In recent years,reducing carbon emissions to achieve carbon neutrality has become an urgent issue for environmental protection and sustainable development.Converting CO_(2) into valuable chemical products through elec...In recent years,reducing carbon emissions to achieve carbon neutrality has become an urgent issue for environmental protection and sustainable development.Converting CO_(2) into valuable chemical products through electrocatalysis powered by renewable electricity exhibits great potential.However,the electroreduction of CO_(2) heavily relies on efficient catalysts to overcome the required energy barrier due to the high stability of CO_(2).p-block metal-based MOFs and MOF-derived catalysts have been proven to be efficient catalysts for electrochemical CO_(2) reduction reaction(CO_(2)RR)due to their unique electronic structure and clear active sites.However,factors such as conductivity and stability limit the practical application of p-block metal-based MOFs and MOF-derived catalysts.In this review,we summarize the latest progress of MOFs and MOF-derived catalysts based on typical p-block metals in the field of CO_(2)RR.Then the modification strategies for MOFs-based catalysts and the related catalytic mechanism are briefly introduced.Furthermore,we offer the challenges and prospects of p-block metal-based MOFs and MOF-derived catalysts in the hope of providing guidance for potential applications.展开更多
In conventional electrides,excess electrons are localized in crystal voids to serve as anions.Most of these electrides are metallic and the metal cations are primarily from the s-block,d-block,or rare-earth elements.H...In conventional electrides,excess electrons are localized in crystal voids to serve as anions.Most of these electrides are metallic and the metal cations are primarily from the s-block,d-block,or rare-earth elements.Here,we report a class of p-block metal-based electrides found in bilayer SnO and PbO,which are semiconducting and feature electride states in both the valence band(VB)and conduction band(CB),as referred to 2D“bipolar”electrides.These bilayers are hybrid electrides where excess electrons are localized in the interlayer region and hybridize with the orbitals of Sn atoms in the VB,exhibiting strong covalent-like interactions with neighboring metal atoms.Compared to previously studied hybrid electrides,the higher electronegativity of Sn and Pb enhances these covalent-like interactions,leading to largely enhanced semiconducting bandgap of up to 2.5 eV.Moreover,the CBM primarily arises from the overlap between metal states and interstitial charges,denoting a potential electride and forming a free-electron-like(FEL)state with small effective mass.This state offers high carrier mobilities for both electron and hole in bilayer SnO,suggesting its potential as a promising p-type semiconductor material.展开更多
The fixation and conversion of CO_(2)frommedium-and high-temperature industrial exhaust gases arescientifically important and challenging tasks owing to theharsh conditions required.Ga_(2)O_(3),a stable p-block compou...The fixation and conversion of CO_(2)frommedium-and high-temperature industrial exhaust gases arescientifically important and challenging tasks owing to theharsh conditions required.Ga_(2)O_(3),a stable p-block compound,is surprisingly active in the thermal conversion of hot CO_(2)waste gas,but its underlying mechanism remains unclear.Inthis study,we investigated CO_(2)adsorption and activationacross 11 different Ga_(2)O_(3)-terminated faces using densityfunctional theory.Charge transfer and chemical bond analysesrevealed the occurrence of two distinct activation mechanismsinvolving synchronous electron gain and loss,driven by astrong synergetic effect between Ga cations and O anions onthe substrate surface.This Ga-O synergy enhances the CO_(2)activation efficiency compared with single active sites,with CO_(2)^(δ+) cation more readily capturing H atom than CO_(2)^(δ–).Tothe best of our knowledge,such a dual activation mechanismhas not been reported before,particularly for p-block catalysts.Our findings provide new insights into the direct catalyticconversion of CO_(2)emissions and offer strategies for the rational design of industrial-grade catalysts for medium-andhigh-temperature CO_(2)tail gas conversion.展开更多
Hydrogen,as a promising alternative to traditional fossil fuels,is crucial for addressing global energy shortage and environmental pollution.Remarkably,the hydrogen can be efficiently conversed and utilized by hydroge...Hydrogen,as a promising alternative to traditional fossil fuels,is crucial for addressing global energy shortage and environmental pollution.Remarkably,the hydrogen can be efficiently conversed and utilized by hydrogen electrocatalysis,consisting of hydrogen evolution reaction(HER)and hydrogen oxidation reaction(HOR).Nevertheless,even for the platinum group metal(PGM)catalysts,there exists the orders-of-magnitude kinetic gap between the HER/HOR in acidic and alkaline electrolytes,which severely restricts the advance of alkaline hydrogen energy technologies.Consequently,developing costeffective and efficient alkaline HER/HOR electrocatalysts is of great significance.Remarkably,the introduction of p-block elements into PGM can induce the p-d orbital hybridization,electron structure regulation,intermediate behavior optimization,and so on,thus greatly enhancing the catalytic performance.Herein,the recent progress in alkaline HER/HOR on PGM-based electrocatalysts modified by p-block elements is summarized.Firstly,the detailed discussions on alkaline HER/HOR mechanism are conducted.Then,the design strategies for p-block non-metal and metal element modified PGM-based catalysts are summarized,respectively.Notably,the inherent correlation between the distinct catalytic component(p-block elements and PGM elements)and corresponding catalytic performance is emphatically explored.Finally,in view of the challenges in alkaline HER/HOR,the research directions in the future are proposed.展开更多
Electrochemical urea synthesis from CO_(2)and NO(EUCN)offers a promising route for sustainable urea production,whereas it still suffers from low C-N coupling efficiency and poor selectivity.Herein,atomically dispersed...Electrochemical urea synthesis from CO_(2)and NO(EUCN)offers a promising route for sustainable urea production,whereas it still suffers from low C-N coupling efficiency and poor selectivity.Herein,atomically dispersed p-block Bi catalyst is explored for highly active and selective EUCN.Theoretical calculations and in situ spectroscopic analyses reveal a unique*CO-mediated C-N coupling mechanism,where isolated Bi sites facilitate CO_(2)reduction for*CO formation and enrichment,while*CO-enriched microenvironment boosts subsequent C-N coupling of*CO and*NO to*CONO,a critical C-N intermediate for urea generation,while simultaneously suppressing the competing side reactions.Notably,by pairing cathodic EUCN with anodic glycerol oxidation in a membrane electrode assembly electrolyzer,we achieve a record-high performance with urea yield rate of 86.5 mmol·h^(-1)·g^(-1)and Faradaic efficiency of 52.1%,as well as the outstanding stability for over 200 h electrolysis.展开更多
Main-group metal(s-and p-block)single atom catalysts(SACs),in which metal cations stabilized by nitrogen atoms(metal-Nx moieties),have emerged as efficient electrocatalysts for oxygen reduction reactions(ORR).However,...Main-group metal(s-and p-block)single atom catalysts(SACs),in which metal cations stabilized by nitrogen atoms(metal-Nx moieties),have emerged as efficient electrocatalysts for oxygen reduction reactions(ORR).However,the closed d shells over main-group metals-based catalysts hinder design of more efficient catalysts than state-of-the-art non-precious Fe single atom catalysts(Fe_(1)/NC).Here we report a p-block Bi-based single-atom electrocatalyst with electronic structure controlled by multi-shell that exhibits high catalytic performance for ORR in alkaline media.Our data suggest the catalyst is composed of single Bi atoms coordinated with four nitrogen atoms on sulfur-phosphorus co-doped carbon nanocages(BiN_(4)/PSNC).The catalyst gives a high half-wave potential of 0.94 V for 4 e^(-)ORR and performs negligible attenuation after 10,000 cycles.In addition,the Zn-air battery assembled by BiN_(4)/PSNC achieves a remarkable peak power density of 452.8 mW·cm^(-2),exceeding other reported main-group metal SACs and most d-band metal SACs.A range of analytical techniques combined with density functional theory calculations reveal that the introduction of S and P sites induces significant electronic modulations to the BiN_(4)active sites,P and S doping promote the electrical activity of BiN_(4)and improve the overall intersite electron transfer within BiN_(4)/PSNC optimizing the adsorption energy of the oxygen intermediates.The 4e-ORR activity was improved.This work offers a unique pathway in designing main-group metals-based SACs for energy conversion devices.展开更多
In this paper, we study some actions of a finite group G on the set of characters of its subgroups, and by using these actions we determine the existence of a p-block with given defect group in some cases.
Electrocatalytic CO_(2) reduction(ECR)to high-value fuels and chemicals offers a promising conversion technology for achieving sustainable carbon cycles.In recent years,although great efforts have been made to develop...Electrocatalytic CO_(2) reduction(ECR)to high-value fuels and chemicals offers a promising conversion technology for achieving sustainable carbon cycles.In recent years,although great efforts have been made to develop highefficiency ECR catalysts,challenges remain in achieving high activity and long durability simultaneously.Taking advantage of the adjustable structure,tunable component,and the M–Ch(M¼Sn,In,Bi,etc.,Ch¼S,Se,Te)covalent bonds stabilized metal centers,the p-block metal chalcogenides(PMC)based electrocatalysts have shown great potential in converting CO_(2) into CO or formates.In addition,the unique p-block electron structure can suppress the competitive hydrogen evolution reaction and enhance the adsorption of ECR intermediates.Seeking to systematically understand the structure–activity relationship of PMC-based ECR catalysts,this review summarizes the recent advances in designing PMC electrocatalysts for CO_(2) reduction based on the fundamental aspects of heterogeneous ECR process,including advanced strategies for optimizing the intrinsic activity and improving the loading density of catalytic sites,constructing highly stable catalysts,and tuning product.展开更多
p-block metal composite oxides Sr_(1.36)Sb_(2)O_(6) and Sr_(2)Sb_(2)O_(7) synthesized by a hydrothermal method as photocatalysts in the degradation of tetracycline hydrochloride under UV light irradiation have been ex...p-block metal composite oxides Sr_(1.36)Sb_(2)O_(6) and Sr_(2)Sb_(2)O_(7) synthesized by a hydrothermal method as photocatalysts in the degradation of tetracycline hydrochloride under UV light irradiation have been extensively studied.The effects of synthesis conditions on the photocatalytic activity were discussed.The Sr_(1.36)Sb_(2)O_(6)-100°C-24 h-5 and Sr_(2)Sb_(2)O_(7)-150℃-24 h^(-2) samples prepared under optimal conditions exhibited remarkably different photocatalytic activities.The essential factors influencing the difference of photocatalytic performance were revealed.The results showed that the different photocatalytic activities observed for Sr_(1.36)Sb_(2)O_(6)and Sr_(2)Sb_(2)O_(7) could be attributed to their different electronic and crystal structures.Our work will provide a new perspective for the screening and design of p-block metal composite oxide photocatalysts to enhance the removal of organic pollutants in the environment.展开更多
Electrochemical reduction of NO_(2)-to NH_(3)(NO_(2)-RR) is recognized as an appealing approach for achieving renewable NH_(3)synthesis and waste NO_(2)-removal.Herein,we report isolated Bi alloyed Ru (Bi1Ru) as an ef...Electrochemical reduction of NO_(2)-to NH_(3)(NO_(2)-RR) is recognized as an appealing approach for achieving renewable NH_(3)synthesis and waste NO_(2)-removal.Herein,we report isolated Bi alloyed Ru (Bi1Ru) as an efficient NO_(2)-RR catalyst.Theoretical calculations and in situ electrochemical measurements reveal the creation of Bi1-Ru dual sites which can remarkably promote NO_(2)-activation and suppress proton adsorption,while accelerating the NO_(2)-RR protonation energetics to render a high NO_(2)--to-NH_(3)conversion efficiency.Remarkably,Bi1Ru assembled in a flow cell delivers an NH_(3)yield rate of 1901.4μmol h^(-1)cm^(-2)and an NH_(3)-Faradaic efficiency of 94.3%at an industrial-level current density of 324.3 mA cm^(-2).This study offers new perspectives for designing and constructing p-block single-atom alloys as robust and high-current-density NO_(2)-RR catalysts toward the ammonia electrosynthesis.展开更多
文章通过两步反应合成共轭超交联聚合物(TPP-CHCP)。TPP-CHCP有较宽的光吸收区间(400~900 nm),可作为光致原子转移自由基聚合(photocatalyzed atom transfer radical polymerization,P-ATRP)的光催化剂。TPP-CHCP可在940 nm近红外光照射...文章通过两步反应合成共轭超交联聚合物(TPP-CHCP)。TPP-CHCP有较宽的光吸收区间(400~900 nm),可作为光致原子转移自由基聚合(photocatalyzed atom transfer radical polymerization,P-ATRP)的光催化剂。TPP-CHCP可在940 nm近红外光照射下,驱动丙烯酸甲酯(MA)和甲基丙烯酸甲酯(MMA)的P-ATRP反应且单体转化率达到99%。所得聚合物的结构明确,分子量可控,分子量分布(D-_(s)<1.18)窄。在太阳光照射条件下,TPP-CHCP依然具有优异的光催化活性,可高效制备嵌段共聚物。展开更多
基金supported by the National Natural Science Foundation of China(Nos.22061019 and 22261021)the Jiangxi Provincial Natural Science Foundation(Nos.20224BAB203002,20232ACB203018,20232BAB203005,and 20224BAB213001)+5 种基金the Jiangxi Province Key Laboratory of Functional Crystalline Materials Chemistry(No.2024SSY05161)the Ganzhou Key Research and Development Program(No.2023PNS26963)the Youth Jinggang Scholars Program in Jiangxi Province(No.QNJG2019053)the Two Thousand Talents Program in Jiangxi Province(No.jxsq2019201068)the Doctor’s Starting Research Foundation of Jiangxi University of Science and Technology(No.205200100597)the Science and Technology Research Project of Jiangxi Provincial Department of Education(No.GJJ2200860).
文摘In recent years,reducing carbon emissions to achieve carbon neutrality has become an urgent issue for environmental protection and sustainable development.Converting CO_(2) into valuable chemical products through electrocatalysis powered by renewable electricity exhibits great potential.However,the electroreduction of CO_(2) heavily relies on efficient catalysts to overcome the required energy barrier due to the high stability of CO_(2).p-block metal-based MOFs and MOF-derived catalysts have been proven to be efficient catalysts for electrochemical CO_(2) reduction reaction(CO_(2)RR)due to their unique electronic structure and clear active sites.However,factors such as conductivity and stability limit the practical application of p-block metal-based MOFs and MOF-derived catalysts.In this review,we summarize the latest progress of MOFs and MOF-derived catalysts based on typical p-block metals in the field of CO_(2)RR.Then the modification strategies for MOFs-based catalysts and the related catalytic mechanism are briefly introduced.Furthermore,we offer the challenges and prospects of p-block metal-based MOFs and MOF-derived catalysts in the hope of providing guidance for potential applications.
基金the financial support from the Ministry of Science and Technology(MOST)of China(Grant No.2023YFA1406500)the National Natural Science Foundation of China(Grant Nos.11974422 and 12104504)+1 种基金the Fundamental Research Funds for the Central Universities,and the Research Funds of Renmin University of China(Grant No.22XNKJ30)(W.J.)supported by the Outstanding Innovative Talents Cultivation Funded Programs 2023 of Renmin University of China.
文摘In conventional electrides,excess electrons are localized in crystal voids to serve as anions.Most of these electrides are metallic and the metal cations are primarily from the s-block,d-block,or rare-earth elements.Here,we report a class of p-block metal-based electrides found in bilayer SnO and PbO,which are semiconducting and feature electride states in both the valence band(VB)and conduction band(CB),as referred to 2D“bipolar”electrides.These bilayers are hybrid electrides where excess electrons are localized in the interlayer region and hybridize with the orbitals of Sn atoms in the VB,exhibiting strong covalent-like interactions with neighboring metal atoms.Compared to previously studied hybrid electrides,the higher electronegativity of Sn and Pb enhances these covalent-like interactions,leading to largely enhanced semiconducting bandgap of up to 2.5 eV.Moreover,the CBM primarily arises from the overlap between metal states and interstitial charges,denoting a potential electride and forming a free-electron-like(FEL)state with small effective mass.This state offers high carrier mobilities for both electron and hole in bilayer SnO,suggesting its potential as a promising p-type semiconductor material.
基金supported by the Key Research and Development Program of Hubei Province(2023BAB032)the Chaozhou Ceramic Industry Talent Revitalization Plan-Talent Support Project for Basic Research Platform of Ceramic Material Application+1 种基金the Self-Innovation Research Funding Project of Hanjiang Laboratory(HJL2023001)the Hubei Provincial Natural Science Foundation of China(2023AFB1000)。
文摘The fixation and conversion of CO_(2)frommedium-and high-temperature industrial exhaust gases arescientifically important and challenging tasks owing to theharsh conditions required.Ga_(2)O_(3),a stable p-block compound,is surprisingly active in the thermal conversion of hot CO_(2)waste gas,but its underlying mechanism remains unclear.Inthis study,we investigated CO_(2)adsorption and activationacross 11 different Ga_(2)O_(3)-terminated faces using densityfunctional theory.Charge transfer and chemical bond analysesrevealed the occurrence of two distinct activation mechanismsinvolving synchronous electron gain and loss,driven by astrong synergetic effect between Ga cations and O anions onthe substrate surface.This Ga-O synergy enhances the CO_(2)activation efficiency compared with single active sites,with CO_(2)^(δ+) cation more readily capturing H atom than CO_(2)^(δ–).Tothe best of our knowledge,such a dual activation mechanismhas not been reported before,particularly for p-block catalysts.Our findings provide new insights into the direct catalyticconversion of CO_(2)emissions and offer strategies for the rational design of industrial-grade catalysts for medium-andhigh-temperature CO_(2)tail gas conversion.
基金supported by the National Natural Science Foundation of China(Nos.52371240 and U1904215)China Postdoctoral Science Foundation(No.2024M762731)+3 种基金Natural Science Foundation of Jiangsu Province(Nos.BK20240894 and BK20200044)Changjiang scholars program of the Ministry of Education(No.Q2018270)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.24KJB150036)Yangzhou Lv-Yang-Jin-Feng Talent Project.
文摘Hydrogen,as a promising alternative to traditional fossil fuels,is crucial for addressing global energy shortage and environmental pollution.Remarkably,the hydrogen can be efficiently conversed and utilized by hydrogen electrocatalysis,consisting of hydrogen evolution reaction(HER)and hydrogen oxidation reaction(HOR).Nevertheless,even for the platinum group metal(PGM)catalysts,there exists the orders-of-magnitude kinetic gap between the HER/HOR in acidic and alkaline electrolytes,which severely restricts the advance of alkaline hydrogen energy technologies.Consequently,developing costeffective and efficient alkaline HER/HOR electrocatalysts is of great significance.Remarkably,the introduction of p-block elements into PGM can induce the p-d orbital hybridization,electron structure regulation,intermediate behavior optimization,and so on,thus greatly enhancing the catalytic performance.Herein,the recent progress in alkaline HER/HOR on PGM-based electrocatalysts modified by p-block elements is summarized.Firstly,the detailed discussions on alkaline HER/HOR mechanism are conducted.Then,the design strategies for p-block non-metal and metal element modified PGM-based catalysts are summarized,respectively.Notably,the inherent correlation between the distinct catalytic component(p-block elements and PGM elements)and corresponding catalytic performance is emphatically explored.Finally,in view of the challenges in alkaline HER/HOR,the research directions in the future are proposed.
基金supported by the National Natural Science Foundation of China(No.52561042)Gansu Province Key Talent Project(2025RCXM008).
文摘Electrochemical urea synthesis from CO_(2)and NO(EUCN)offers a promising route for sustainable urea production,whereas it still suffers from low C-N coupling efficiency and poor selectivity.Herein,atomically dispersed p-block Bi catalyst is explored for highly active and selective EUCN.Theoretical calculations and in situ spectroscopic analyses reveal a unique*CO-mediated C-N coupling mechanism,where isolated Bi sites facilitate CO_(2)reduction for*CO formation and enrichment,while*CO-enriched microenvironment boosts subsequent C-N coupling of*CO and*NO to*CONO,a critical C-N intermediate for urea generation,while simultaneously suppressing the competing side reactions.Notably,by pairing cathodic EUCN with anodic glycerol oxidation in a membrane electrode assembly electrolyzer,we achieve a record-high performance with urea yield rate of 86.5 mmol·h^(-1)·g^(-1)and Faradaic efficiency of 52.1%,as well as the outstanding stability for over 200 h electrolysis.
基金supported by the Key Laboratory of High-Performance fibers&the National Natural Science Foundation of China(No.52103355).
文摘Main-group metal(s-and p-block)single atom catalysts(SACs),in which metal cations stabilized by nitrogen atoms(metal-Nx moieties),have emerged as efficient electrocatalysts for oxygen reduction reactions(ORR).However,the closed d shells over main-group metals-based catalysts hinder design of more efficient catalysts than state-of-the-art non-precious Fe single atom catalysts(Fe_(1)/NC).Here we report a p-block Bi-based single-atom electrocatalyst with electronic structure controlled by multi-shell that exhibits high catalytic performance for ORR in alkaline media.Our data suggest the catalyst is composed of single Bi atoms coordinated with four nitrogen atoms on sulfur-phosphorus co-doped carbon nanocages(BiN_(4)/PSNC).The catalyst gives a high half-wave potential of 0.94 V for 4 e^(-)ORR and performs negligible attenuation after 10,000 cycles.In addition,the Zn-air battery assembled by BiN_(4)/PSNC achieves a remarkable peak power density of 452.8 mW·cm^(-2),exceeding other reported main-group metal SACs and most d-band metal SACs.A range of analytical techniques combined with density functional theory calculations reveal that the introduction of S and P sites induces significant electronic modulations to the BiN_(4)active sites,P and S doping promote the electrical activity of BiN_(4)and improve the overall intersite electron transfer within BiN_(4)/PSNC optimizing the adsorption energy of the oxygen intermediates.The 4e-ORR activity was improved.This work offers a unique pathway in designing main-group metals-based SACs for energy conversion devices.
文摘In this paper, we study some actions of a finite group G on the set of characters of its subgroups, and by using these actions we determine the existence of a p-block with given defect group in some cases.
基金support from the National Key Research and Development Program of China(No.2020YFB1505801)the National Natural Science Foundation of China(Nos.22025208,22075300,and 22102191)the Chinese Academy of Sciences,and the Key Laboratory of Education department of Shaanxi Province(20JS157).
文摘Electrocatalytic CO_(2) reduction(ECR)to high-value fuels and chemicals offers a promising conversion technology for achieving sustainable carbon cycles.In recent years,although great efforts have been made to develop highefficiency ECR catalysts,challenges remain in achieving high activity and long durability simultaneously.Taking advantage of the adjustable structure,tunable component,and the M–Ch(M¼Sn,In,Bi,etc.,Ch¼S,Se,Te)covalent bonds stabilized metal centers,the p-block metal chalcogenides(PMC)based electrocatalysts have shown great potential in converting CO_(2) into CO or formates.In addition,the unique p-block electron structure can suppress the competitive hydrogen evolution reaction and enhance the adsorption of ECR intermediates.Seeking to systematically understand the structure–activity relationship of PMC-based ECR catalysts,this review summarizes the recent advances in designing PMC electrocatalysts for CO_(2) reduction based on the fundamental aspects of heterogeneous ECR process,including advanced strategies for optimizing the intrinsic activity and improving the loading density of catalytic sites,constructing highly stable catalysts,and tuning product.
基金financially supported by the National Natural Science Foundation of China(21875037,51502036)the National Key Research and Development Program of China(2016YFB0302303,2019YFC1908203)the Natural Science Foundation of Distinguished Young Scholars of Fujian Province(2019J06015)。
文摘p-block metal composite oxides Sr_(1.36)Sb_(2)O_(6) and Sr_(2)Sb_(2)O_(7) synthesized by a hydrothermal method as photocatalysts in the degradation of tetracycline hydrochloride under UV light irradiation have been extensively studied.The effects of synthesis conditions on the photocatalytic activity were discussed.The Sr_(1.36)Sb_(2)O_(6)-100°C-24 h-5 and Sr_(2)Sb_(2)O_(7)-150℃-24 h^(-2) samples prepared under optimal conditions exhibited remarkably different photocatalytic activities.The essential factors influencing the difference of photocatalytic performance were revealed.The results showed that the different photocatalytic activities observed for Sr_(1.36)Sb_(2)O_(6)and Sr_(2)Sb_(2)O_(7) could be attributed to their different electronic and crystal structures.Our work will provide a new perspective for the screening and design of p-block metal composite oxide photocatalysts to enhance the removal of organic pollutants in the environment.
基金Longyuan Youth Innovative and Entrepreneurial Talents ProjectProgram for Top Leading Talents of Gansu Province。
文摘Electrochemical reduction of NO_(2)-to NH_(3)(NO_(2)-RR) is recognized as an appealing approach for achieving renewable NH_(3)synthesis and waste NO_(2)-removal.Herein,we report isolated Bi alloyed Ru (Bi1Ru) as an efficient NO_(2)-RR catalyst.Theoretical calculations and in situ electrochemical measurements reveal the creation of Bi1-Ru dual sites which can remarkably promote NO_(2)-activation and suppress proton adsorption,while accelerating the NO_(2)-RR protonation energetics to render a high NO_(2)--to-NH_(3)conversion efficiency.Remarkably,Bi1Ru assembled in a flow cell delivers an NH_(3)yield rate of 1901.4μmol h^(-1)cm^(-2)and an NH_(3)-Faradaic efficiency of 94.3%at an industrial-level current density of 324.3 mA cm^(-2).This study offers new perspectives for designing and constructing p-block single-atom alloys as robust and high-current-density NO_(2)-RR catalysts toward the ammonia electrosynthesis.
文摘文章通过两步反应合成共轭超交联聚合物(TPP-CHCP)。TPP-CHCP有较宽的光吸收区间(400~900 nm),可作为光致原子转移自由基聚合(photocatalyzed atom transfer radical polymerization,P-ATRP)的光催化剂。TPP-CHCP可在940 nm近红外光照射下,驱动丙烯酸甲酯(MA)和甲基丙烯酸甲酯(MMA)的P-ATRP反应且单体转化率达到99%。所得聚合物的结构明确,分子量可控,分子量分布(D-_(s)<1.18)窄。在太阳光照射条件下,TPP-CHCP依然具有优异的光催化活性,可高效制备嵌段共聚物。
