The plasma-coupled electrocatalytic cascade technology with NO_x~-as intermediate product is a potential method to realize green ammonia synthesis.The matching of the formation rate and consumption rate of NO_(2)^(-)a...The plasma-coupled electrocatalytic cascade technology with NO_x~-as intermediate product is a potential method to realize green ammonia synthesis.The matching of the formation rate and consumption rate of NO_(2)^(-)as the main absorption product is an important prerequisite for the system to achieve stable operation.Therefore,this paper firstly emphasizes the importance of operating parameters on the cascade system based on the single factor experiment.Secondly,the empirical equation between electrocatalytic operating conditions and NO_(2)^(-)consumption rate was established by response surface analysis.Based on this equation,the electrocatalytic operating parameters were optimized to achieve the dynamic equilibrium between NO_(2)^(-)formation rate and consumption rate.Finally,the techno-economic assessment model was established to calculate the levelized cost of ammonia based on the cascade system,and the single-variable sensitivity analysis was performed to provide the clear guidance for cost reduction.展开更多
The diffusion,adsorption/desorption behaviors of water molecules and hydrogen molecules are of great importance in heterogeneous photocatalytic hydrogen production.In the study of structure-property-performance relati...The diffusion,adsorption/desorption behaviors of water molecules and hydrogen molecules are of great importance in heterogeneous photocatalytic hydrogen production.In the study of structure-property-performance relationships,nanoconfined space provides an ideal platform to promote mass diffusion and transfer due to their extraordinary properties that are different from the bulk systems.Herein,we designed and prepared a nanoconfined CdS@SiO_(2)-NH_(2) nanoreactor,whose shell is composed of amino-functionalized silica nanochannels,and encapsulates spherical CdS as a photocatalyst inside.Experimental and simulated results reveal that the amino-functionalized nanochannels promote water molecules’and hydrogen molecules’directional diffusion and transport.Water molecules are enriched in the nanocavity between the core and the shell,and promote the interfacial photocatalytic reaction.As a result,the maximized water enrichment and minimized hydrogen-occupied active sites enable photocatalyst with optimized mass transfer kinetics and localization electron distribution on the CdS surface,leading to superior hydrogen production performance with activity as high as 37.1 mmol·g^(-1)·h^(-1).展开更多
Organic conjugated polymers have received extensive attention due to their unique electronic properties.However,there have been relatively few reports on the dark photocatalytic reactions utilizing organic conjugated ...Organic conjugated polymers have received extensive attention due to their unique electronic properties.However,there have been relatively few reports on the dark photocatalytic reactions utilizing organic conjugated polymers.Herein,we report the successful synthesis of an organic conjugated polymer based on poly(heptazine imide)nanocrystals(CNNCs)for H_(2)O_(2)evolution and biomedical applications using a simple salt molten method and sonication-centrifugation process.The results show that these colloid CNNCs have the characteristics of photogenerated electrons accumulation and realize dark photocatalysis with high reducibility under visible light irradiation.Notably,these accumulating photogenerated electrons can reduce O_(2)in darkness to produce H_(2)O_(2).In addition,cytotoxicity tests were conducted and it was found that H_(2)O_(2)produced under dark conditions could oxidize L-arginine(L-Arg)to NO,which effectively killed tumors in the dark.This work provides an important strategy to construct organic conjugated semiconductor nanocrystals and applying them to future energy and biomedical fields.展开更多
Electrocatalysis for C–N coupling reactions(EcnRR)plays a crucial role in the synthesis of various organic molecules.However,the C–N coupling process is inherently complex and kinetically sluggish.Single atom cataly...Electrocatalysis for C–N coupling reactions(EcnRR)plays a crucial role in the synthesis of various organic molecules.However,the C–N coupling process is inherently complex and kinetically sluggish.Single atom catalysts(SACs),with their high atomic efficiency,tunable structures,and remarkable catalytic activity,exhibit exceptional performance and hold great promise for C–N coupling reactions.The design of SACs requires a deep understanding of the reaction mechanisms,particularly the dynamic evolution of multicomponent reactions.This necessitates systematic studies of multi-species coupling mechanisms to move beyond traditional trial-and-error approaches.This review elucidates the activation mechanisms of carbon-and nitrogen-containing molecules,providing fundamental insights into the SACs-mediated electrocatalytic C–N coupling process.Notably,the core focus lies in proposing novel design principles for SACs systems tailored for C–N coupling,based on theoretical frameworks and experimental findings.These insights not only guide the improvement of existing methodologies but also offer transformative pathways for electrocatalytic organic nitrogenation via C–N coupling chemistry,potentially reshaping the landscape of organic synthesis.Looking ahead,a comprehensive understanding of the structure–activity relationships in SAC design will be key to advancing this rapidly evolving field.展开更多
基金financially supported by National Key Research and Development Program of China(2020YFA0710000)National Natural Science Foundation of China(U22A20391,22308274)+2 种基金Postdoctoral Fellowship Program of CPSF(GZB20240600,2023TQ0265,2024M752589)Innovation Capability Support Program of Shaanxi(NO.2023-CX-TD-26)the Programme of Introducing Talents of Discipline to Universities(B23025)。
文摘The plasma-coupled electrocatalytic cascade technology with NO_x~-as intermediate product is a potential method to realize green ammonia synthesis.The matching of the formation rate and consumption rate of NO_(2)^(-)as the main absorption product is an important prerequisite for the system to achieve stable operation.Therefore,this paper firstly emphasizes the importance of operating parameters on the cascade system based on the single factor experiment.Secondly,the empirical equation between electrocatalytic operating conditions and NO_(2)^(-)consumption rate was established by response surface analysis.Based on this equation,the electrocatalytic operating parameters were optimized to achieve the dynamic equilibrium between NO_(2)^(-)formation rate and consumption rate.Finally,the techno-economic assessment model was established to calculate the levelized cost of ammonia based on the cascade system,and the single-variable sensitivity analysis was performed to provide the clear guidance for cost reduction.
基金supported by the National Natural Science Foundation of China(No.22108214)Joint Funds of the National Natural Science Foundation of China(No.U22A20391).
文摘The diffusion,adsorption/desorption behaviors of water molecules and hydrogen molecules are of great importance in heterogeneous photocatalytic hydrogen production.In the study of structure-property-performance relationships,nanoconfined space provides an ideal platform to promote mass diffusion and transfer due to their extraordinary properties that are different from the bulk systems.Herein,we designed and prepared a nanoconfined CdS@SiO_(2)-NH_(2) nanoreactor,whose shell is composed of amino-functionalized silica nanochannels,and encapsulates spherical CdS as a photocatalyst inside.Experimental and simulated results reveal that the amino-functionalized nanochannels promote water molecules’and hydrogen molecules’directional diffusion and transport.Water molecules are enriched in the nanocavity between the core and the shell,and promote the interfacial photocatalytic reaction.As a result,the maximized water enrichment and minimized hydrogen-occupied active sites enable photocatalyst with optimized mass transfer kinetics and localization electron distribution on the CdS surface,leading to superior hydrogen production performance with activity as high as 37.1 mmol·g^(-1)·h^(-1).
基金supported by the National Natural Science Foundation of China(Nos.22302154,U22A20391,22078256,22202043 and 82202355)Innovation Capability Support Program of Shanxi(No.2023-CX-TD-26)+3 种基金the Programme of Introducing Talents of Discipline to Universities(No.B23025)the“Young Talent Support Plan”of Xi’an Jiaotong University(No.HG6J030)the high-level innovation and entrepreneurship talent project of Qinchuangyuan(No.QCYRCXM-2023-98)the Young and Middle-aged Scholars Project of Fujian Province(No.JAT210368).
文摘Organic conjugated polymers have received extensive attention due to their unique electronic properties.However,there have been relatively few reports on the dark photocatalytic reactions utilizing organic conjugated polymers.Herein,we report the successful synthesis of an organic conjugated polymer based on poly(heptazine imide)nanocrystals(CNNCs)for H_(2)O_(2)evolution and biomedical applications using a simple salt molten method and sonication-centrifugation process.The results show that these colloid CNNCs have the characteristics of photogenerated electrons accumulation and realize dark photocatalysis with high reducibility under visible light irradiation.Notably,these accumulating photogenerated electrons can reduce O_(2)in darkness to produce H_(2)O_(2).In addition,cytotoxicity tests were conducted and it was found that H_(2)O_(2)produced under dark conditions could oxidize L-arginine(L-Arg)to NO,which effectively killed tumors in the dark.This work provides an important strategy to construct organic conjugated semiconductor nanocrystals and applying them to future energy and biomedical fields.
基金supported by the National Key R&D Program of China(No.2020YFA0710000)the National Natural Science Foundation of China(No.22302154)+2 种基金the Key Projects in Shaanxi Province(No.2024CY2-GJHX-75)the Joint Funds of the National Natural Science Foundation of China(No.U22A20391)the Innovation Capability Support Program of Shaanxi(No.2023-CXTD-26).
文摘Electrocatalysis for C–N coupling reactions(EcnRR)plays a crucial role in the synthesis of various organic molecules.However,the C–N coupling process is inherently complex and kinetically sluggish.Single atom catalysts(SACs),with their high atomic efficiency,tunable structures,and remarkable catalytic activity,exhibit exceptional performance and hold great promise for C–N coupling reactions.The design of SACs requires a deep understanding of the reaction mechanisms,particularly the dynamic evolution of multicomponent reactions.This necessitates systematic studies of multi-species coupling mechanisms to move beyond traditional trial-and-error approaches.This review elucidates the activation mechanisms of carbon-and nitrogen-containing molecules,providing fundamental insights into the SACs-mediated electrocatalytic C–N coupling process.Notably,the core focus lies in proposing novel design principles for SACs systems tailored for C–N coupling,based on theoretical frameworks and experimental findings.These insights not only guide the improvement of existing methodologies but also offer transformative pathways for electrocatalytic organic nitrogenation via C–N coupling chemistry,potentially reshaping the landscape of organic synthesis.Looking ahead,a comprehensive understanding of the structure–activity relationships in SAC design will be key to advancing this rapidly evolving field.
