses new problems for mechanistic studies.One apparent problem is the inapplicability to HEA catalysts of the currently most popular mechanistic study method,which uses the electrocatalytic theoretical framework(ETF)based on the computational hydrogen electrode(CHE).The ETF uses a single adsorption energy to represent the catalyst,i.e.,a catalyst is represented by a'point'in the volcanic relationship.It naturally does not involve the multiplicity of active sites of a catalyst,and hence loses brevity in expressing the cocktail effect and scaling-relation breaking effect in HEA catalysis.This paper attempts to solve this inapplicability.Based on the fact that the adsorption energy distribution of HEAs is close to a normal distribution,the mean and variance of the adsorption energy distribution are introduced as descriptors of the ETF,replacing the original single adsorption energy.A quantitative relationship between the variance and the cocktail and scaling-relation braking effects is established.We believe the method described in this work will make the ETF more effective in mechanistic studies of HEA electrocatalysis.展开更多
The design of optimal heterogeneous catalysts for N_(2)-to-NH_(3) conversion is often dictated by the scaling relations,which result in a volcano curve that poses a limit on the catalytic performance.Herein,we reveal ...The design of optimal heterogeneous catalysts for N_(2)-to-NH_(3) conversion is often dictated by the scaling relations,which result in a volcano curve that poses a limit on the catalytic performance.Herein,we reveal a bowl active site that can break the scaling relations,through investigating the catalytic mechanisms of N_(2)-to-NH_(3) conversion on the lanthanide intermetallic electride catalyst LaRuSi by first-principles modeling.This bowl active site,composed of four surface La cations and one subsurface Si atom rich in electrons,plays the key role in enabling efficient catalysis.With adaptive electrostatic and orbital interactions,the bowl active site promotes the adsorption and activation of N_(2) that delivers facile cleavage of N-N bond,while destabilizes the adsorptions of ^(*)NH_(x)(x=1,2,3)species,which facilitates the release of the final NH_(3) product.By comparison with other electride catalysts isostructural to LaRuSi,we confirm the breaking of scaling relations between the adsorptions of ^(*)NH_(x) species and that of^(*)N on the bowl active site.Thus,this bowl active site presents a design concept that breaks the scaling relations for highly efficient heterogeneous catalysis of N_(2)-to-NH_(3) conversion.展开更多
The Qinghai-Tibet Plateau encompasses a large quantity of wetlands, some of which have been degraded to varying severity levels. In the literature, a number of degradation indicators have been proposed to evaluate eco...The Qinghai-Tibet Plateau encompasses a large quantity of wetlands, some of which have been degraded to varying severity levels. In the literature, a number of degradation indicators have been proposed to evaluate ecological health of wetlands, but their effectiveness in the plateau environment remains unknown. In this study, we assessed the effectiveness of three degradation indicators, soil moisture content at lo em deep, vegetative cover, and density of pika burrows. The degradation severity of wetlands in Maduo County on the Qinghai-Tibet Plateau is enumerated at four levels, intact, slight, moderate and severe. Analysis of xo6 samples collected in the field demonstrates that the density of pika burrows is the least reliable indicator. By comparison, vegetative cover and underlying soil moisture content are more reliable, even though neither is a perfect indicator as the difference among adjacent levels of severity as revealed by t-test is not always statistically significant. The imperfection of vegetative cover as an indicator is due to its variation among different types of wetlands. The limitation of moisture content is attributed to its non-linear relationship with wetland degradation. Above the threshold of about 50% in moisture content wetlands are unlikely to be degraded. It is recommended that moisture be measured at the point near the surface and vegetative cover be further differentiated by species in order to improve their effectiveness.展开更多
文摘High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic materials.This increased multiplicity stimulates a cocktail effect and a scaling-relation breaking effect,and results in improved activity.However,the multiplicity of active sites in HEAs also poses new problems for mechanistic studies.One apparent problem is the inapplicability to HEA catalysts of the currently most popular mechanistic study method,which uses the electrocatalytic theoretical framework(ETF)based on the computational hydrogen electrode(CHE).The ETF uses a single adsorption energy to represent the catalyst,i.e.,a catalyst is represented by a'point'in the volcanic relationship.It naturally does not involve the multiplicity of active sites of a catalyst,and hence loses brevity in expressing the cocktail effect and scaling-relation breaking effect in HEA catalysis.This paper attempts to solve this inapplicability.Based on the fact that the adsorption energy distribution of HEAs is close to a normal distribution,the mean and variance of the adsorption energy distribution are introduced as descriptors of the ETF,replacing the original single adsorption energy.A quantitative relationship between the variance and the cocktail and scaling-relation braking effects is established.We believe the method described in this work will make the ETF more effective in mechanistic studies of HEA electrocatalysis.
文摘The design of optimal heterogeneous catalysts for N_(2)-to-NH_(3) conversion is often dictated by the scaling relations,which result in a volcano curve that poses a limit on the catalytic performance.Herein,we reveal a bowl active site that can break the scaling relations,through investigating the catalytic mechanisms of N_(2)-to-NH_(3) conversion on the lanthanide intermetallic electride catalyst LaRuSi by first-principles modeling.This bowl active site,composed of four surface La cations and one subsurface Si atom rich in electrons,plays the key role in enabling efficient catalysis.With adaptive electrostatic and orbital interactions,the bowl active site promotes the adsorption and activation of N_(2) that delivers facile cleavage of N-N bond,while destabilizes the adsorptions of ^(*)NH_(x)(x=1,2,3)species,which facilitates the release of the final NH_(3) product.By comparison with other electride catalysts isostructural to LaRuSi,we confirm the breaking of scaling relations between the adsorptions of ^(*)NH_(x) species and that of^(*)N on the bowl active site.Thus,this bowl active site presents a design concept that breaks the scaling relations for highly efficient heterogeneous catalysis of N_(2)-to-NH_(3) conversion.
基金supported by the International Science&Technology Cooperation Program of China(Grant No.2011DFG93160,2011DFA20820)the National Natural Sciences Foundation of China(Grant No.41161084)+1 种基金Special Fund for Agroscientific Research in the Public Interest(Grant No.201203041)the Scientific Research Collaboration and Training of Top Scientists project(Document No.2010-1595),Department of International Exchange&Cooperation of the Chinese Ministry of Education
文摘The Qinghai-Tibet Plateau encompasses a large quantity of wetlands, some of which have been degraded to varying severity levels. In the literature, a number of degradation indicators have been proposed to evaluate ecological health of wetlands, but their effectiveness in the plateau environment remains unknown. In this study, we assessed the effectiveness of three degradation indicators, soil moisture content at lo em deep, vegetative cover, and density of pika burrows. The degradation severity of wetlands in Maduo County on the Qinghai-Tibet Plateau is enumerated at four levels, intact, slight, moderate and severe. Analysis of xo6 samples collected in the field demonstrates that the density of pika burrows is the least reliable indicator. By comparison, vegetative cover and underlying soil moisture content are more reliable, even though neither is a perfect indicator as the difference among adjacent levels of severity as revealed by t-test is not always statistically significant. The imperfection of vegetative cover as an indicator is due to its variation among different types of wetlands. The limitation of moisture content is attributed to its non-linear relationship with wetland degradation. Above the threshold of about 50% in moisture content wetlands are unlikely to be degraded. It is recommended that moisture be measured at the point near the surface and vegetative cover be further differentiated by species in order to improve their effectiveness.
