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 persistent increase of CO_(2) levels in the atmosphere,already exceeding 400 ppm,urges the exploration of CO_(2) emission reduction and recycling technologies.Ideally,photocatalytic conversion of CO_(2) into valua...The persistent increase of CO_(2) levels in the atmosphere,already exceeding 400 ppm,urges the exploration of CO_(2) emission reduction and recycling technologies.Ideally,photocatalytic conversion of CO_(2) into valuable hydrocarbons realizes solar-to-chemical energy conversion,which is a desirable“kill two birds with one stone”strategy;namely,CO_(2) photoreduction can simultaneously tackle energy shortage and keep global carbon balance.Graphitic carbon nitride(g-C_(3)N_(4))working on CO_(2) reduction reaction deserves a highlight not only for the metal-free feature that endows it with low cost,tunable electronic structure,and easy fabrication properties but also because of its strong reduction ability.The present review concisely summarizes the latest advances of g-C_(3)N_(4)-based photocatalysts toward CO_(2) reduction.It starts with the discussion of thermodynamics and dynamics aspects of the CO_(2) reduction process.Then the modification strategies to promote g-C_(3)N_(4)-based photocatalysts in CO_(2) photoreduction have been discussed in detail,including surface functionalization,molecule structure engineering,crystallization,morphology engineering,loading cocatalyst,and constructing heterojunction.Meanwhile,the intrinsic factors affecting CO_(2) reduction activity and selectivity are analyzed and summarized.In the end,the challenges and prospects for the future development of highly g-C_(3)N_(4)-based photocatalysts in CO_(2) reduction are also presented.展开更多
Green energy generation is an indispensable task to concurrently resolve fossil fuel depletion and environmental issues to align with the global goals of achieving carbon neutrality.Photocatalysis,a process that trans...Green energy generation is an indispensable task to concurrently resolve fossil fuel depletion and environmental issues to align with the global goals of achieving carbon neutrality.Photocatalysis,a process that transforms solar energy into clean fuels through a photocatalyst,represents a felicitous direction toward sustainability.Eco-rich metal-free graphitic carbon nitride(g-C_(3)N_(4))is profiled as an attractive photocatalyst due to its fascinating properties,including excellent chemical and thermal stability,moderate band gap,visible light-active nature,and ease of fabrication.Nonetheless,the shortcomings of g-C_(3)N_(4)include fast charge recombination and limited surface-active sites,which adversely affect photocatalytic reactions.Among the modification strategies,point-to-face contact engineering of 2D g-C_(3)N_(4)with 0D nanomaterials represents an innovative and promising synergy owing to several intriguing attributes such as the high specific surface area,short effective charge-transfer pathways,and quantum confinement effects.This review introduces recent advances achieved in experimental and computational studies on the interfacial design of 0D nanostructures on 2D g-C_(3)N_(4)in the construction of point-to-face heterojunction interfaces.Notably,0D materials such as metals,metal oxides,metal sulfides,metal selenides,metal phosphides,and nonmetals on g-C_(3)N_(4)with different charge-transfer mechanisms are systematically discussed along with controllable synthesis strategies.The applications of 0D/2D g-C_(3)N_(4)-based photocatalysts are focused on solar-to-energy conversion via the hydrogen evolution reaction,the CO_(2)reduction reaction,and the N2 reduction reaction to evaluate the photocatalyst activity and elucidate reaction pathways.Finally,future perspectives for developing high-efficiency 0D/2D photocatalysts are proposed to explore potential emerging carbon nitride allotropes,large-scale production,machine learning integration,and multidisciplinary advances for technological breakthroughs.展开更多
Artificial photocatalytic energy conversion is considered as the most potential strategy for solving the increasingly serious energy crisis and environmental pollution problems by directly capturing solar energy.There...Artificial photocatalytic energy conversion is considered as the most potential strategy for solving the increasingly serious energy crisis and environmental pollution problems by directly capturing solar energy.Therefore,high efficiency photocatalyst has drawn significant research attention in recent years.Due to the excellent electronic,optical,structural,and physicochemical performances,silver-based g-C_(3)N_(4)have become promising photocatalysts.This review emphasizes the recent progresses and challenges on g-C_(3)N_(4)decorated with silver for photocatalytic energy conversion.The extensive use of g-C_(3)N_(4)decorated with silver in diverse photocatalytic reactions,including hydrogen evolution,pollutant degradation and carbon dioxide reduction,is also fully introduced.In addition,we propose the perspectives of g-C_(3)N_(4)decorated with silver on photocatalytic applications.We hope that this review will shed some light on the photocatalytic energy conversion of g-C_(3)N_(4)decorated with silver.展开更多
Retaining the ultrathin structure of two-dimensional materials is very important for stabilizing their catalytic performances.However,aggregation and restacking are unavoidable,to some extent,due to the van der Waals ...Retaining the ultrathin structure of two-dimensional materials is very important for stabilizing their catalytic performances.However,aggregation and restacking are unavoidable,to some extent,due to the van der Waals interlayer interaction of two-dimensional materials.Here,we address this challenge by preparing an origami accordion structure of ultrathin twodimensional graphitized carbon nitride(oa-C_(3)N_(4))with rich vacancies.This novel structured oa-C_(3)N_(4) shows exceptional photocatalytic activity for the CO_(2) reduction reaction,which is 8.1 times that of the pristine C_(3)N_(4).The unique structure not only prevents restacking but also increases light harvesting and the density of vacancy defects,which leads to modification of the electronic structure,regulation of the CO_(2) adsorption energy,and a decrease in the energy barrier of the carbon dioxide to carboxylic acid intermediate reaction.This study provides a new avenue for the development of stable highperformance two-dimensional catalytic materials.展开更多
Heterojunction design in a two-dimensional(2D)fashion has been deemed beneficial for improving the photocatalytic activity of g-C_(3)N_(4)because of the promoted interfacial charge transfer,yet still facing challenges...Heterojunction design in a two-dimensional(2D)fashion has been deemed beneficial for improving the photocatalytic activity of g-C_(3)N_(4)because of the promoted interfacial charge transfer,yet still facing challenges.Herein,we construct a novel 2D/2D Cu_(3)P nanosheet/P-doped g-C_(3)N_(4)(PCN)nanosheet heterojunction photocatalyst(PCN/Cu_(3)P)through a simple in-situ phosphorization treatment of 2D/2D CuS/g-C_(3)N_(4)composite for photocatalytic H2 evolution.We demonstrate that the 2D lamellar structure of both CuS and g-C_(3)N_(4)could be well reserved in the phosphorization process,while CuS and g-C_(3)N_(4)in-situ transformed into Cu_(3)P and PCN,respectively,leading to the formation of PCN/Cu_(3)P tight 2D/2D heterojunction.Owing to the large contact area provided by intimate face-to-face 2D/2D structure,the PCN/Cu_(3)P photocatalyst exhibits significantly enhanced charge separation efficiency,thus achieving a boosted visible-light-driven photocatalytic behavior.The highest rate for H2 evolution reaches 5.12 umol·h^(-1),nearly 24 times and 368 times higher than that of pristine PCN and g-C_(3)N_(4),respectively.This work represents an excellent example in elaborately con-structing g-C_(3)N_(4)-based 2D/2D heterostructure and could be extended to other photocatalyst/co-catalyst system.展开更多
A two-dimensional(2D)/2D hybrid heterojunction with face-to-face interfacial assembly is a desirable dimensionality design with significant potential for various photocatalytic applications due to the large interfacia...A two-dimensional(2D)/2D hybrid heterojunction with face-to-face interfacial assembly is a desirable dimensionality design with significant potential for various photocatalytic applications due to the large interfacial contact area,which facilitates charge migration and separation.Herein,we developed an ef-ficient 2D/2D hybrid heterojunction consisting of BiOIO 3 nanoplates(BIO)and g-C_(3)N_(4) nanosheets(CN)using a simple but effective in situ growth method for photocatalytic aqueous antibiotic degradation and H_(2) generation.The face-to-face interfacial assembly of the BIO and CN components in the BIO/CN hy-brid heterojunction was verified using electron microscopy.Remarkably,the BIO/CN hybrid heterojunc-tion outperformed both the BIO and CN counterparts in terms of norfloxacin degradation and H_(2) gen-eration under simulated solar light irradiation.Moreover,the photocatalytic performance of the hybrid catalyst remained nearly unchanged throughout five consecutive test runs.The exceptional performance and stability of the hybrid catalyst are attributable to its extended optical absorption range,large interfa-cial contact area provided by the face-to-face assembly in the 2D/2D hybrid configuration,and enhanced photoexcited charge separation efficiency and redox power of the separated charges,which are supported by an efficient S-scheme charge transfer mechanism.This study illuminates the rational construction of novel 2D/2D S-scheme hybrid heterojunction photocatalysts with practical applications in environmental remediation and sustainable energy generation.展开更多
The synthesis of high value-added chemical products using CO_(2)and CH_(4)is a promising CO_(2)conversion technology that can reduce greenhouse gas emissions while also alleviating the energy crisis.However,problems s...The synthesis of high value-added chemical products using CO_(2)and CH_(4)is a promising CO_(2)conversion technology that can reduce greenhouse gas emissions while also alleviating the energy crisis.However,problems such as high energy consumption and strict reaction conditions in reforming process hinder the further development of the technology.In this work,carbon-nitrogen based composites were prepared for the first time according to the design principle from morphology to heterojunction,which is innovatively applied in the process of photocatalytic CH4reforming.Firstly,C_(3)N_(4)materials with different dimensions(D) are prepared and applied to a CO_(2)-CH_(4)photocatalytic system.Additionally,the 2D/2D TiO_(2)/g-C_(3)N_(4)heterostructure is constructed with the ultrasonic impregnation method to further improve charge generation,transfer,and separation efficiency.It is worth noting that the yield of CO reaches173.80 μmol g^(-1),and the catalytic performance is improved by 1546% compared to bulk C_(3)N_(4).Moreover,the physical and chemical properties of 2D/2D TiO_(2)/g-C_(3)N_(4)materials are studied using a variety of cha racterization methods.Furthermore,the work fu nction and adsorption energy of different C3N4/TiO_(2)models for CO_(2)adsorption are calculated by density functional theory(DFT).Then,a possible catalytic mechanism for photocatalytic CO_(2)and CH_(4) conversion is proposed based on DFT calculations and experimental results.This work provides a new technical route for the rapid conversion of CO_(2)and CH_(4) at room temperature,as well as a new research concept for achieving carbon neutrality.展开更多
The catalytic performance of light-derived CO_(2)reduction with H_(2)O is strongly dependent on the sepa-ration efficiency of photogenerated carriers.Herein,the direct Z-scheme catalysts(g-C_(3)N_(4)/3DOM-WO_(3))of gr...The catalytic performance of light-derived CO_(2)reduction with H_(2)O is strongly dependent on the sepa-ration efficiency of photogenerated carriers.Herein,the direct Z-scheme catalysts(g-C_(3)N_(4)/3DOM-WO_(3))of graphitic carbon nitride(g-C_(3)N_(4))nanosheets decorated three-dimensional ordered macroporous WO_(3)(3DOM-WO_(3))were successfully fabricated by using the in-situ colloidal crystal template method.The slow light effect of 3DOM-WO_(3)photonic crystals expands the absorption of visible light and improves the uti-lization of light energy.The Z-scheme structure of g-C_(3)N_(4)/3DOM-WO_(3)catalysts is able to upgrade the separation efficiency of photogenerated electron-hole pairs.The g-C_(3)N_(4)/3DOM-WO_(3)photocatalyst,whose formation rate of CO product is 48.7μmol g^(−1)h^(−1),exhibits the excellent catalytic activity for CO_(2)reduc-tion.The transfer pathway of stimulated electrons over the g-C_(3)N_(4)/3DOM-WO_(3)photocatalyst is proposed and discussed.The present approach provides unique insights into the rational development of high-performance photochemical systems for efficient CO_(2)reduction into valuable carbon-containing chemicals and energy fuels.展开更多
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Natural Science Foundation of Xinjiang Province,Grant/Award Numbers:2019D01C064,2020D01A49,2020D01B25,2021D01B40National Natural Science Foundation of China,Grant/Award Numbers:21905209,52072273Tianshan innovation team project of Xinjiang Uygur Autonomous Region,Grant/Award Number:2021D14013。
文摘The persistent increase of CO_(2) levels in the atmosphere,already exceeding 400 ppm,urges the exploration of CO_(2) emission reduction and recycling technologies.Ideally,photocatalytic conversion of CO_(2) into valuable hydrocarbons realizes solar-to-chemical energy conversion,which is a desirable“kill two birds with one stone”strategy;namely,CO_(2) photoreduction can simultaneously tackle energy shortage and keep global carbon balance.Graphitic carbon nitride(g-C_(3)N_(4))working on CO_(2) reduction reaction deserves a highlight not only for the metal-free feature that endows it with low cost,tunable electronic structure,and easy fabrication properties but also because of its strong reduction ability.The present review concisely summarizes the latest advances of g-C_(3)N_(4)-based photocatalysts toward CO_(2) reduction.It starts with the discussion of thermodynamics and dynamics aspects of the CO_(2) reduction process.Then the modification strategies to promote g-C_(3)N_(4)-based photocatalysts in CO_(2) photoreduction have been discussed in detail,including surface functionalization,molecule structure engineering,crystallization,morphology engineering,loading cocatalyst,and constructing heterojunction.Meanwhile,the intrinsic factors affecting CO_(2) reduction activity and selectivity are analyzed and summarized.In the end,the challenges and prospects for the future development of highly g-C_(3)N_(4)-based photocatalysts in CO_(2) reduction are also presented.
基金Ministry of Higher Education,Malaysia,Grant/Award Number:FRGS/1/2020/TK0/XMU/02/1Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2021A1515111019+1 种基金Hengyuan International Sdn.Bhd.,Grant/Award Number:EENG/0003Xiamen University Malaysia,Grant/Award Numbers:IENG/0038,ICOE/0001,XMUMRF/2019-C3/IENG/0013,XMUMRF/2021-C8/IENG/0041。
文摘Green energy generation is an indispensable task to concurrently resolve fossil fuel depletion and environmental issues to align with the global goals of achieving carbon neutrality.Photocatalysis,a process that transforms solar energy into clean fuels through a photocatalyst,represents a felicitous direction toward sustainability.Eco-rich metal-free graphitic carbon nitride(g-C_(3)N_(4))is profiled as an attractive photocatalyst due to its fascinating properties,including excellent chemical and thermal stability,moderate band gap,visible light-active nature,and ease of fabrication.Nonetheless,the shortcomings of g-C_(3)N_(4)include fast charge recombination and limited surface-active sites,which adversely affect photocatalytic reactions.Among the modification strategies,point-to-face contact engineering of 2D g-C_(3)N_(4)with 0D nanomaterials represents an innovative and promising synergy owing to several intriguing attributes such as the high specific surface area,short effective charge-transfer pathways,and quantum confinement effects.This review introduces recent advances achieved in experimental and computational studies on the interfacial design of 0D nanostructures on 2D g-C_(3)N_(4)in the construction of point-to-face heterojunction interfaces.Notably,0D materials such as metals,metal oxides,metal sulfides,metal selenides,metal phosphides,and nonmetals on g-C_(3)N_(4)with different charge-transfer mechanisms are systematically discussed along with controllable synthesis strategies.The applications of 0D/2D g-C_(3)N_(4)-based photocatalysts are focused on solar-to-energy conversion via the hydrogen evolution reaction,the CO_(2)reduction reaction,and the N2 reduction reaction to evaluate the photocatalyst activity and elucidate reaction pathways.Finally,future perspectives for developing high-efficiency 0D/2D photocatalysts are proposed to explore potential emerging carbon nitride allotropes,large-scale production,machine learning integration,and multidisciplinary advances for technological breakthroughs.
基金financially supported by the Shenzhen Science and Technology Program(No.JCYJ20220531093205013)the National Natural Science Foundation of China(No.52100069).
文摘Artificial photocatalytic energy conversion is considered as the most potential strategy for solving the increasingly serious energy crisis and environmental pollution problems by directly capturing solar energy.Therefore,high efficiency photocatalyst has drawn significant research attention in recent years.Due to the excellent electronic,optical,structural,and physicochemical performances,silver-based g-C_(3)N_(4)have become promising photocatalysts.This review emphasizes the recent progresses and challenges on g-C_(3)N_(4)decorated with silver for photocatalytic energy conversion.The extensive use of g-C_(3)N_(4)decorated with silver in diverse photocatalytic reactions,including hydrogen evolution,pollutant degradation and carbon dioxide reduction,is also fully introduced.In addition,we propose the perspectives of g-C_(3)N_(4)decorated with silver on photocatalytic applications.We hope that this review will shed some light on the photocatalytic energy conversion of g-C_(3)N_(4)decorated with silver.
基金Jilin Province Science and Technology Development Program,Grant/Award Number:20190201233JCProject for Self-innovation Capability Construction of Jilin Province Development and Reform Commission,Grant/Award Number:2021C026+3 种基金Program for JLU Science and Technology Innovative Research Team,Grant/Award Numbers:JLUSTIRT,2017TD-09National Natural Science Foundation of China,Grant/Award Numbers:12034002,51872116Natural Science Funds for Distinguished Young Scholar of Heilongjiang Province,Grant/Award Number:JC2018004Excellent Young Foundation of Harbin Normal University,Grant/Award Number:XKYQ201304。
文摘Retaining the ultrathin structure of two-dimensional materials is very important for stabilizing their catalytic performances.However,aggregation and restacking are unavoidable,to some extent,due to the van der Waals interlayer interaction of two-dimensional materials.Here,we address this challenge by preparing an origami accordion structure of ultrathin twodimensional graphitized carbon nitride(oa-C_(3)N_(4))with rich vacancies.This novel structured oa-C_(3)N_(4) shows exceptional photocatalytic activity for the CO_(2) reduction reaction,which is 8.1 times that of the pristine C_(3)N_(4).The unique structure not only prevents restacking but also increases light harvesting and the density of vacancy defects,which leads to modification of the electronic structure,regulation of the CO_(2) adsorption energy,and a decrease in the energy barrier of the carbon dioxide to carboxylic acid intermediate reaction.This study provides a new avenue for the development of stable highperformance two-dimensional catalytic materials.
基金We acknowledge the support from the National Natural Science Foundation of China(Nos.51876173 and 52142604)the Natural Science Foundation of Jiangsu Province(No.BK20190054)+2 种基金the Suzhou Science and Technology Program(SYG202101)Fok Ying-Tung Education Foundation(No.171048)the China Fundamental Research Funds for the Central Universities.
文摘Heterojunction design in a two-dimensional(2D)fashion has been deemed beneficial for improving the photocatalytic activity of g-C_(3)N_(4)because of the promoted interfacial charge transfer,yet still facing challenges.Herein,we construct a novel 2D/2D Cu_(3)P nanosheet/P-doped g-C_(3)N_(4)(PCN)nanosheet heterojunction photocatalyst(PCN/Cu_(3)P)through a simple in-situ phosphorization treatment of 2D/2D CuS/g-C_(3)N_(4)composite for photocatalytic H2 evolution.We demonstrate that the 2D lamellar structure of both CuS and g-C_(3)N_(4)could be well reserved in the phosphorization process,while CuS and g-C_(3)N_(4)in-situ transformed into Cu_(3)P and PCN,respectively,leading to the formation of PCN/Cu_(3)P tight 2D/2D heterojunction.Owing to the large contact area provided by intimate face-to-face 2D/2D structure,the PCN/Cu_(3)P photocatalyst exhibits significantly enhanced charge separation efficiency,thus achieving a boosted visible-light-driven photocatalytic behavior.The highest rate for H2 evolution reaches 5.12 umol·h^(-1),nearly 24 times and 368 times higher than that of pristine PCN and g-C_(3)N_(4),respectively.This work represents an excellent example in elaborately con-structing g-C_(3)N_(4)-based 2D/2D heterostructure and could be extended to other photocatalyst/co-catalyst system.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.NRF-2018R1A5A1025137).
文摘A two-dimensional(2D)/2D hybrid heterojunction with face-to-face interfacial assembly is a desirable dimensionality design with significant potential for various photocatalytic applications due to the large interfacial contact area,which facilitates charge migration and separation.Herein,we developed an ef-ficient 2D/2D hybrid heterojunction consisting of BiOIO 3 nanoplates(BIO)and g-C_(3)N_(4) nanosheets(CN)using a simple but effective in situ growth method for photocatalytic aqueous antibiotic degradation and H_(2) generation.The face-to-face interfacial assembly of the BIO and CN components in the BIO/CN hy-brid heterojunction was verified using electron microscopy.Remarkably,the BIO/CN hybrid heterojunc-tion outperformed both the BIO and CN counterparts in terms of norfloxacin degradation and H_(2) gen-eration under simulated solar light irradiation.Moreover,the photocatalytic performance of the hybrid catalyst remained nearly unchanged throughout five consecutive test runs.The exceptional performance and stability of the hybrid catalyst are attributable to its extended optical absorption range,large interfa-cial contact area provided by the face-to-face assembly in the 2D/2D hybrid configuration,and enhanced photoexcited charge separation efficiency and redox power of the separated charges,which are supported by an efficient S-scheme charge transfer mechanism.This study illuminates the rational construction of novel 2D/2D S-scheme hybrid heterojunction photocatalysts with practical applications in environmental remediation and sustainable energy generation.
基金The financial support from the National Natural Science Foundation of China (22178089)the Hunan Provincial Innovation Foundation for Postgraduate (CX20220392)。
文摘The synthesis of high value-added chemical products using CO_(2)and CH_(4)is a promising CO_(2)conversion technology that can reduce greenhouse gas emissions while also alleviating the energy crisis.However,problems such as high energy consumption and strict reaction conditions in reforming process hinder the further development of the technology.In this work,carbon-nitrogen based composites were prepared for the first time according to the design principle from morphology to heterojunction,which is innovatively applied in the process of photocatalytic CH4reforming.Firstly,C_(3)N_(4)materials with different dimensions(D) are prepared and applied to a CO_(2)-CH_(4)photocatalytic system.Additionally,the 2D/2D TiO_(2)/g-C_(3)N_(4)heterostructure is constructed with the ultrasonic impregnation method to further improve charge generation,transfer,and separation efficiency.It is worth noting that the yield of CO reaches173.80 μmol g^(-1),and the catalytic performance is improved by 1546% compared to bulk C_(3)N_(4).Moreover,the physical and chemical properties of 2D/2D TiO_(2)/g-C_(3)N_(4)materials are studied using a variety of cha racterization methods.Furthermore,the work fu nction and adsorption energy of different C3N4/TiO_(2)models for CO_(2)adsorption are calculated by density functional theory(DFT).Then,a possible catalytic mechanism for photocatalytic CO_(2)and CH_(4) conversion is proposed based on DFT calculations and experimental results.This work provides a new technical route for the rapid conversion of CO_(2)and CH_(4) at room temperature,as well as a new research concept for achieving carbon neutrality.
基金supported by the National Natural Science Foundation of China (No.21972166)Beijing Natural Science Foundation (No.2202045)National Key Research and Development Program of China (No.2019YFC1907600)。
文摘The catalytic performance of light-derived CO_(2)reduction with H_(2)O is strongly dependent on the sepa-ration efficiency of photogenerated carriers.Herein,the direct Z-scheme catalysts(g-C_(3)N_(4)/3DOM-WO_(3))of graphitic carbon nitride(g-C_(3)N_(4))nanosheets decorated three-dimensional ordered macroporous WO_(3)(3DOM-WO_(3))were successfully fabricated by using the in-situ colloidal crystal template method.The slow light effect of 3DOM-WO_(3)photonic crystals expands the absorption of visible light and improves the uti-lization of light energy.The Z-scheme structure of g-C_(3)N_(4)/3DOM-WO_(3)catalysts is able to upgrade the separation efficiency of photogenerated electron-hole pairs.The g-C_(3)N_(4)/3DOM-WO_(3)photocatalyst,whose formation rate of CO product is 48.7μmol g^(−1)h^(−1),exhibits the excellent catalytic activity for CO_(2)reduc-tion.The transfer pathway of stimulated electrons over the g-C_(3)N_(4)/3DOM-WO_(3)photocatalyst is proposed and discussed.The present approach provides unique insights into the rational development of high-performance photochemical systems for efficient CO_(2)reduction into valuable carbon-containing chemicals and energy fuels.
