UiO-66-NH_(2),an important metal-organic framework,is usually synthesized by solvothermal method and the particle size is generally larger than 200 nm,which limits its catalytic applications in chemical reactions.It i...UiO-66-NH_(2),an important metal-organic framework,is usually synthesized by solvothermal method and the particle size is generally larger than 200 nm,which limits its catalytic applications in chemical reactions.It is very meaningful to produce UiO-66-NH_(2) nanoparticles with ultrasmall size,but remains challenging.Herein,we synthesized UiO-66-NH_(2) nanoparticles in size of 8-15 nm that are immobilized on g-C_(3)N_(4)nanosheets.Compared with the UiO-66-NH_(2) synthesized by the traditional solvothermal method(>200 nm),the ultra-small UiO-66-NH_(2) nanoparticles immobilized on g-C_(3)N_(4)have more unsaturated coordination positions and increased Lewis acidity.Owing to these combined advantages,the ultra-small UiO-66-NH_(2)nanoparticles exhibit greatly improved catalytic activity for Meerwein-Ponndorf-Verley reaction than larger UiO-66-NH_(2)particles.展开更多
It is of great importance to develop facile strategies to synthesize catalysts with desirable compositions and structures for high-performance photocatalytic hydrogen generation. In this work, we put forward an ionic ...It is of great importance to develop facile strategies to synthesize catalysts with desirable compositions and structures for high-performance photocatalytic hydrogen generation. In this work, we put forward an ionic liquid assisted one-pot route for the synthesis of heteroatom-doped Pt/TiO2 composite material. This route is simple, environmentally benign and adjustable owing to the designable properties of ionic liquids. The as-synthesized Pt/TiO2 nanocrystals exhibit high activity and stability for the photocatalytic hydrogen generation under simulated solar irradiation. This method can be easily applied to the synthesis of various kinds of metal/TiO2 composites doped with desirable heteroatoms (e.g., F, Cl, Br, etc).展开更多
To construct the heterojunctions of TiO2 with other compounds is of great importance for overcoming its inherent shortages and improving the visible-light photocatalytic performance.Here we propose the construction of...To construct the heterojunctions of TiO2 with other compounds is of great importance for overcoming its inherent shortages and improving the visible-light photocatalytic performance.Here we propose the construction of TiO2/covalent organic framework(COF)heterojunction with tight connection by a supercritical CO2(SC CO2)method,which helps bridging the transformation paths for photo-induced charge between T i02 and COF.The produced T i02/COF heterojunction performs a H2 evolution of 3,962 nmol·g^-1·h^-1 under visible-light irradiation,which is-25 times higher than that of pure TiO2 and 4.5 folds higher than that of TiO2/COF synthesized by the conventional solvothermal method.This study opens up new possibilities for constructing heterojunctions for solar energy utilization.展开更多
The application of nickel in electrocatalytic reduction of CO2 has been largely restricted by side reaction (hydrogen evolution reaction) and catalyst poisoning.Here we report a new strategy to improve the electrocata...The application of nickel in electrocatalytic reduction of CO2 has been largely restricted by side reaction (hydrogen evolution reaction) and catalyst poisoning.Here we report a new strategy to improve the electrocatalytic performance of nickel for CO2 reduction by employing a nitrogen-carbon layer for nickel nanoparticles.Such a nickel electrocatalyst exhibits high Faradaic efficiency 97.5% at relatively low potential of-0.61 V for the conversion of CO2 to CO.Density functional theory calculation reveals that it is thermodynamically accomplishable for the reduction product CO to be removed from the catalyst surface,thus avoiding catalyst poisoning.Also,the catalyst renders hydrogen evolution reaction to be suppressed and hence reasonably improves catalytic performance.展开更多
The sluggish reaction kinetics of alkaline hydrogen oxidation reaction(HOR)is one of the key challenges for anion exchange membrane fuel cells(AEMFCs).To achieve robust alkaline HOR with minimized cost,we developed a ...The sluggish reaction kinetics of alkaline hydrogen oxidation reaction(HOR)is one of the key challenges for anion exchange membrane fuel cells(AEMFCs).To achieve robust alkaline HOR with minimized cost,we developed a single atom-cluster multiscale structure with isolated Pt single atoms anchored on Ru nanoclusters supported on nitrogen-doped carbon nanosheets(Pt1-Ru/NC).The well-defined structure not only provides multiple sites with varied affinity with the intermediates but also enables simultaneous modulation of different sites via interfacial interaction.In addition to weakening Ru–H bond strength,the isolated Pt sites are heavily involved in hydrogen adsorption and synergistically accelerate the Volmer step with the help of Ru sites.Furthermore,this catalyst configuration inhibits the excessive occupancy of oxygen-containing species on Ru sites and facilitates the HOR at elevated potentials.The Pt1-Ru/NC catalyst exhibits superior alkaline HOR performance with extremely high activity and excellent CO-tolerance.An AEMFC with a 0.1 mg·cmPGM^(−2)loading of Pt1-Ru/NC anode catalyst achieves a peak powder density of 1172 mW·cm^(−2),which is 2.17 and 1.55 times higher than that of Pt/C and PtRu/C,respectively.This work provides a new catalyst concept to address the sluggish kinetics of electrocatalytic reactions containing multiple intermediates and elemental steps.展开更多
基金financial supports from National Natural Science Foundation of China(21525316,21673254)Ministry of Science and Technology of China(2017YFA0403003)+1 种基金Chinese Academy of Sciences(QYZDYSSW-SLH013)Beijing Municipal Science&Technology Commission(Z191100007219009)。
文摘UiO-66-NH_(2),an important metal-organic framework,is usually synthesized by solvothermal method and the particle size is generally larger than 200 nm,which limits its catalytic applications in chemical reactions.It is very meaningful to produce UiO-66-NH_(2) nanoparticles with ultrasmall size,but remains challenging.Herein,we synthesized UiO-66-NH_(2) nanoparticles in size of 8-15 nm that are immobilized on g-C_(3)N_(4)nanosheets.Compared with the UiO-66-NH_(2) synthesized by the traditional solvothermal method(>200 nm),the ultra-small UiO-66-NH_(2) nanoparticles immobilized on g-C_(3)N_(4)have more unsaturated coordination positions and increased Lewis acidity.Owing to these combined advantages,the ultra-small UiO-66-NH_(2)nanoparticles exhibit greatly improved catalytic activity for Meerwein-Ponndorf-Verley reaction than larger UiO-66-NH_(2)particles.
基金the National Natural Science Foundation of China (Nos.21525316 and 21673254)Ministry of Science and Technology of China (No.2017YFA0403003)+1 种基金Chinese Academy of Sciences (No.QYZDY-SSW-SLH013)Beijing Municipal Science & Technology Commission (No.Z181100004218004).
文摘It is of great importance to develop facile strategies to synthesize catalysts with desirable compositions and structures for high-performance photocatalytic hydrogen generation. In this work, we put forward an ionic liquid assisted one-pot route for the synthesis of heteroatom-doped Pt/TiO2 composite material. This route is simple, environmentally benign and adjustable owing to the designable properties of ionic liquids. The as-synthesized Pt/TiO2 nanocrystals exhibit high activity and stability for the photocatalytic hydrogen generation under simulated solar irradiation. This method can be easily applied to the synthesis of various kinds of metal/TiO2 composites doped with desirable heteroatoms (e.g., F, Cl, Br, etc).
基金The authors thank the financial supports from M inistry of Science and Technology of China(No.2017YFA0403003)the National Natural Science Foundation of China(Nos.21525316 and 21673254)+1 种基金Chinese Academy of Sciences(No.QYZDYSSW-SLH013)Beijing Municipal Science&Technology Commission(No.Z191100007219009).
文摘To construct the heterojunctions of TiO2 with other compounds is of great importance for overcoming its inherent shortages and improving the visible-light photocatalytic performance.Here we propose the construction of TiO2/covalent organic framework(COF)heterojunction with tight connection by a supercritical CO2(SC CO2)method,which helps bridging the transformation paths for photo-induced charge between T i02 and COF.The produced T i02/COF heterojunction performs a H2 evolution of 3,962 nmol·g^-1·h^-1 under visible-light irradiation,which is-25 times higher than that of pure TiO2 and 4.5 folds higher than that of TiO2/COF synthesized by the conventional solvothermal method.This study opens up new possibilities for constructing heterojunctions for solar energy utilization.
基金the National Natural Science Foundation of China (Nos.21525316,21802146,and 21673254)Ministry of Science and Technology of China (No.2017YFA0403003)+1 种基金Chinese Academy of Sciences (No.QYZDY-SSW-SLH013)Beijing Municipal Science & Technology Commission (No.Z181100004218004).
文摘The application of nickel in electrocatalytic reduction of CO2 has been largely restricted by side reaction (hydrogen evolution reaction) and catalyst poisoning.Here we report a new strategy to improve the electrocatalytic performance of nickel for CO2 reduction by employing a nitrogen-carbon layer for nickel nanoparticles.Such a nickel electrocatalyst exhibits high Faradaic efficiency 97.5% at relatively low potential of-0.61 V for the conversion of CO2 to CO.Density functional theory calculation reveals that it is thermodynamically accomplishable for the reduction product CO to be removed from the catalyst surface,thus avoiding catalyst poisoning.Also,the catalyst renders hydrogen evolution reaction to be suppressed and hence reasonably improves catalytic performance.
基金financially supported by the National Natural Science Foundation of China(Nos.52171224 and 92261119)J.M.W.acknowledges support from Zhejiang Province Postdoctoral Science Foundation(No.ZJ2022003)China Postdoctoral Science Foundation(No.2023M733020).
文摘The sluggish reaction kinetics of alkaline hydrogen oxidation reaction(HOR)is one of the key challenges for anion exchange membrane fuel cells(AEMFCs).To achieve robust alkaline HOR with minimized cost,we developed a single atom-cluster multiscale structure with isolated Pt single atoms anchored on Ru nanoclusters supported on nitrogen-doped carbon nanosheets(Pt1-Ru/NC).The well-defined structure not only provides multiple sites with varied affinity with the intermediates but also enables simultaneous modulation of different sites via interfacial interaction.In addition to weakening Ru–H bond strength,the isolated Pt sites are heavily involved in hydrogen adsorption and synergistically accelerate the Volmer step with the help of Ru sites.Furthermore,this catalyst configuration inhibits the excessive occupancy of oxygen-containing species on Ru sites and facilitates the HOR at elevated potentials.The Pt1-Ru/NC catalyst exhibits superior alkaline HOR performance with extremely high activity and excellent CO-tolerance.An AEMFC with a 0.1 mg·cmPGM^(−2)loading of Pt1-Ru/NC anode catalyst achieves a peak powder density of 1172 mW·cm^(−2),which is 2.17 and 1.55 times higher than that of Pt/C and PtRu/C,respectively.This work provides a new catalyst concept to address the sluggish kinetics of electrocatalytic reactions containing multiple intermediates and elemental steps.
