Elemental doping confined in atomically-thin 2 D semiconductors offers a compelling strategy for constructing high performance photocatalysts.Although impressive progress has been achieved based on co-thermolysis meth...Elemental doping confined in atomically-thin 2 D semiconductors offers a compelling strategy for constructing high performance photocatalysts.Although impressive progress has been achieved based on co-thermolysis method,the choices of dopants as well as semiconductor hosts are still quite limited to yield the elaborate photocatalyst with atomic-layer-confined doping defects,owing to the difficulty in balancing the reaction kinetics of different precursors.This study shows that the cation exchange reaction,which is dictated by the Pearson's hard and soft acids and bases(HSAB)theory and allowed to proceed at mild temperatures,can be developed into a conceptually new protocol for engineering elemental doping confined in semiconductor atomic layers.To this aim,the two atomic layers of a new type of 2 D photocatalyst PdSe0_(3)(PdSe0_(3)2 ALs,1.1 nm)are created by liquid exfoliation and exploited as a proof-of-concept prototype.It is demonstrated that the Mn(Ⅱ)dopants with controlled concentrations can be incorporated into PdSeO_(3)2 ALs via topological Mn^(2+) for-Pd^(2+) cation exchange performed in water/isopropanol solution at 30℃.The resulting Mn-doped PdSeO_(3)2 ALs present enhanced capacity for driving photocatalytic oxidation reactions in comparison with their undoped counterparts.The findings here suggest that the new route mediated by post synthetic cation exchange promises to give access to manifold 2 D confined-doping photocatalysts,with little perturbations on the thickness,morphology,and crystal structure of the atomically-thin semiconductor hosts.展开更多
Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetalli...Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetallic alloy nanoparticles on N-doped carbon support(RuCoMn@NC)via the pyrolysis-adsorption-pyrolysis process using ZIF-67 as a precursor.The RuCoMn@NC catalyst exhibited excellent electrocatalytic performance for the hydrogen evolution reaction(HER)over a wide range of pH and glucose oxidation reaction in alkaline media.It showed exceptional HER activity in alkaline medium,superior to that of the commercial Pt/C catalyst(20 wt%),and good electrochemical stability.Further,a two-electrode alkaline electrolyzer pairing RuCoMn@NC as both cathode and anode was employed,and only a cell voltage of 1.63 V was required to attain a current density of 10 mA cm^(-2)in glucose electrolysis,which is about 270 mV lower than that in the overall water-splitting electrolyzer.This paper provides a promising method for developing efficiently bifunctional electrocatalysts driving redox electrocatalysis,and it would be beneficial to energy-saving electrolytic H_(2) production.展开更多
Enantioselective recognition and separation are the most important issues in the fields of chemistry,pharmacy,agrochemical,and food science.Here,we developed two optically active diamines showing aggregation-induced e...Enantioselective recognition and separation are the most important issues in the fields of chemistry,pharmacy,agrochemical,and food science.Here,we developed two optically active diamines showing aggregation-induced emission(AIE)that can discriminate 5 kinds of chiral acids with high enantioselectivity.Especially,a very high fluorescence intensity ratio(IL/ID)of 281 for(±)-Dibenzoyl-D/L-tartaric acid was obtained through the collection of fluorescence change after interaction with chiral AIE-active diamine.By virtue of AIE property and intermolecular acidbase interaction,enantioselective separation was facilely realized by simple filtration of the precipitates formed by chiral AIE luminogen(AIEgen)and one enantiomer in the racemic solution.The chiral HPLC data indicated that the precipitates of AIEgen/chiral acid possessed 82%L-analyte(the enantiomeric excess value was assessed to be 64%ee).Therefore,this method can serve as a simple,convenient,and low-cost tool for chiral detection and separation.展开更多
Here we report a synthetic strategy for controllable construction of yolk-shell and core-shell plasmonic metal@semiconductor hybrid nanocrystals through modulating the kinetics of sulfurization reaction followed by ca...Here we report a synthetic strategy for controllable construction of yolk-shell and core-shell plasmonic metal@semiconductor hybrid nanocrystals through modulating the kinetics of sulfurization reaction followed by cation exchange.The yielded yolk-shell structured products feature exceptional crystallinity and more importantly,the intimately adjoined and sharp interface between plasmonic metal and semiconductor which facilitates efficient charge carrier communications between them.By exploiting the system composed of Au nanorods and p-type PbS as a demonstration,we show that the Au@PbS yolk-shell nanorods manifest notable improvement in visible and near infrared light absorption compared to the Au@PbS core-shell nanorods as well as hollow PbS nanorods.Moreover,the photocathode constituted by Au@PbS yolk-shell nanorods affords the highest photoelectrochemical activities both under simulated sunlight andλ>700 nm light irradiation.The superior performance of Au@PbS yolk-shell nanorods is considered arising from the combination of the favorable structural advantages of yolk-shell configuration and the surface plasmon resonance enhancement effect.We envision that the reported synthetic strategy can offer a valuable means to create hybrid nanocrystals with desirable structures and functions that enable to harness the photogenerated charge carriers,including the plasmonic hot holes,in wide-range solar-to-fuel conversion.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52072035,51631001,21801015,51702016,51902023,51872030)Joint R&D Plan of Hongkong+3 种基金MacaoTaiwan and Beijing(No.Z191100001619002)the Fundamental Research Funds for the Central Universities(No.2017CX01003)the Beijing Institute of Technology Research Fund Program for Young Scholars。
文摘Elemental doping confined in atomically-thin 2 D semiconductors offers a compelling strategy for constructing high performance photocatalysts.Although impressive progress has been achieved based on co-thermolysis method,the choices of dopants as well as semiconductor hosts are still quite limited to yield the elaborate photocatalyst with atomic-layer-confined doping defects,owing to the difficulty in balancing the reaction kinetics of different precursors.This study shows that the cation exchange reaction,which is dictated by the Pearson's hard and soft acids and bases(HSAB)theory and allowed to proceed at mild temperatures,can be developed into a conceptually new protocol for engineering elemental doping confined in semiconductor atomic layers.To this aim,the two atomic layers of a new type of 2 D photocatalyst PdSe0_(3)(PdSe0_(3)2 ALs,1.1 nm)are created by liquid exfoliation and exploited as a proof-of-concept prototype.It is demonstrated that the Mn(Ⅱ)dopants with controlled concentrations can be incorporated into PdSeO_(3)2 ALs via topological Mn^(2+) for-Pd^(2+) cation exchange performed in water/isopropanol solution at 30℃.The resulting Mn-doped PdSeO_(3)2 ALs present enhanced capacity for driving photocatalytic oxidation reactions in comparison with their undoped counterparts.The findings here suggest that the new route mediated by post synthetic cation exchange promises to give access to manifold 2 D confined-doping photocatalysts,with little perturbations on the thickness,morphology,and crystal structure of the atomically-thin semiconductor hosts.
基金supported by the National Natural Science Foundation of China(52072035,51631001,21801015,51902023 and 51872030)the Fundamental Research Funds for the Central Universities(2017CX01003)+1 种基金Beijing Institute of Technology Research Fund Program for Young Scholarsthe Joint R&D Plan of Hong Kong,Macao,Taiwan,and Beijing(Z191100001619002).
文摘Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetallic alloy nanoparticles on N-doped carbon support(RuCoMn@NC)via the pyrolysis-adsorption-pyrolysis process using ZIF-67 as a precursor.The RuCoMn@NC catalyst exhibited excellent electrocatalytic performance for the hydrogen evolution reaction(HER)over a wide range of pH and glucose oxidation reaction in alkaline media.It showed exceptional HER activity in alkaline medium,superior to that of the commercial Pt/C catalyst(20 wt%),and good electrochemical stability.Further,a two-electrode alkaline electrolyzer pairing RuCoMn@NC as both cathode and anode was employed,and only a cell voltage of 1.63 V was required to attain a current density of 10 mA cm^(-2)in glucose electrolysis,which is about 270 mV lower than that in the overall water-splitting electrolyzer.This paper provides a promising method for developing efficiently bifunctional electrocatalysts driving redox electrocatalysis,and it would be beneficial to energy-saving electrolytic H_(2) production.
基金National Natural Science Foundation of China,Grant/Award Numbers:52173152,21805002Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110476+4 种基金Fund of the Rising Stars of Shaanxi Province,Grant/Award Number:2021KJXX-48Natural Science Basic Research Plan in Shaanxi Province of China,Grant/Award Numbers:2019JQ-302,2021JQ-801Research Foundation of Education Department of Shaanxi Province,Grant/Award Number:20JS005Young Talent fund of University Association for Science and Technology in Shaanxi,China,Grant/Award Numbers:20190610,20210606Scientific and Technological Innovation Team of Shaanxi Province,Grant/Award Number:2022TD-36。
文摘Enantioselective recognition and separation are the most important issues in the fields of chemistry,pharmacy,agrochemical,and food science.Here,we developed two optically active diamines showing aggregation-induced emission(AIE)that can discriminate 5 kinds of chiral acids with high enantioselectivity.Especially,a very high fluorescence intensity ratio(IL/ID)of 281 for(±)-Dibenzoyl-D/L-tartaric acid was obtained through the collection of fluorescence change after interaction with chiral AIE-active diamine.By virtue of AIE property and intermolecular acidbase interaction,enantioselective separation was facilely realized by simple filtration of the precipitates formed by chiral AIE luminogen(AIEgen)and one enantiomer in the racemic solution.The chiral HPLC data indicated that the precipitates of AIEgen/chiral acid possessed 82%L-analyte(the enantiomeric excess value was assessed to be 64%ee).Therefore,this method can serve as a simple,convenient,and low-cost tool for chiral detection and separation.
基金This work was supported by the National Natural Science Foundation of China(Nos.51702016,51631001,21801015,51902023,51872030)the Fundamental Research Funds for the Central Universities(No.2017CX01003)the Beijing Institute of Technology Research Fund Program for Young Scholars.The characterization results were supported by Beijing Zhongkebaice Technology Service Co.,Ltd.
文摘Here we report a synthetic strategy for controllable construction of yolk-shell and core-shell plasmonic metal@semiconductor hybrid nanocrystals through modulating the kinetics of sulfurization reaction followed by cation exchange.The yielded yolk-shell structured products feature exceptional crystallinity and more importantly,the intimately adjoined and sharp interface between plasmonic metal and semiconductor which facilitates efficient charge carrier communications between them.By exploiting the system composed of Au nanorods and p-type PbS as a demonstration,we show that the Au@PbS yolk-shell nanorods manifest notable improvement in visible and near infrared light absorption compared to the Au@PbS core-shell nanorods as well as hollow PbS nanorods.Moreover,the photocathode constituted by Au@PbS yolk-shell nanorods affords the highest photoelectrochemical activities both under simulated sunlight andλ>700 nm light irradiation.The superior performance of Au@PbS yolk-shell nanorods is considered arising from the combination of the favorable structural advantages of yolk-shell configuration and the surface plasmon resonance enhancement effect.We envision that the reported synthetic strategy can offer a valuable means to create hybrid nanocrystals with desirable structures and functions that enable to harness the photogenerated charge carriers,including the plasmonic hot holes,in wide-range solar-to-fuel conversion.
