As a highly tempting technology to close the carbon cycle,electrochemical CO_(2)reduction calls for the development of highly efficient and durable electrocatalysts.In the current study,Design of Experiments utilizing...As a highly tempting technology to close the carbon cycle,electrochemical CO_(2)reduction calls for the development of highly efficient and durable electrocatalysts.In the current study,Design of Experiments utilizing the response surface method is exploited to predict the optimal process variables for preparing high-performance Cu catalysts,unraveling that the selectivity towards methane or ethylene can be simply modulated by varying the evaporation parameters,among which the Cu film thickness is the most pivotal factor to determine the product selectivity.The predicted optimal catalyst with a low Cu thickness affords a high methane Faradaic efficiency of 70.6%at the partial current density of 211.8 m A cm^(-2),whereas that of a high Cu thickness achieves a high ethylene selectivity of 66.8%at267.2 m A cm^(-2)in the flow cell.Further structure-performance correlation and in-situ electrospectroscopic measurements attribute the high methane selectivity to isolated Cu clusters with low packing density and monotonous lattice structure,and the high ethylene efficiency to coalesced Cu nanoparticles with rich grain boundaries and lattice defects.The high Cu packing density and crystallographic diversity is of essence to promoting C–C coupling by stabilizing*CO and suppressing*H coverage on the catalyst surface.This work highlights the implementation of scientific and mathematic methods to uncover optimal catalysts and mechanistic understandings toward selective electrochemical CO_(2)reduction.展开更多
Assembly of two-dimensional(2D)metal–organic layers(MOLs)based on the hard and soft acid–base theorem represents an exquisite strategy for the construction of photocatalytic platforms in virtue of the highly exposed...Assembly of two-dimensional(2D)metal–organic layers(MOLs)based on the hard and soft acid–base theorem represents an exquisite strategy for the construction of photocatalytic platforms in virtue of the highly exposed active sites,much improved mass transport,and greatly elevated stability.Herein,nanocages composed of MOLs are produced for the first time through a cosolvent approach utilizing zirconium-based UiO-66-(OH)2 as the structural precursor.To endow the catalytic activity for CO_(2) conversion,single atomic Co^(2+)sites are appended to the Zr-oxo nodes of the MOL cages,demonstrating a remarkable CO yield of 7.74 mmol·g^(-1)·h^(-1) and operational stability of 97.1%product retention after five repeated cycles.Such an outstanding photocatalytic performance is mainly attributed to the unique nanocage morphology comprising enormous 2D nanosheets for augmented Co^(2+)exposure and the abundant surface hydroxyl groups for local CO_(2) enrichment.This work underlines the tailoring of both metal–organic framework(MOF)morphology and functionality to boost the turnover rate of photocatalytic CO_(2) reduction reaction(CO_(2)RR).展开更多
The development of robust photocatalytic systems is key to harvest the solar power for hydrogen production. In the current study, a series of aluminum-based porphyrinic metal organic frameworks (AlTCPP) with various m...The development of robust photocatalytic systems is key to harvest the solar power for hydrogen production. In the current study, a series of aluminum-based porphyrinic metal organic frameworks (AlTCPP) with various morphologies of bulk, carambola-like and nanosheets are synthesized with modulated layer thickness. Morphology-dependent photocatalytic activities in hydrogen production are witnessed and inversely correlate to the thickness of the Al-TCPP micro-platelets or nanosheets. Particularly, the exfoliated metal organic layers (MOLs) of Al-TCPP demonstrated a high hydrogen yield rate of 1.32×10^(4)μmol h^(-1)g^(-1)that is 21-fold of that from the bulk catalyst, as well as an exceptional TON of6704 that seldom seen in literature. Through comprehensive photochemical characterizations, the remarkable photocatalytic performance of Al-TCPP-MOL is attributed to the great charge separation efficiency and transfer kinetics endowed by the ultrathin 2D morphology with extended active surface area.展开更多
基金supported by the National Key R&D Program of China(2020YFB1505703)the National Natural Science Foundation of China(22072101,22075193)+2 种基金supported by the Natural Science Foundation of Jiangsu Province(BK20211306)the Six Talent Peaks Project in Jiangsu Province(TD-XCL-006)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions。
文摘As a highly tempting technology to close the carbon cycle,electrochemical CO_(2)reduction calls for the development of highly efficient and durable electrocatalysts.In the current study,Design of Experiments utilizing the response surface method is exploited to predict the optimal process variables for preparing high-performance Cu catalysts,unraveling that the selectivity towards methane or ethylene can be simply modulated by varying the evaporation parameters,among which the Cu film thickness is the most pivotal factor to determine the product selectivity.The predicted optimal catalyst with a low Cu thickness affords a high methane Faradaic efficiency of 70.6%at the partial current density of 211.8 m A cm^(-2),whereas that of a high Cu thickness achieves a high ethylene selectivity of 66.8%at267.2 m A cm^(-2)in the flow cell.Further structure-performance correlation and in-situ electrospectroscopic measurements attribute the high methane selectivity to isolated Cu clusters with low packing density and monotonous lattice structure,and the high ethylene efficiency to coalesced Cu nanoparticles with rich grain boundaries and lattice defects.The high Cu packing density and crystallographic diversity is of essence to promoting C–C coupling by stabilizing*CO and suppressing*H coverage on the catalyst surface.This work highlights the implementation of scientific and mathematic methods to uncover optimal catalysts and mechanistic understandings toward selective electrochemical CO_(2)reduction.
基金supported by the National Natural Science Foundation of China(Nos.22075193 and 22072101)the Natural Science Foundation of Jiangsu Province(Nos.BK20221239,BK20211306,and BK20220027)+1 种基金the Six Talent Peaks Project in Jiangsu Province(No.TD-XCL-006)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions.
文摘Assembly of two-dimensional(2D)metal–organic layers(MOLs)based on the hard and soft acid–base theorem represents an exquisite strategy for the construction of photocatalytic platforms in virtue of the highly exposed active sites,much improved mass transport,and greatly elevated stability.Herein,nanocages composed of MOLs are produced for the first time through a cosolvent approach utilizing zirconium-based UiO-66-(OH)2 as the structural precursor.To endow the catalytic activity for CO_(2) conversion,single atomic Co^(2+)sites are appended to the Zr-oxo nodes of the MOL cages,demonstrating a remarkable CO yield of 7.74 mmol·g^(-1)·h^(-1) and operational stability of 97.1%product retention after five repeated cycles.Such an outstanding photocatalytic performance is mainly attributed to the unique nanocage morphology comprising enormous 2D nanosheets for augmented Co^(2+)exposure and the abundant surface hydroxyl groups for local CO_(2) enrichment.This work underlines the tailoring of both metal–organic framework(MOF)morphology and functionality to boost the turnover rate of photocatalytic CO_(2) reduction reaction(CO_(2)RR).
基金financially supported by National Natural Science Foundation of China (Nos. 22072101, 22075193, 51911540473)Natural Science Research Project of Jiangsu Higher Education Institutions of China (No. 18KJA480004)+2 种基金the Key Technology Initiative of Suzhou Municipal Science and Technology Bureau (No. SYG201934)Six Talent Peaks Project in Jiangsu Province (No. TD-XCL-006)Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions。
文摘The development of robust photocatalytic systems is key to harvest the solar power for hydrogen production. In the current study, a series of aluminum-based porphyrinic metal organic frameworks (AlTCPP) with various morphologies of bulk, carambola-like and nanosheets are synthesized with modulated layer thickness. Morphology-dependent photocatalytic activities in hydrogen production are witnessed and inversely correlate to the thickness of the Al-TCPP micro-platelets or nanosheets. Particularly, the exfoliated metal organic layers (MOLs) of Al-TCPP demonstrated a high hydrogen yield rate of 1.32×10^(4)μmol h^(-1)g^(-1)that is 21-fold of that from the bulk catalyst, as well as an exceptional TON of6704 that seldom seen in literature. Through comprehensive photochemical characterizations, the remarkable photocatalytic performance of Al-TCPP-MOL is attributed to the great charge separation efficiency and transfer kinetics endowed by the ultrathin 2D morphology with extended active surface area.