One of the most unique properties of two-dimensional carbides and nitrides of transition metals(MXenes)is their excellent water dispersibility and yet possessing superior electrical conductivity but their industrial-s...One of the most unique properties of two-dimensional carbides and nitrides of transition metals(MXenes)is their excellent water dispersibility and yet possessing superior electrical conductivity but their industrial-scale application is limited by their costly chemical synthesis methods.In this work,the niche feature of MXenes was capitalized in the packed-bed electrochemical reactor to produce MXenes at an unprecedented reaction rate and yield with minimal chemical waste.A simple NH4F solution was employed as the green electrolyte,which could be used repeatedly without any loss in its efficacy.Surprisingly,both fluoride and ammonium were found to play critical roles in the electrochemical etching,functionalization,and expansion of the layered parent materials(MAXs)through which the liberation of ammonia gas was observed.The electrochemically produced MXenes with excellent conductivity,applied as supercapacitor electrodes,could deliver an ultrahigh volumetric capacity(1408 F cm^(−3))and a volumetric energy density(75.8 Wh L^(−1)).This revolutionary green,energy-efficient,and scalable electrochemical route will not only pave the way for industrial-scale production of MXenes but also open up a myriad of versatile electrochemical modifications for improved functional MXenes.展开更多
Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the ...Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the half‐life of drug metabolism,enhance the efficacy of drugs,close metabolic sites,and decrease side effects.Thus,there is a rising demand for the practical construction of deuterium‐labeled drugs and their intermediates under mild conditions.This paper timely provides an overview of the recent advances in both photo‐and electro‐catalytic mild and selective deuteration of fine chemicals and pharmaceuticals with low‐cost and sustainable deuterium source.Three types of deuteration strategies are discussed according to the deuteration mode,named deuterium atom transfer strategy,deuterium atom abstraction strategy and deuterated water splitting strategy respectively.The application scope and mechanistic insights are discussed comprehensively.Finally,the perspective on the challenges and future development trends for photo‐and electro‐catalytic deuteration strategies are also presented.展开更多
Single-atom catalysts(SACs),with atomically dispersed metal atoms anchored on a typical support,representing the utmost utilization effi ciency of the atoms,have recently emerged as promising catalysts for a variety o...Single-atom catalysts(SACs),with atomically dispersed metal atoms anchored on a typical support,representing the utmost utilization effi ciency of the atoms,have recently emerged as promising catalysts for a variety of catalytic applications.The electronic properties of the active center of SACs are highly dependent on the local environment constituted by the single metal atom and its surrounding coordination elements.Therefore,engineering the coordination environment near single metal sites,from the fi rst coordination shell to the second shell or higher,would be a rational way to design effi cient SACs with optimized electronic structure for catalytic applications.The wide range of coordination confi gurations,guaranteed by the multiple choices of the type and heterogeneity of the coordination element(N,O,P,S,etc.),further off er a large opportunity to rationally design SACs for satisfactory activities and investigate the structure-performance relationship.In this review,the coordination engineering of SACs by varying the type of coordination element was elaborated and the photocatalytic water splitting of SACs was highlighted.Finally,challenging issues related to the coordination engineering of SACs and their photocatalytic applications were discussed to call for more eff orts devoted to the further development of single-atom catalysis.展开更多
Hydrogenation/deuteration of carbon chloride(C–Cl)bonds is of high significance but remains a remarkable challenge in synthetic chemistry,especially using safe and inexpensive hydrogen donors.In this article,a visibl...Hydrogenation/deuteration of carbon chloride(C–Cl)bonds is of high significance but remains a remarkable challenge in synthetic chemistry,especially using safe and inexpensive hydrogen donors.In this article,a visible-light-photocatalytic watersplitting hydrogenation technology(WSHT)is proposed to in-situ generate active H-species(i.e.,Had)for controllable hydrogenation of aryl chlorides instead of using flammable H2.When applying heavy water-splitting systems,we could selectively install deuterium at the C–Cl position of aryl chlorides under mild conditions for the sustainable synthesis of high-valued added deuterated chemicals.Sub-micrometer Pd nanosheets(Pd NSs)decorated crystallined polymeric carbon nitrides(CPCN)is developed as the bifunctional photocatalyst,whereas Pd NSs not only serve as a cocatalyst of CPCN to generate and stabilize H(D)-species but also play a significant role in the sequential activation and hydrogenation/deuteration of C–Cl bonds.This article highlights a photocatalytic-WSHT for controllable hydrogenation/deuteration of low-cost aryl chlorides,providing a promising way for the photosynthesis of high-valued added chemicals instead of the hydrogen evolution.展开更多
Tandem water electrolysis for the transformation of universal feedstock to value-added chemicals integrated with hydrogen generation and in situ utilization is a promising approach to address the economic challenges o...Tandem water electrolysis for the transformation of universal feedstock to value-added chemicals integrated with hydrogen generation and in situ utilization is a promising approach to address the economic challenges of electrochemical hydrogen evolution and storage.Herein,we present the controllable electrocatalytic deuteration of halides using inexpensive and reusable heavy water(D2 O)as a D-source for the preparation of valuable D-labelled chemicals and pharmaceuticals under mild conditions.This electrochemical deuteration method with high efficiency and selectivity furnishes a series of D-labelled chemicals and pharmaceuticals in high yields with excellent D-incorporation.The reaction efficiency and selectivity,that is,the precise substitution of deuterium atoms at different halogen positions,can be tuned by varying the applied voltages.The results show the great potential of green and economical electrocatalytic methods for producing value-added fine chemicals in addition to hydrogen evolution.展开更多
Pyrimidines and their derivatives are widely found in natural products,agrochemicals,and pharmaceutical compounds,such as osimertinib,tofacitinnib,nilotinib,and fluoxastrobin(Fig.S1 online)[1].Considering their signif...Pyrimidines and their derivatives are widely found in natural products,agrochemicals,and pharmaceutical compounds,such as osimertinib,tofacitinnib,nilotinib,and fluoxastrobin(Fig.S1 online)[1].Considering their significance,the effective construction of pyrimidines has gained considerable attention[2,3].展开更多
Tandem electrocatalysis is an emerging concept for effective electrochemical CO_(2) reduction reaction(CO_(2)RR)towards multicarbons(C_(2+)).This decouples the multiple steps of CO_(2)-to-C_(2+)into two steps of CO_(2...Tandem electrocatalysis is an emerging concept for effective electrochemical CO_(2) reduction reaction(CO_(2)RR)towards multicarbons(C_(2+)).This decouples the multiple steps of CO_(2)-to-C_(2+)into two steps of CO_(2)-to-CO and CO-to-C_(2+)catalyzed by individual catalysts,to improve the Faradic efficiency(FE).However,due to the mass-transport limitation of CO from the generation site to the long-distance consumption site,such a strategy still remains challenge for high-rate production of C_(2+)products.Herein,we designed CuO/Ni single atoms tandem catalyst,which made the catalytic sites of Ni and Cu for independently catalyzing CO_(2)-to-CO and CO-to-C_(2+)compactly neighbored,enabling the in-situ generation and rapid consumption of CO.The CuO/Ni SAs tandem catalyst achieved a particularly high partial current density of C_(2+)products(1220.8 mA/cm^(2)),while still maintained outstanding C_(2+)products FE(81.4%)and excellent selectivities towards ethylene(FE 54.1%)and ethanol(FE 28.8%),enabling the profitable production of multicarbons by CO_(2)RR.展开更多
A merger of copper catalysis and semiconductor photocatalysis using polymeric carbon nitride(PCN)for multi-type cross-coupling reactions was developed.This dual-catalytic system enables mild C-H arylation,chalcogenati...A merger of copper catalysis and semiconductor photocatalysis using polymeric carbon nitride(PCN)for multi-type cross-coupling reactions was developed.This dual-catalytic system enables mild C-H arylation,chalcogenation,and C-N cross-coupling reactions under visible light irradiation with a broad substrate scope.Good-to-excellent yields were obtained with appreciable site selectivity and functional group tolerance.Metal-free and low-cost PCN photocatalyst can easily be recovered and reused several times.展开更多
Direct ink writing(DIW)has recently emerged as an appealing method for designing and fabricating three-dimensional(3D)objects.Complex 3D structures can be built layer-by-layer via digitally controlled extrusion and de...Direct ink writing(DIW)has recently emerged as an appealing method for designing and fabricating three-dimensional(3D)objects.Complex 3D structures can be built layer-by-layer via digitally controlled extrusion and deposition of aqueous-based colloidal pastes.The formulation of well-dispersed suspensions with specific rheological behaviors is a prerequisite for the use of this route.In this review article,the fundamental concepts of DIW are presented,including the operation principles and basic features.Typical strategies used for ink formulation are discussed with a focus on the most widely used electrode materials,including graphene,Mxenes,and carbon nanotubes.The recent progress in printing design of emerging energy storage systems,encompassing rechargeable batteries,supercapacitors,and hybrid capacitors,is summarized.Challenges and future perspectives are also covered to provide guidance for the future development of DIW.展开更多
2D transition metal dichalcogenides(TMDs)have been considered as promising non-precious electrocatalysts for the hydrogen evolution reaction(HER).However,their limited active sites and poor electric conductivity pose ...2D transition metal dichalcogenides(TMDs)have been considered as promising non-precious electrocatalysts for the hydrogen evolution reaction(HER).However,their limited active sites and poor electric conductivity pose a significant hurdle to their HER performance,resulting in a large overpotential.Here,we report the defect engineering in ultrathin tungsten telluride(WTe_(2))nanosheets with semimetal nature to improve hydrogen evolution effectively.We find that the oxygen plasma etching imposes a cutting effect on WTe_(2)nanosheets,resulting in a large number of tungsten vacancies.Particularly,the sample after plasma treatment for 10 min shows a feather-like structure with an overpotential of 251m V at 10 m A/cm~2and a Tafel slope of 94 m V/dec,which is 4 times lower than the Tafel slope of pristine nanosheets.Further first-principles calculations shed light on the evolution of defect-rich WTe_(2)nanosheets and offer rational explanation to their superiority in efficient hydrogen evolution.展开更多
Ultrabroad spectral absorption is required for semiconductor photocatalysts utilized for solar-to-chemical energy conversion.The light response range can be extended by element doping,but the photocatalytic performanc...Ultrabroad spectral absorption is required for semiconductor photocatalysts utilized for solar-to-chemical energy conversion.The light response range can be extended by element doping,but the photocatalytic performance is generally not enhanced correspondingly.Here we present a solid alkali activation strategy to synthesize near-infrared(NIR)light-activated carbon-doped polymeric carbon nitride(A-cPCN)by combining the copolymerization of melamine and 1,3,5-trimesic acid.The prepared A-cPCN is highly crystalline with a narrowed bandgap and enhanced efficiency in the separation of photogenerated electrons and holes.Under irradiation with NIR light(780 nm≥λ≥700 nm),A-cPCN shows an excellent photocatalytic activity for H_(2)generation from water with rate of 165µmol g^(−1)h^(−1),and the photo-redox activity for H_(2)O_(2)production(109µmol g^(−1)h^(−1))from H_(2)O and O_(2),whereas no observed photocatalytic activity over pure PCN.The NIR photocatalytic activity is due to carbon doping,which leads to the formation of an interband level,and the alkali activation that achieved shrinking the transfer distance of photocarriers.The current synergistic strategy may open insights to fabricate other carbon-nitrogen-based photocatalysts for enhanced solar energy capture and conversion.展开更多
Two‐dimensional transition metal dichalcogenides(TMDs)play host to a wide range of novel topological states,such as quantum spin Hall insulators,superconductors,and Weyl semimetals.The rich polymorphism in TMDs sugge...Two‐dimensional transition metal dichalcogenides(TMDs)play host to a wide range of novel topological states,such as quantum spin Hall insulators,superconductors,and Weyl semimetals.The rich polymorphism in TMDs suggests that phase engineering can be used to switch between different charge order states.Intercalation of atoms or molecules into the van der Waals gap of TMDs has emerged as a powerful approach to modify the properties of the material,leading to phase transition or the formation of substoichiometric phases via compositional tuning,thus broadening the electronic and optical landscape of these materials for a wide range of applications.Here,we review the current efforts in the preparation of intercalated TMD.The challenges and opportunities for intercalated TMDs to create a new device paradigm for material science are discussed.展开更多
Herein,a series of carbazolyl cyanobenzene(CCB)-based organic photocatalysts with a broad range of photoredox capabilities were designed and synthesized,allowing precise control of the photocatalytic reactivity for th...Herein,a series of carbazolyl cyanobenzene(CCB)-based organic photocatalysts with a broad range of photoredox capabilities were designed and synthesized,allowing precise control of the photocatalytic reactivity for the controllable reduction of aryl halides via a metal-free process.The screened-out CCB(5CzBN),a metal-free,low-cost,scalable and sustainable photocatalyst with both strong oxidative and reductive ability,exhibits superior performance for both dehalogenation and C—C bond-forming arylation reactions.展开更多
Platinum based alloys are hereinto the mostly used methanol oxidation catalysts.However,there are limited ways to improve the methanol oxidation reaction(MOR)performance of catalysts in terms of both activity and stab...Platinum based alloys are hereinto the mostly used methanol oxidation catalysts.However,there are limited ways to improve the methanol oxidation reaction(MOR)performance of catalysts in terms of both activity and stability.Herein we developed a simple heat-treatment method to synthesize PtCu_(3)/C intermetallic compound catalyst with lattice compression.The as-prepared PtCu_(3)/C-1000 exhibited high specific activity of 3.23 mA·cm^(-1) and mass activity of 1,200 mA·mgPt^(-1),which is much higher than the PtCu_(3)/C-untreated and commercial Pt/C catalysts,respectively.The XAS and DFT results shows the high activity of the catalyst towards MOR comes from the tightening of the Pt-M bond,which leads to the decrease of Fermi energy level and the make it difficulty in adsorbing carbon intermediates,thus releasing more active sites to promote the improvement of MOR performance.Moreover,the PtCu_(3)/C-1000 shows better stability which is due to the surface-rich Pt prevents Cu from dissolution.展开更多
The on-surface self-assembly of inorganic atomic clusters and organic molecules offers significant opportunities to design novel hybrid materials with tailored functionalities.By adopting the advantages from both inor...The on-surface self-assembly of inorganic atomic clusters and organic molecules offers significant opportunities to design novel hybrid materials with tailored functionalities.By adopting the advantages from both inorganic and organic components,the hybrid self-assembly molecules have shown great potential in future optoelectrical devices.Herein,we report the co-deposition of 4,8-diethynylbenzo[1,2-d-4,5-d0]bisoxazole(DEBBA)and Se atoms to produce a motif-adjustable organic–inorganic hybrid self-assembly system via the non-covalent interactions.By controlling the coverage of Se atoms,various chiral molecular networks containing Se,Se_(6),Se_(8),and terminal alkynes evolved on the Ag(111)surface.In particular,with the highest coverage of Se atoms,phase segregation into alternating one-dimensional chains of non-covalently bonded Se_(8) clusters and organic ligands has been noticed.The atom-coverage dependent evolution of self-assembly structures reflects the remarkable structural adaptability of Se clusters as building blocks based on the spontaneous resize to reach the maximum non-covalent interactions.This work has significantly extended the possibilities of flexible control in self-assembly nanostructures to enable more potential functions for broad applications.展开更多
With the ever-increasing demands of grid-scale energy storage,aqueous zinc-ion batteries(ZIBs)have garnered increasing attention around the world.However,limited Zn^(2+)host materials have hindered the commercializati...With the ever-increasing demands of grid-scale energy storage,aqueous zinc-ion batteries(ZIBs)have garnered increasing attention around the world.However,limited Zn^(2+)host materials have hindered the commercialization of ZIBs.Hence,Mo-V oxides with different phase structures(orth-,tri-,and tetra-MoVO)were precisely constructed to develop phase-dependent Mo-V oxide cathodes for Zn^(2+)storage in ZIBs.The open frameworks and varied tunnel structures formed a favorable alternative for achieving suitable Zn^(2+)diffusion kinetics.With optimized phase engineering,the high specific capacity of approximately 400 mA h g^(−1) and excellent cyclic stability of 1000 cycles were achieved with orth-MoVO as the cathode.The large amount of six-and seven-member rings in the orth-MoVO phase,which allow for alternative Zn^(2+)insertion,play a vital role in hosting Zn^(2+)ions reversibly.The proposed phase engineering strategy provides a new approach toward cathode design in ZIBs.展开更多
Nature has provided us the assurance and inspiration for thousands of years in synthesizing value-added chemicals,with the assistance of reactive hydrogen species,and water as the ultimate hydrogen source.However,the ...Nature has provided us the assurance and inspiration for thousands of years in synthesizing value-added chemicals,with the assistance of reactive hydrogen species,and water as the ultimate hydrogen source.However,the natural photosynthesis is inefficient due to some intrinsic properties,urging people not only to learn from but also surpass during nature imitation.In this review,we summarized recent progresses on reactive hydrogen species-assisted nanocatalytic reduction of organic molecules towards value-added fine chemicals and pharmaceuticals,with water as the hydrogen source,and especially highlighted how photocatalytically or electrocatalytically evolved reactive hydrogen species synergize with biocatalytic centers and nanocatalytic sites for reduction of organic molecules.The design principles of collaborative semi-artificial systems and nanocatalytic artificial systems,the structure tuning of catalysts for the evolution and utilization of hydrogen species,and the determination of reactive hydrogen species for mechanistic insights were discussed in detail.Finally,perspectives were provided for further advancing this emerging area of nanocatalytic reduction of organic molecules from water(or proton)and organics.展开更多
基金Australian Research Council,Grant/Award Numbers:DP190100120,FT200100015National Key Research and Development Program,Grant/Award Number:2021YFA1600800Shenzhen Science and Technology Program,Grant/Award Numbers:RCJC20200714114434086,JCYJ20190808142001745,JCYJ20200812160737002,20180921273B。
文摘One of the most unique properties of two-dimensional carbides and nitrides of transition metals(MXenes)is their excellent water dispersibility and yet possessing superior electrical conductivity but their industrial-scale application is limited by their costly chemical synthesis methods.In this work,the niche feature of MXenes was capitalized in the packed-bed electrochemical reactor to produce MXenes at an unprecedented reaction rate and yield with minimal chemical waste.A simple NH4F solution was employed as the green electrolyte,which could be used repeatedly without any loss in its efficacy.Surprisingly,both fluoride and ammonium were found to play critical roles in the electrochemical etching,functionalization,and expansion of the layered parent materials(MAXs)through which the liberation of ammonia gas was observed.The electrochemically produced MXenes with excellent conductivity,applied as supercapacitor electrodes,could deliver an ultrahigh volumetric capacity(1408 F cm^(−3))and a volumetric energy density(75.8 Wh L^(−1)).This revolutionary green,energy-efficient,and scalable electrochemical route will not only pave the way for industrial-scale production of MXenes but also open up a myriad of versatile electrochemical modifications for improved functional MXenes.
文摘Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the half‐life of drug metabolism,enhance the efficacy of drugs,close metabolic sites,and decrease side effects.Thus,there is a rising demand for the practical construction of deuterium‐labeled drugs and their intermediates under mild conditions.This paper timely provides an overview of the recent advances in both photo‐and electro‐catalytic mild and selective deuteration of fine chemicals and pharmaceuticals with low‐cost and sustainable deuterium source.Three types of deuteration strategies are discussed according to the deuteration mode,named deuterium atom transfer strategy,deuterium atom abstraction strategy and deuterated water splitting strategy respectively.The application scope and mechanistic insights are discussed comprehensively.Finally,the perspective on the challenges and future development trends for photo‐and electro‐catalytic deuteration strategies are also presented.
基金the National Natural Science Foundation of China(Nos.21805191 and 21972094)the Guangdong Basic and Applied Basic Research Founda-tion(No.2020A1515010982)+1 种基金Shenzhen Pengcheng Scholar Program,Shenzhen Peacock Plan(No.KQTD2016053112042971)Shenzhen Science and Technology Program(Nos.KQJSCX20170727100802505 and RCJC20200714114434086).
文摘Single-atom catalysts(SACs),with atomically dispersed metal atoms anchored on a typical support,representing the utmost utilization effi ciency of the atoms,have recently emerged as promising catalysts for a variety of catalytic applications.The electronic properties of the active center of SACs are highly dependent on the local environment constituted by the single metal atom and its surrounding coordination elements.Therefore,engineering the coordination environment near single metal sites,from the fi rst coordination shell to the second shell or higher,would be a rational way to design effi cient SACs with optimized electronic structure for catalytic applications.The wide range of coordination confi gurations,guaranteed by the multiple choices of the type and heterogeneity of the coordination element(N,O,P,S,etc.),further off er a large opportunity to rationally design SACs for satisfactory activities and investigate the structure-performance relationship.In this review,the coordination engineering of SACs by varying the type of coordination element was elaborated and the photocatalytic water splitting of SACs was highlighted.Finally,challenging issues related to the coordination engineering of SACs and their photocatalytic applications were discussed to call for more eff orts devoted to the further development of single-atom catalysis.
基金supported by the National Natural Science Foundation of China(21972094,51701127,21401190)China Postdoctoral Science Foundation(2017M612709)+5 种基金Guangdong Special Support ProgramPengcheng Scholar ProgramShenzhen Peacock Plan(KQJSCX20170727100802505,KQTD2016053112042971)Educational Commission of Guangdong Province(2016KTSCX126)Foundation for Distinguished Young Talents in Higher Education of Guangdong(2018KQNCX221)Shenzhen Innovation Program(JCYJ20170818142642395).
文摘Hydrogenation/deuteration of carbon chloride(C–Cl)bonds is of high significance but remains a remarkable challenge in synthetic chemistry,especially using safe and inexpensive hydrogen donors.In this article,a visible-light-photocatalytic watersplitting hydrogenation technology(WSHT)is proposed to in-situ generate active H-species(i.e.,Had)for controllable hydrogenation of aryl chlorides instead of using flammable H2.When applying heavy water-splitting systems,we could selectively install deuterium at the C–Cl position of aryl chlorides under mild conditions for the sustainable synthesis of high-valued added deuterated chemicals.Sub-micrometer Pd nanosheets(Pd NSs)decorated crystallined polymeric carbon nitrides(CPCN)is developed as the bifunctional photocatalyst,whereas Pd NSs not only serve as a cocatalyst of CPCN to generate and stabilize H(D)-species but also play a significant role in the sequential activation and hydrogenation/deuteration of C–Cl bonds.This article highlights a photocatalytic-WSHT for controllable hydrogenation/deuteration of low-cost aryl chlorides,providing a promising way for the photosynthesis of high-valued added chemicals instead of the hydrogen evolution.
基金supported by the National Natural Science Foundation of China(21972094,21902105)the National Postdoctoral Program for Innovative Talents(BX20180203)+4 种基金China Postdoctoral Science Foundation(2018M643176)Guangdong Special Support ProgramPengcheng Scholar programShenzhen Peacock Plan(KQJSCX20170727100802505 and KQTD2016053112042971)Foundation for Distinguished Young Talents in Higher Education of Guangdong(2018KQNCX221)。
文摘Tandem water electrolysis for the transformation of universal feedstock to value-added chemicals integrated with hydrogen generation and in situ utilization is a promising approach to address the economic challenges of electrochemical hydrogen evolution and storage.Herein,we present the controllable electrocatalytic deuteration of halides using inexpensive and reusable heavy water(D2 O)as a D-source for the preparation of valuable D-labelled chemicals and pharmaceuticals under mild conditions.This electrochemical deuteration method with high efficiency and selectivity furnishes a series of D-labelled chemicals and pharmaceuticals in high yields with excellent D-incorporation.The reaction efficiency and selectivity,that is,the precise substitution of deuterium atoms at different halogen positions,can be tuned by varying the applied voltages.The results show the great potential of green and economical electrocatalytic methods for producing value-added fine chemicals in addition to hydrogen evolution.
基金supported by the National Key Research and Development Program of China(2021YFA1600800)the National Natural Science Foundation of China(21972094,22372102,and22102102)+3 种基金the Educational Commission of Guangdong Province(839-0000013131)Guangdong Basic and Applied Basic Re-search Foundation(2020A1515010982)Shenzhen Science and Technology Program(RCJC20200714114434086 and 20221425)the Research Team Cultivation Program of Shenzhen University(2023QNT013)。
文摘Pyrimidines and their derivatives are widely found in natural products,agrochemicals,and pharmaceutical compounds,such as osimertinib,tofacitinnib,nilotinib,and fluoxastrobin(Fig.S1 online)[1].Considering their significance,the effective construction of pyrimidines has gained considerable attention[2,3].
基金supported by the National Key R&D Program of China(2020YFA0710200)the DNL Cooperation Fund,Chinese Academy of Sciences(DNL201918)+6 种基金the Fundamental Research Funds for the Central Universities(WK2060000004,WK2060000021,WK2060000025,KY2060000180,and KY2060000195)the National Natural Science Foundation of China(21805191)Pengcheng Scholar Program,China Postdoctoral Science Foundation(2019M653004)Shenzhen Peacock Plan(KQTD2016053112042971)Shenzhen Science and Technology Program(JCYJ20190808142001745,JCYJ20200812160737002,and RCJC20200714114434086)Guangdong Basic and Applied Basic Research Foundation(2020A1515010982)Shenzhen Stable Support Project(20200812122947002)。
文摘Tandem electrocatalysis is an emerging concept for effective electrochemical CO_(2) reduction reaction(CO_(2)RR)towards multicarbons(C_(2+)).This decouples the multiple steps of CO_(2)-to-C_(2+)into two steps of CO_(2)-to-CO and CO-to-C_(2+)catalyzed by individual catalysts,to improve the Faradic efficiency(FE).However,due to the mass-transport limitation of CO from the generation site to the long-distance consumption site,such a strategy still remains challenge for high-rate production of C_(2+)products.Herein,we designed CuO/Ni single atoms tandem catalyst,which made the catalytic sites of Ni and Cu for independently catalyzing CO_(2)-to-CO and CO-to-C_(2+)compactly neighbored,enabling the in-situ generation and rapid consumption of CO.The CuO/Ni SAs tandem catalyst achieved a particularly high partial current density of C_(2+)products(1220.8 mA/cm^(2)),while still maintained outstanding C_(2+)products FE(81.4%)and excellent selectivities towards ethylene(FE 54.1%)and ethanol(FE 28.8%),enabling the profitable production of multicarbons by CO_(2)RR.
基金supported by the National Natural Science Foundation of China(21972094 and 21805191)Guangdong Special Support Program+4 种基金Pengcheng Scholar ProgramChina Postdoctoral Science Foundation(2019M653004)Shenzhen Peacock Plan(KQTD2016053112042971)Shenzhen Science and Technology Program(JCYJ20190808142001745,JCYJ20200812160737002,and RCJC20200714114434086)Guangdong Basic and Applied Basic Research Foundation(2020A1515010982)。
文摘A merger of copper catalysis and semiconductor photocatalysis using polymeric carbon nitride(PCN)for multi-type cross-coupling reactions was developed.This dual-catalytic system enables mild C-H arylation,chalcogenation,and C-N cross-coupling reactions under visible light irradiation with a broad substrate scope.Good-to-excellent yields were obtained with appreciable site selectivity and functional group tolerance.Metal-free and low-cost PCN photocatalyst can easily be recovered and reused several times.
基金supported by the National Natural Science Foundation of China(No.52073177)Key Project of Department of Education of Guangdong Province(No.2020KTSCX118)The authors acknowledge the support from Suzhou Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies,Suzhou,China.
文摘Direct ink writing(DIW)has recently emerged as an appealing method for designing and fabricating three-dimensional(3D)objects.Complex 3D structures can be built layer-by-layer via digitally controlled extrusion and deposition of aqueous-based colloidal pastes.The formulation of well-dispersed suspensions with specific rheological behaviors is a prerequisite for the use of this route.In this review article,the fundamental concepts of DIW are presented,including the operation principles and basic features.Typical strategies used for ink formulation are discussed with a focus on the most widely used electrode materials,including graphene,Mxenes,and carbon nanotubes.The recent progress in printing design of emerging energy storage systems,encompassing rechargeable batteries,supercapacitors,and hybrid capacitors,is summarized.Challenges and future perspectives are also covered to provide guidance for the future development of DIW.
基金the National Natural Science Foundation of China(Nos.51728202 and 51909165)the China Postdoctoral Science Foundation(Nos.2020TQ0109 and 2018M630986)+3 种基金the Shenzhen Peacock Plan(No.827-000113)the Science and Technology Planning Project of Guangdong Province(No.2016B050501005)the project Nanotechnology Based Functional Solutions(No.NORTE01-0145-FEDER-000019)Norte Portugal Regional Operational Programme(NORTE2020)under the PORTUGAL 2020。
文摘2D transition metal dichalcogenides(TMDs)have been considered as promising non-precious electrocatalysts for the hydrogen evolution reaction(HER).However,their limited active sites and poor electric conductivity pose a significant hurdle to their HER performance,resulting in a large overpotential.Here,we report the defect engineering in ultrathin tungsten telluride(WTe_(2))nanosheets with semimetal nature to improve hydrogen evolution effectively.We find that the oxygen plasma etching imposes a cutting effect on WTe_(2)nanosheets,resulting in a large number of tungsten vacancies.Particularly,the sample after plasma treatment for 10 min shows a feather-like structure with an overpotential of 251m V at 10 m A/cm~2and a Tafel slope of 94 m V/dec,which is 4 times lower than the Tafel slope of pristine nanosheets.Further first-principles calculations shed light on the evolution of defect-rich WTe_(2)nanosheets and offer rational explanation to their superiority in efficient hydrogen evolution.
基金supported by the National Natural Science Foundation of China(Nos.21972094,21902105,21805191,51701127,21401190)Guangdong Special Support Program,Pengcheng Scholar Program,Shenzhen Innovation Program(Nos.JCYJ20170818142642395,JCYJ20190808142001745)the Natural Science Foundation of Guangdong Province(No.2020A1515010982).
文摘Ultrabroad spectral absorption is required for semiconductor photocatalysts utilized for solar-to-chemical energy conversion.The light response range can be extended by element doping,but the photocatalytic performance is generally not enhanced correspondingly.Here we present a solid alkali activation strategy to synthesize near-infrared(NIR)light-activated carbon-doped polymeric carbon nitride(A-cPCN)by combining the copolymerization of melamine and 1,3,5-trimesic acid.The prepared A-cPCN is highly crystalline with a narrowed bandgap and enhanced efficiency in the separation of photogenerated electrons and holes.Under irradiation with NIR light(780 nm≥λ≥700 nm),A-cPCN shows an excellent photocatalytic activity for H_(2)generation from water with rate of 165µmol g^(−1)h^(−1),and the photo-redox activity for H_(2)O_(2)production(109µmol g^(−1)h^(−1))from H_(2)O and O_(2),whereas no observed photocatalytic activity over pure PCN.The NIR photocatalytic activity is due to carbon doping,which leads to the formation of an interband level,and the alkali activation that achieved shrinking the transfer distance of photocarriers.The current synergistic strategy may open insights to fabricate other carbon-nitrogen-based photocatalysts for enhanced solar energy capture and conversion.
基金Ministry of Education—Singapore,Grant/Award Number:MOE2018‐T3‐1‐005。
文摘Two‐dimensional transition metal dichalcogenides(TMDs)play host to a wide range of novel topological states,such as quantum spin Hall insulators,superconductors,and Weyl semimetals.The rich polymorphism in TMDs suggests that phase engineering can be used to switch between different charge order states.Intercalation of atoms or molecules into the van der Waals gap of TMDs has emerged as a powerful approach to modify the properties of the material,leading to phase transition or the formation of substoichiometric phases via compositional tuning,thus broadening the electronic and optical landscape of these materials for a wide range of applications.Here,we review the current efforts in the preparation of intercalated TMD.The challenges and opportunities for intercalated TMDs to create a new device paradigm for material science are discussed.
基金the National Natural Scie nce Foundation of China(No.21972094)Guangdong Special Support Program+2 种基金Pengcheng Scholar programShenzhen Peacock Plan(Nos.KQJSCX20170727100802505,KQTD2016053112042971)the Educational Commission of Guangdong Province(No.2016KTSCX126)。
文摘Herein,a series of carbazolyl cyanobenzene(CCB)-based organic photocatalysts with a broad range of photoredox capabilities were designed and synthesized,allowing precise control of the photocatalytic reactivity for the controllable reduction of aryl halides via a metal-free process.The screened-out CCB(5CzBN),a metal-free,low-cost,scalable and sustainable photocatalyst with both strong oxidative and reductive ability,exhibits superior performance for both dehalogenation and C—C bond-forming arylation reactions.
基金This work was supported by the National Natural Science Foundation of China(Nos.51872209 and 51972239)the Key programs for Science and Technology Innovation of Wenzhou(No.2018ZG005).
文摘Platinum based alloys are hereinto the mostly used methanol oxidation catalysts.However,there are limited ways to improve the methanol oxidation reaction(MOR)performance of catalysts in terms of both activity and stability.Herein we developed a simple heat-treatment method to synthesize PtCu_(3)/C intermetallic compound catalyst with lattice compression.The as-prepared PtCu_(3)/C-1000 exhibited high specific activity of 3.23 mA·cm^(-1) and mass activity of 1,200 mA·mgPt^(-1),which is much higher than the PtCu_(3)/C-untreated and commercial Pt/C catalysts,respectively.The XAS and DFT results shows the high activity of the catalyst towards MOR comes from the tightening of the Pt-M bond,which leads to the decrease of Fermi energy level and the make it difficulty in adsorbing carbon intermediates,thus releasing more active sites to promote the improvement of MOR performance.Moreover,the PtCu_(3)/C-1000 shows better stability which is due to the surface-rich Pt prevents Cu from dissolution.
基金the Guangdong Basic and Applied Basic Research Foundation(Nos.2019A1515110819 and 2020A1515010767)NRF-CRP grant“Two Dimensional Covalent Organic Framework:Synthesis and Applications”(No.NRF-CRP16-2015-02,funded by National Research Foundation,Prime Minister’s Office,Singapore)+1 种基金the Shenzhen Peacock Plan(No.KQTD2016053112042971)the National Natural Science Foundation of China(Nos.21802067 and 21771156).
文摘The on-surface self-assembly of inorganic atomic clusters and organic molecules offers significant opportunities to design novel hybrid materials with tailored functionalities.By adopting the advantages from both inorganic and organic components,the hybrid self-assembly molecules have shown great potential in future optoelectrical devices.Herein,we report the co-deposition of 4,8-diethynylbenzo[1,2-d-4,5-d0]bisoxazole(DEBBA)and Se atoms to produce a motif-adjustable organic–inorganic hybrid self-assembly system via the non-covalent interactions.By controlling the coverage of Se atoms,various chiral molecular networks containing Se,Se_(6),Se_(8),and terminal alkynes evolved on the Ag(111)surface.In particular,with the highest coverage of Se atoms,phase segregation into alternating one-dimensional chains of non-covalently bonded Se_(8) clusters and organic ligands has been noticed.The atom-coverage dependent evolution of self-assembly structures reflects the remarkable structural adaptability of Se clusters as building blocks based on the spontaneous resize to reach the maximum non-covalent interactions.This work has significantly extended the possibilities of flexible control in self-assembly nanostructures to enable more potential functions for broad applications.
基金supported by Guangdong Natural Science Foundation(2019A1515010675)the Science and Technology Project of Shenzhen(JCYJ20180305125106329,KQJSCX20180328094001794)。
文摘With the ever-increasing demands of grid-scale energy storage,aqueous zinc-ion batteries(ZIBs)have garnered increasing attention around the world.However,limited Zn^(2+)host materials have hindered the commercialization of ZIBs.Hence,Mo-V oxides with different phase structures(orth-,tri-,and tetra-MoVO)were precisely constructed to develop phase-dependent Mo-V oxide cathodes for Zn^(2+)storage in ZIBs.The open frameworks and varied tunnel structures formed a favorable alternative for achieving suitable Zn^(2+)diffusion kinetics.With optimized phase engineering,the high specific capacity of approximately 400 mA h g^(−1) and excellent cyclic stability of 1000 cycles were achieved with orth-MoVO as the cathode.The large amount of six-and seven-member rings in the orth-MoVO phase,which allow for alternative Zn^(2+)insertion,play a vital role in hosting Zn^(2+)ions reversibly.The proposed phase engineering strategy provides a new approach toward cathode design in ZIBs.
基金the financial support of the National Natural Science Foundation of China(Nos.22102102,21805191 and 21972094)China Postdoctoral Science Foundation(No.2021T140472)+4 种基金Guangdong Basic and Applied Basic Research Foundation(No.2020A1515010982)Educational Commission of Guangdong Province(No.839-0000013131)Shenzhen Stable Support Project(Nos.20200812160737002 and 20200812122947002)Shenzhen Peacock Plan(Nos.KQTD2016053112042971,20210308299C,20180921273B,20210802524B,and 827-000421)Shenzhen Science and Technology Program(Nos.JCYJ20190808142001745 and RCJC20200714114434086)。
文摘Nature has provided us the assurance and inspiration for thousands of years in synthesizing value-added chemicals,with the assistance of reactive hydrogen species,and water as the ultimate hydrogen source.However,the natural photosynthesis is inefficient due to some intrinsic properties,urging people not only to learn from but also surpass during nature imitation.In this review,we summarized recent progresses on reactive hydrogen species-assisted nanocatalytic reduction of organic molecules towards value-added fine chemicals and pharmaceuticals,with water as the hydrogen source,and especially highlighted how photocatalytically or electrocatalytically evolved reactive hydrogen species synergize with biocatalytic centers and nanocatalytic sites for reduction of organic molecules.The design principles of collaborative semi-artificial systems and nanocatalytic artificial systems,the structure tuning of catalysts for the evolution and utilization of hydrogen species,and the determination of reactive hydrogen species for mechanistic insights were discussed in detail.Finally,perspectives were provided for further advancing this emerging area of nanocatalytic reduction of organic molecules from water(or proton)and organics.
