Inosine monophosphate(IMP),as a critical umami substance,is one of the most important indicators for evaluating the quality of meat products.Here,a sensitive electrochemiluminescence(ECL)biosensor based on graphdiyne(...Inosine monophosphate(IMP),as a critical umami substance,is one of the most important indicators for evaluating the quality of meat products.Here,a sensitive electrochemiluminescence(ECL)biosensor based on graphdiyne(GDY)/AuNPs/luminol nanocomposites was constructed to detect IMP.The GDY/AuNPs/luminol nanocomposites were synthesized by using simple one-pot method.GDY utilized its 2D framework to disperse and fix gold nanoparticles,which inhibited the agglomeration of gold nanoparticles and greatly improved its stability and catalytic properties.Importantly,GDY/AuNPs/luminol nanocomposites showed excellent catalytic ability and superior ECL activity towards luminol-H_(2)O_(2) systems due to the synergistic effect of GDY and AuNPs.Under optimal conditions,the prepared biosensor exhibited a wide linear range from 0.01 g/L to 20 g/L,a satisfactory limit detection of 0.0013 g/L,as well as an excellent specificity.Moreover,we carried out the precise analysis of IMP in actual meat samples with acceptable results compared to the liquid chromatography.We believe that this work could offer an efficient ECL platform for accurate and reliable report of IMP levels,which is significant for maintaining food quality and safety.展开更多
Developing efficient electrocatalysts for nitrogen reduction reaction(NRR)is crucial to replace the both energy-intensive and environment-malignant Haber-Bosch process.Here using density functional theory calculations...Developing efficient electrocatalysts for nitrogen reduction reaction(NRR)is crucial to replace the both energy-intensive and environment-malignant Haber-Bosch process.Here using density functional theory calculations,we systematically studied the potential of the heteronuclear 3 d transition metal dimers anchored graphdiyne monolayers(FeM@and NiM@GDY,M=Ti,V,Cr,Mn,Fe,Co,Ni,and Cu)as efficient NRR catalysts.Among all the studied double-atom catalysts(DACs),FeCo@and NiCo@GDY are the most promising with excellent NRR catalytic activity,high ability to suppress the competing hydrogen evolution reaction(HER),and good stability.For both FeCo@and NiCo@GDY,NRR prefers to the distal pathway with the calculated onset potentials of -0.44 and -0.36 V,respectively,which are comparable and even better than their homonuclear counterparts.Moreover,FeCo@and NiCo@GDY have higher ability to suppress HER than Fe_(2)@ and Co_(2)@GDY,which may result from the modulated d state electronic structure due to the synergy effect of the heteronuclear atoms in the DACs.Our work not only suggests that FeCo@and NiCo@GDY hold great promises as efficient,low-cost,and stable DACs for NRR,but also further provides a strategy,i.e.alloying the atomic metal catalysts,to improve the NRR catalytic activity and/or selectivity.展开更多
Tensile strain of porous membrane materials can broaden their capacity in gas separation.In this work,using van der Waals corrected density functional theory(DFT)and molecular dynamics(MD)simulations,the performance a...Tensile strain of porous membrane materials can broaden their capacity in gas separation.In this work,using van der Waals corrected density functional theory(DFT)and molecular dynamics(MD)simulations,the performance and mechanism of CO2/CH4 separation through strain-oriented graphdiyne(GDY)monolayer were studied by applying lateral strain.It is demonstrated that the CO2 permeance peaks at 1.29×10^6 gas permeation units(GPU)accompanied with CO2/CH4 selectivity of 5.27×10^3 under ultimate strain,both of which are far beyond the Robeson’s limit.Furthermore,the GDY membrane exhibited a decreasing gas diffusion energy barrier and increasing permeance with the increase of applied tensile strain.CO2 molecule tends to reoriented itself vertically to permeate the membrane.Finally,the CO2 permeability decreases with the increase of the temperature from300 K to 500 K due to conserving of rotational freedom,suggesting an abnormal permeance of CO2 in relation to temperature.Our theoretical results suggest that the stretchable GDY monolayer holds great promise to be an excellent candidate for CO2/CH4 separation,owing to its extremely high selectivity and permeability of CO2.展开更多
Transition metal sulfides are an important category for hydrogen evolution reaction(HER).However,only few edge unsaturated sulfurs functionalize as catalytic sites,which has dramatically limited the catalytic activity...Transition metal sulfides are an important category for hydrogen evolution reaction(HER).However,only few edge unsaturated sulfurs functionalize as catalytic sites,which has dramatically limited the catalytic activity and stability.In this work,planar unsaturated sulfurs in(211)plane of the CoS_(2)nanowires have been successfully activated through constructing Graphdiyne-CoS_(2)heterojunction nanocomposites.The corresponding electrons transfer energy barriers for these planar unsaturated sulfurs have been significantly diminished,which are induced by the synergetic effects of the sp~1 hybridized carbons and unsaturated planar sulfurs.In addition,DFT simulations reveal the synergetic effects of the sp~1 hybridized carbons and unsaturated planar sulfurs can promote electron transfer kinetics of the key step,VolmerHeyrovsky step,of the reaction.As expected,the Graphdiyne-CoS_(2)heterojunction nanocomposites exhibit superior HER catalytic performance with low overpotential of 97 mV at 10 mA cm^(-2),and the Tafel slope of 56 mV dec^(-1).Furthermore,the heterojunction shows outstanding stability as well due to the pr tection of the Graphdiyne(GDY).The approach thus paves the way for the further efficient transition metal disulfides catalyst manufactures.展开更多
Chemical doping is verified to be a promising strategy to regulate local electron distribution and further promote the poor intrinsic catalytic activity of graphdiyne.However,the current doping approach still faces pr...Chemical doping is verified to be a promising strategy to regulate local electron distribution and further promote the poor intrinsic catalytic activity of graphdiyne.However,the current doping approach still faces problems such as precise doping for creating active sites and the destruction of graphdiyne skeleton calling for high temperature.Here,we achieved charge redistribution on graphdiyne surface through molecule functionalization.A p-type molecule–F4 TCNQ(2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodime thane)was introduced and the site-defined functionalization was accomplished.Theoretical calculations showed that the charge transfer ability is improved and graphdiyne becomes positively charged.The oxygen reduction electrocatalysis was conducted as a proof of principle,where the electronic states of sp hybridized C active site was tuned toward favorable reaction intermediates’adsorption.Such work from both theoretical prediction and experimental validation,found that molecule functionalization is effective to promote the electrocatalytic oxygen reduction,which creates new possibilities for graphdiyne’s applications in different electrochemical reactions.展开更多
On-surface synthesis of semiconducting graphdiyne nanowires usually su er severe side re- actions owing to the high reactivity of the butadiynylene units at noble metal surfaces, limiting the production of isolated na...On-surface synthesis of semiconducting graphdiyne nanowires usually su er severe side re- actions owing to the high reactivity of the butadiynylene units at noble metal surfaces, limiting the production of isolated nanowires. In this work, we report the high-yield synthesis of branchless graphdiyne nanowires [-C≡C-Ph2-C≡C-]n via on-surface Ullmann coupling of 1,4-bis(4-bromophenyl)-1,3-butadiyne molecules with chemical vapor deposition method. Non-contact atomic force microscopy with single-bond resolution reveals that single gold adatoms act as e ective protecting groups for butadiynylene units by forming Au-π ligand bonds, preventing unwanted branched coupling reactions and enabling the synthesis of ultralong isolated graphdiyne nanowires. This study will stimulate further investigation on the role of various surface adatoms in protecting on-surface reactions.展开更多
Compared to single-atom catalysts,supported metal clusters can exhibit enhanced activity and designated selectivity in heterogeneous catalysis due to their unique geometric and electronic features.Herein,by means of c...Compared to single-atom catalysts,supported metal clusters can exhibit enhanced activity and designated selectivity in heterogeneous catalysis due to their unique geometric and electronic features.Herein,by means of comprehensive density functional theory (DFT) computations,we systematically investigated the potential of several Ni clusters supported on graphdiyne (Ni_(x)/GDY,x=1–6) for CO_(2) reduction reaction (CO_(2)RR).Our results revealed that,due to the strong interaction between Ni atoms and sp-hybridized C atoms,these supported Ni clusters on GDY exhibit high stabilities and excellent electronic properties.In particular,according to the computed free energy profiles for CO_(2)RR on these Ni_(x)/GDY systems,the anchored Ni_(4) cluster was revealed to exhibit high CO_(2)RR catalytic activity with a small limiting potential and moderate kinetic barrier for C–C coupling,and CH_(4),C_(2)H_(5)OH,and C_(3)H_(7)OH were identified as the main products,which can be attributed to its strong capacity for CO_(2) activation due to its unique configuration and excellent electronic properties.Thus,by carefully controlling the precise numbers of atoms in sub-nano clusters,the spatially confined Ni clusters can perform as promising CO_(2)RR catalysts with high-efficiency and high-selectivity,which may provide a useful guidance to further develop novel and low-cost metal clusters-based catalysts for sustain CO_(2)conversion to valuable chemicals and fuels.展开更多
The mechanical behavior of single-layer graphdiyne(SLGDY)subjected to high-velocity micro-ballistic impacts is analyzed by molecular dynamics(MD)simulations.The ballistic limits of SLGDY is obtained for the first time...The mechanical behavior of single-layer graphdiyne(SLGDY)subjected to high-velocity micro-ballistic impacts is analyzed by molecular dynamics(MD)simulations.The ballistic limits of SLGDY is obtained for the first time.The temperature deterioration effects of the impact resistance are also investigated.The results show that the ballistic limits can reach 75.4%of single-layer graphene(SLGR)at about 1/2 density,leading to approximately the same specific energy absorption(SEA)as SLGR.The ballistic limits of SLGDY and SLGR with single atomic thickness agree with the predictions of macroscopic penetration limits equations,implying the applicability of continuum penetration theories for two-dimensional(2D)materials.In addition,the dynamic responses involving stress wave propagation,conic deformation,and damage evolution are investigated to illuminate the mechanisms of the dynamic energy dissipation.The superior impact resistance of SLGDY and SLGR can be attributed to both the ultra-fast elastic and conic waves and the excellent deformation capabilities.This study provides a deep understanding of the impact behavior of SLGDY,indicating it is a promising protective material.展开更多
Modulating electronic structure of metal nanoparticles via metal–support interaction has attracted intense interest in the field of catalytic science.However,the roles of supporting substrates in regulating catalytic...Modulating electronic structure of metal nanoparticles via metal–support interaction has attracted intense interest in the field of catalytic science.However,the roles of supporting substrates in regulating catalytic properties of nanozymes remain elusive.In this study,we find that the use of graphdiyne oxide(GDYO)as the substrate for self-terminating growth of Ru nanoparticles(Ru@GDYO)endows the peroxidase-like activity of Ru nanoparticles with intrinsic physiological pH preference and natural horseradish peroxidase(HRP)comparable performance.Ru nanoparticles electrolessly deposited onto GDYO possess a partially oxidized electronic structure owing to limited charge transfer between Ru and GDYO,contributing to the intrinsic physiological pH preference of the peroxidase-mimicking nanozyme.More importantly,the substrate GDYO plays an influential factor in enhancing catalytic activity,that is,the activity of Ru@GDYO is much higher than that of Ru nanoparticles deposited on other carbon substrates including graphene oxides and graphdiyne.To demonstrate the application of Ru@GDYO nanozyme in neutral solutions,we employ Ru@GDYO with nicotinamide adenine dinucleotide(NAD+)-dependent dehydrogenases in physiological conditions to realize a sustainable cascade reaction by means of forming continuous NAD^(+)/dihydronicotiamide adenine dinucleotide(NADH)recycling.Our finding represents a promising perspective on designing high-performance peroxidase-mimicking nanozymes with broader applicability,raising fundamental understanding of structure–activity relationship,and investigating new applications of nanozymes in biological systems.展开更多
Polyoxometalate-based nanocomposites with electrocatalytic activity have been applied in hydrogen evolution reactions(HER).Seawater as the main water resource on the earth should be developed as the water electrolysis...Polyoxometalate-based nanocomposites with electrocatalytic activity have been applied in hydrogen evolution reactions(HER).Seawater as the main water resource on the earth should be developed as the water electrolysis to prepare high-purity hydrogen.In this paper,we used two synthesis strategies to prepare the nanocomposite Co_(4)-POM@Co-PGDY(Co_(4)-POM:the Kegging-type microcrystals of K_(10)[Co_(4)(PW_(9)O_(3)4)2]and Co-PGDY:cobalt-porphyrin linked graphdiyne)with excellent activity for HER.Co-PGDY as the porous material is applied not only as the protection of microcrystals towards the metal ion in seawater but also as the co-electrocatalyst of Co_(4)-POM.Co_(4)-POM@Co-PGDY exhibits excellent HER performance in seawater electrolytes with low overpotential and high stability at high density.Moreover,we have observed a key H_(3)O+intermediate emergence on the surface of nanocomposite during hydrogen evolution process in seawater by Raman synchrotron radiation-based Fourier transform infrared(SR-FTIR).The results in this paper provide an effective strategy for preparing polyoxometalate-based electrocatalysts with high-performance toward hydrogen evolution reaction.展开更多
Lithium (Li)-CO_(2) battery is rising as an attractive energy-storage system with the competence of CO_(2) conversion/fixation. However, its practical development is seriously hindered by the high overpotential. Herei...Lithium (Li)-CO_(2) battery is rising as an attractive energy-storage system with the competence of CO_(2) conversion/fixation. However, its practical development is seriously hindered by the high overpotential. Herein, a rational design on a highly catalytic Li-CO_(2) battery electrode built by graphdiyne powder as a multi-functional laminar scaffold with anchored highly dispersed Ru nanoparticles is explored. The strong interaction between the abundant acetylenic bond sites of graphdiyne scaffold and Ru nanoparticles can effectively promote the electrochemical progress and reduce the voltage polarization. The unique channels architecture of the cathodic catalyst with enough space not only accelerates CO_(2) diffusion and electrons/Li+ transport, but also allows a large amount of accommodation for discharged product (Li2CO3) to assure an advanced capacity. The corresponding Li-CO_(2) battery displays an advanced discharged capacity of 15,030 mAh/g at 500 mA/g, great capacity retention of 8873 mAh/g at 2 A/g, high coulombic efficiency of 97.6% at 500 mA/g and superior life span for 120 cycles with voltage gap of 1.67 V under a restricted capacity of 1000 mAh/g at 500 mA/g. Ex/in-situ studies prove that synergy between Ru nanoparticles and acetylene bonds of GDY can boost the round-trip CO_(2)RR and CO_(2)ER kinetics.展开更多
The direct cleavage of C–NO_(2)bonds for reductive denitration of nitroarenes remains a challenging transformation in synthetic organic chemistry.Herein,we report a biocompatible palladium-deposited graphdiyne nanoca...The direct cleavage of C–NO_(2)bonds for reductive denitration of nitroarenes remains a challenging transformation in synthetic organic chemistry.Herein,we report a biocompatible palladium-deposited graphdiyne nanocatalyst(Pd@GDY/DSPE-PEG)that can catalyze reductive denitration of nitroarenes under ambient physiological conditions.Mechanistic studies support this transformation via the oxidative addition of nitroarenes with Pd(0)and subsequent ligand exchange to form arylpalladium hydride.This one-step reductive denitration via Pd@GDY/DSPE-PEG successfully facilitates the repair of the nitrated proteins arising from endogenic ONOO−and restores their physiological function,including blocking the apoptosis pathway in living cells.Moreover,Pd@GDY/DSPE-PEG was further successfully applied for catalytic denitration to reduce the level of 3-nitrotyrosine residues of proteins located in the mouse brain hippocampus in vivo.This study provides an ideal strategy for designing highly active enzymatic mimicking synthetic catalysts for the regulation of the nitrated protein level and the detoxification of nitrative damage of living cells and tissues.展开更多
The sluggish lithium-ion(Li-ion)transport kinetics in graphite anode hinders its application in fast-charging Li-ion batteries(LIBs).Here,we develop an ionpumping interphase(IPI)on graphdiyne(GDY)/graphite heterojunct...The sluggish lithium-ion(Li-ion)transport kinetics in graphite anode hinders its application in fast-charging Li-ion batteries(LIBs).Here,we develop an ionpumping interphase(IPI)on graphdiyne(GDY)/graphite heterojunction anodes to boost the ionic transport kinetics and enable high-performance,fast-charging LIBs.The IPI changed the ion solvation/desolvation environment by covalent/non-covalent interactions with Li ions or solvents to optimize solid-electrolyte interphase(SEI)and regulate Li-ion transport behavior.We studied the in situ growth of few-layer GDY on graphite surface(GDY/graphite)as the IPI and found that the strong interaction between GDY and Li ions enabled surface-induced modification of the ion solvation behavior and surface-assisted desolvation effect to accelerate the Li-ion desolvation process.A functional anion-derived SEI layer with improved Li-ion conductivity was created.Together with the generated built-in electric field at GDY/graphite hetero-interface self-pumping Li ions to intercalate into the graphite,the Li-ion transport kinetics was significantly enhanced to effectively eliminate Li plating and large voltage polarization of the graphite anodes.A fast Li intercalation in GDY/graphite without Li oversaturation at the edge of the graphite was directly observed.The superior performance with high capacity(139.2 mA h g^(-1))and long lifespan(1650 cycles)under extremely fast-charging conditions(20 C,1 C=372 mA g^(-1))was achieved on GDY/graphite anodes.Even at low temperatures(-20℃),a specific capacity of 128.4 mA h g^(-1) was achieved with a capacity retention of 80%after 500 cycles at a 2 C rate.展开更多
After years of development,graphdiyne(GDY)has demonstrated the characteristics of transformative materials in many fields and has promoted great progress in fundamental and applied research.In practice,some important ...After years of development,graphdiyne(GDY)has demonstrated the characteristics of transformative materials in many fields and has promoted great progress in fundamental and applied research.In practice,some important new concepts have been proposed,such as natural surface charge distribution inhomogeneity,multicavity space limiting effect,incomplete charge transfer effect on the atomic level,alkyne-alkene conversion of a chemical bond,in situ induction of constrained growth,reversible transition from high to low valence state,and so on.These characteristics originating from the special electronic structure and chemical structure of GDY have rapidly promoted the development of GDY science in recent years and produced many exciting results in fundamental and applied science.Therefore,we systematically introduce the recent theoretical and experimental progress of GDY in terms of its new structural,electronic,mechanical,thermal,and optical properties and its promising applications in the energy fields of membrane sciences,catalysis,energy storage,and conversion.Specifically,the great breakthrough of GDY zero-valence atomic catalysts,quantum dots catalysts,and heterostructure catalysts for catalytic applications are discussed in detail.We believe this review will provide some significant guidelines for the design and development of GDYbased high-performance materials and devices in energy fields.展开更多
The photocatalytic performance can be significantly improved by constructing suitable heterojunction photocatalysts.It is well known that graphdiyne possesses a unique conjugated carbon network nanostructure,which giv...The photocatalytic performance can be significantly improved by constructing suitable heterojunction photocatalysts.It is well known that graphdiyne possesses a unique conjugated carbon network nanostructure,which gives it ample active sites on its surface and facilitates the reduction of protons.In this study,a unique new double S-scheme heterojunction photocatalyst was constructed by simple self-assembly of GDY prepared via organic synthesis methods and ZnAl-LDH.According to the study,an internal electric field controlling the transfer direction of the electron hole is formed between the interface of CuI-GDY and ZnAl-LDH,which broadens the light absorption range of the catalyst and improves the redox ability of the photocatalytic system.CuI-GDY and ZnAl-LDH are tightly bound together,which helps to separate the photogenerated carriers while preserving the strong reduction electrons in the GDY conduction band and the strong oxidation holes in the ZnAl-LDH valence band so that they can fully participate in the redox reaction.The charge-transfer paths on the S-scheme heterojunction interface were analyzed by in situ irradiation XPS.This work provides an effective strategy for the construction of double S-scheme heterojunction photocatalysts.展开更多
Here we report an in situ assembly growth method that controls the growth of NiTCNQ on the surface of graphdiyne(GDY).The catalytic system of donor–acceptor–donor(GDY/TCNQ/Ni)structure with multiple charge transfer(...Here we report an in situ assembly growth method that controls the growth of NiTCNQ on the surface of graphdiyne(GDY).The catalytic system of donor–acceptor–donor(GDY/TCNQ/Ni)structure with multiple charge transfer(CT)was achieved by controlling the growth of NiTCNQ on the surface of GDY.Significantly,a controlled double layer interface of GDY/TCNQ/Ni was formed.This system implemented simultaneously the two elements we expected(1)an incomplete CT,and(2)the infinite distribution of active sites originating from highly asymmetric surface charge distribution.The high conductivity and typical semiconductor characteristics of the catalyst endows it with high catalytic activity.We found that an electrolytic cell consisting of the CT salt as a catalyst provided a 1.40 V ultra-small cell voltage up to 10 mA cm−2 and the outer GDY film effectively prevented the corrosion of the catalyst.Our study is the first to introduce CT complexes to a novel catalytic material platform for high selectivity of catalysts,and undoubtedly demonstrates the high selectivity,stability,and activity of such catalytic systems,which provides a new space for the development of novel conceptual catalysts.展开更多
While heterogeneous single-atom catalysts(SACs)have achieved great success in the past decade,their application is potentially limited by their simplistic single-atom active centers,which make single-cluster catalysts...While heterogeneous single-atom catalysts(SACs)have achieved great success in the past decade,their application is potentially limited by their simplistic single-atom active centers,which make single-cluster catalysts(SCCs)a natural extension in the domain of heterogeneous catalysis.SCCs with precise numbers of atoms and structural configurations possess SAC merits,yet have greater potential for catalyzing complex reactions and/or bulky reactants.Through systematic quantum-chemical studies and computational screening,we report here the rational design of transition metal three-atom clusters anchored on graphdiyne(GDY)as a novel kind of stable SCC with great promise for efficient and atomically precise heterogenous catalysis.By investigating their structure and catalytic performance for the oxygen reduction reaction,the hydrogen evolution reaction,and the CO_(2)reduction reaction,we have provided theoretical guidelines for their potential applications as heterogeneous catalysts.These GDY-supported three-atom SCCs provide an ideal benchmark scaffold for rational design of atomically precise heterogeneous catalysts for industrially important chemical reactions.展开更多
Graphdiyne(GDY)is fascinating in the construction of efficient and stable catalysts,but their performance is still somewhat restricted due to GDY’s thicker layers,as well as hydrophobic and relatively chemically iner...Graphdiyne(GDY)is fascinating in the construction of efficient and stable catalysts,but their performance is still somewhat restricted due to GDY’s thicker layers,as well as hydrophobic and relatively chemically inert surfaces.Herein,via oxidationexfoliation-reduction strategy,the self-supported electrode material of CoP nanosheets with ultrathin oxygen-containing GDY wrapping(CoP@RGDYO)for effective HER is constructed.The wrapping of ultrathin oxygen-containing GDY promotes charge transfer,improves the surface property,and enhances the acid and alkali resistance as well as the structural stability of the catalyst.As a result,CoP@RGDYO shows enhanced activity and stability in both acidic and alkaline media.Especially,it exhibits a low overpotential of 86 mV and exceptional stability under a 14000-cycle cyclic voltammetry scanning in alkaline media.This work provides new ideas for the design of GDY hybrid materials and the preparation of high-efficiency catalysts.展开更多
Interface engineering of photocatalysts is an effective way to enhance their photocatalytic activity.In this work,the MOF-on-MOF strategy was used to construct the ZIF-9(Co)/Cu_(3)BTC_(2) photocatalyst in situ.Moreove...Interface engineering of photocatalysts is an effective way to enhance their photocatalytic activity.In this work,the MOF-on-MOF strategy was used to construct the ZIF-9(Co)/Cu_(3)BTC_(2) photocatalyst in situ.Moreover,graph-diyne,possessing an inherent capability to facilitate rapid electron transfer at the interface,has been introduced into the ZIF-9(Co)/Cu_(3)BTC_(2) interface to regulate the interfacial carrier migration.The photogenerated carrier transfer capability has been significantly enhanced by the interfacial synergy,while retaining the original active sites and high specific surface area.The exceptional efficiency performance of the composite catalyst under identical conditions could be attributed to the following two key factors:(i)The interfacial S-scheme hetero-junction in ZIF-9(Co)/Cu_(3)BTC_(2) provides the composite catalyst with strong reduction activity,facilitating the involvement of additional electrons in the reduction reaction through bended bands and an internal electric field.(ii)Carrier dynamics analysis shows that graphdiyne,as an electron transport layer,accelerates the charge migration rate at the S-scheme heterojunction interface through the electron relay effect.The incorporation of graphdiyne greatly improves the catalytic activity of MOFs and also demonstrates the great potential of graph-diyne in photocatalysis.This work provides a feasible idea for the interface engineering design of graphdiyne in photocatalysts.展开更多
Tuning the coordination atoms of central metal is an effective means to improve the electrocatalytic activity of atomic catalysts.Herein,iridium(Ir) is proposed to be asymmetrically anchored by sp-N and pyridinic N of...Tuning the coordination atoms of central metal is an effective means to improve the electrocatalytic activity of atomic catalysts.Herein,iridium(Ir) is proposed to be asymmetrically anchored by sp-N and pyridinic N of hydrogen-substituted graphdiyne(HsGDY),and coordinated with OH as an Ir atomic catalyst(Ir_(1)-N-HsGDY).The electron structures,especially the d-band center of Ir atom,are optimized by these specific coordination atoms.Thus,the as-synthesized Ir_(1)-N-HsGDY exhibits excellent electrocatalytic performances for oxygen reduction and hydrogen evolution reactions in both acidic and alkaline media.Benefiting from the unique structure of HsGDY,IrN_(2)(OH)_(3) has been developed and demonstrated to act as the active site in these electrochemical reactions.All those indicate the fresh role of the sp-N in graphdiyne in producing a new anchor way and contributing to promote the electrocatalytic activity,showing a new strategy to design novel electrochemical catalysts.展开更多
基金supported by The National Natural Science Foundation of China(31972198,31622042)The National Key R&D Program of China(2016YFD0400803,2016YFD0401501).
文摘Inosine monophosphate(IMP),as a critical umami substance,is one of the most important indicators for evaluating the quality of meat products.Here,a sensitive electrochemiluminescence(ECL)biosensor based on graphdiyne(GDY)/AuNPs/luminol nanocomposites was constructed to detect IMP.The GDY/AuNPs/luminol nanocomposites were synthesized by using simple one-pot method.GDY utilized its 2D framework to disperse and fix gold nanoparticles,which inhibited the agglomeration of gold nanoparticles and greatly improved its stability and catalytic properties.Importantly,GDY/AuNPs/luminol nanocomposites showed excellent catalytic ability and superior ECL activity towards luminol-H_(2)O_(2) systems due to the synergistic effect of GDY and AuNPs.Under optimal conditions,the prepared biosensor exhibited a wide linear range from 0.01 g/L to 20 g/L,a satisfactory limit detection of 0.0013 g/L,as well as an excellent specificity.Moreover,we carried out the precise analysis of IMP in actual meat samples with acceptable results compared to the liquid chromatography.We believe that this work could offer an efficient ECL platform for accurate and reliable report of IMP levels,which is significant for maintaining food quality and safety.
基金supported by the National Natural Science Foundation of China(Grant Nos.11704005 and 11774078)the Program for Science&Technology Innovation Talents in Universities of Henan Province(Grant No.20HASTIT028)。
文摘Developing efficient electrocatalysts for nitrogen reduction reaction(NRR)is crucial to replace the both energy-intensive and environment-malignant Haber-Bosch process.Here using density functional theory calculations,we systematically studied the potential of the heteronuclear 3 d transition metal dimers anchored graphdiyne monolayers(FeM@and NiM@GDY,M=Ti,V,Cr,Mn,Fe,Co,Ni,and Cu)as efficient NRR catalysts.Among all the studied double-atom catalysts(DACs),FeCo@and NiCo@GDY are the most promising with excellent NRR catalytic activity,high ability to suppress the competing hydrogen evolution reaction(HER),and good stability.For both FeCo@and NiCo@GDY,NRR prefers to the distal pathway with the calculated onset potentials of -0.44 and -0.36 V,respectively,which are comparable and even better than their homonuclear counterparts.Moreover,FeCo@and NiCo@GDY have higher ability to suppress HER than Fe_(2)@ and Co_(2)@GDY,which may result from the modulated d state electronic structure due to the synergy effect of the heteronuclear atoms in the DACs.Our work not only suggests that FeCo@and NiCo@GDY hold great promises as efficient,low-cost,and stable DACs for NRR,but also further provides a strategy,i.e.alloying the atomic metal catalysts,to improve the NRR catalytic activity and/or selectivity.
基金financial support received from the National Natural Science Foundation of China(21776301)the Science Foundation of China University of Petroleum,Beijing(2462018BJC004)。
文摘Tensile strain of porous membrane materials can broaden their capacity in gas separation.In this work,using van der Waals corrected density functional theory(DFT)and molecular dynamics(MD)simulations,the performance and mechanism of CO2/CH4 separation through strain-oriented graphdiyne(GDY)monolayer were studied by applying lateral strain.It is demonstrated that the CO2 permeance peaks at 1.29×10^6 gas permeation units(GPU)accompanied with CO2/CH4 selectivity of 5.27×10^3 under ultimate strain,both of which are far beyond the Robeson’s limit.Furthermore,the GDY membrane exhibited a decreasing gas diffusion energy barrier and increasing permeance with the increase of applied tensile strain.CO2 molecule tends to reoriented itself vertically to permeate the membrane.Finally,the CO2 permeability decreases with the increase of the temperature from300 K to 500 K due to conserving of rotational freedom,suggesting an abnormal permeance of CO2 in relation to temperature.Our theoretical results suggest that the stretchable GDY monolayer holds great promise to be an excellent candidate for CO2/CH4 separation,owing to its extremely high selectivity and permeability of CO2.
基金financially supported by the National Natural Science Foundation of China(No.51972175)the Natural Science Foundation of Tianjin(17JCYBJC40900,18YFZCGX00580)+3 种基金The National Natural Science Foundation of China(Grant No.21872174 and U1932148)the International S&T Cooperation Program of China(2017YFE0127800)the Hundred Youth Talents Program of Hunan.National Natural Science Foundation of China(No.21601171)the Natural Science Foundation of Shandong Province(No.ZR2016BB08)。
文摘Transition metal sulfides are an important category for hydrogen evolution reaction(HER).However,only few edge unsaturated sulfurs functionalize as catalytic sites,which has dramatically limited the catalytic activity and stability.In this work,planar unsaturated sulfurs in(211)plane of the CoS_(2)nanowires have been successfully activated through constructing Graphdiyne-CoS_(2)heterojunction nanocomposites.The corresponding electrons transfer energy barriers for these planar unsaturated sulfurs have been significantly diminished,which are induced by the synergetic effects of the sp~1 hybridized carbons and unsaturated planar sulfurs.In addition,DFT simulations reveal the synergetic effects of the sp~1 hybridized carbons and unsaturated planar sulfurs can promote electron transfer kinetics of the key step,VolmerHeyrovsky step,of the reaction.As expected,the Graphdiyne-CoS_(2)heterojunction nanocomposites exhibit superior HER catalytic performance with low overpotential of 97 mV at 10 mA cm^(-2),and the Tafel slope of 56 mV dec^(-1).Furthermore,the heterojunction shows outstanding stability as well due to the pr tection of the Graphdiyne(GDY).The approach thus paves the way for the further efficient transition metal disulfides catalyst manufactures.
基金supported by the National Natural Science Foundation of China(21773016,21971244,51932001)the National Key R&D Program of China(2018YFA0703504)。
文摘Chemical doping is verified to be a promising strategy to regulate local electron distribution and further promote the poor intrinsic catalytic activity of graphdiyne.However,the current doping approach still faces problems such as precise doping for creating active sites and the destruction of graphdiyne skeleton calling for high temperature.Here,we achieved charge redistribution on graphdiyne surface through molecule functionalization.A p-type molecule–F4 TCNQ(2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodime thane)was introduced and the site-defined functionalization was accomplished.Theoretical calculations showed that the charge transfer ability is improved and graphdiyne becomes positively charged.The oxygen reduction electrocatalysis was conducted as a proof of principle,where the electronic states of sp hybridized C active site was tuned toward favorable reaction intermediates’adsorption.Such work from both theoretical prediction and experimental validation,found that molecule functionalization is effective to promote the electrocatalytic oxygen reduction,which creates new possibilities for graphdiyne’s applications in different electrochemical reactions.
基金the National Key R&D Program of China(No.2016YFA0200603 No.2017YFA0205004)the Anhui Initiative in Quantum Information Technologies(AHY090300)+2 种基金the National Natural Science Foundation of China(No.21473174)the Fundamental Research Funds for the Central Universities(No.WK2060190084 and No.WK2340000082)Ai-di Zhao acknowledges a fellow-ship from the Youth Innovation Promotion Association of Chinese Academy of Science(2011322).
文摘On-surface synthesis of semiconducting graphdiyne nanowires usually su er severe side re- actions owing to the high reactivity of the butadiynylene units at noble metal surfaces, limiting the production of isolated nanowires. In this work, we report the high-yield synthesis of branchless graphdiyne nanowires [-C≡C-Ph2-C≡C-]n via on-surface Ullmann coupling of 1,4-bis(4-bromophenyl)-1,3-butadiyne molecules with chemical vapor deposition method. Non-contact atomic force microscopy with single-bond resolution reveals that single gold adatoms act as e ective protecting groups for butadiynylene units by forming Au-π ligand bonds, preventing unwanted branched coupling reactions and enabling the synthesis of ultralong isolated graphdiyne nanowires. This study will stimulate further investigation on the role of various surface adatoms in protecting on-surface reactions.
基金financially supported by the Natural Science Funds (NSF) for Distinguished Young Scholar of Heilongjiang Province (JC2018004)the Specialized Fund for the Doctoral Research of Jilin Engineering Normal University (BSKJ201916)。
文摘Compared to single-atom catalysts,supported metal clusters can exhibit enhanced activity and designated selectivity in heterogeneous catalysis due to their unique geometric and electronic features.Herein,by means of comprehensive density functional theory (DFT) computations,we systematically investigated the potential of several Ni clusters supported on graphdiyne (Ni_(x)/GDY,x=1–6) for CO_(2) reduction reaction (CO_(2)RR).Our results revealed that,due to the strong interaction between Ni atoms and sp-hybridized C atoms,these supported Ni clusters on GDY exhibit high stabilities and excellent electronic properties.In particular,according to the computed free energy profiles for CO_(2)RR on these Ni_(x)/GDY systems,the anchored Ni_(4) cluster was revealed to exhibit high CO_(2)RR catalytic activity with a small limiting potential and moderate kinetic barrier for C–C coupling,and CH_(4),C_(2)H_(5)OH,and C_(3)H_(7)OH were identified as the main products,which can be attributed to its strong capacity for CO_(2) activation due to its unique configuration and excellent electronic properties.Thus,by carefully controlling the precise numbers of atoms in sub-nano clusters,the spatially confined Ni clusters can perform as promising CO_(2)RR catalysts with high-efficiency and high-selectivity,which may provide a useful guidance to further develop novel and low-cost metal clusters-based catalysts for sustain CO_(2)conversion to valuable chemicals and fuels.
基金supported by the National Natural Science Foundation of China(Grant Nos.11672315,and 11772347)the Science Challenge Project(Grant No.TZ2018001)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant Nos.XDB22040302XDB22040303)。
文摘The mechanical behavior of single-layer graphdiyne(SLGDY)subjected to high-velocity micro-ballistic impacts is analyzed by molecular dynamics(MD)simulations.The ballistic limits of SLGDY is obtained for the first time.The temperature deterioration effects of the impact resistance are also investigated.The results show that the ballistic limits can reach 75.4%of single-layer graphene(SLGR)at about 1/2 density,leading to approximately the same specific energy absorption(SEA)as SLGR.The ballistic limits of SLGDY and SLGR with single atomic thickness agree with the predictions of macroscopic penetration limits equations,implying the applicability of continuum penetration theories for two-dimensional(2D)materials.In addition,the dynamic responses involving stress wave propagation,conic deformation,and damage evolution are investigated to illuminate the mechanisms of the dynamic energy dissipation.The superior impact resistance of SLGDY and SLGR can be attributed to both the ultra-fast elastic and conic waves and the excellent deformation capabilities.This study provides a deep understanding of the impact behavior of SLGDY,indicating it is a promising protective material.
基金supported by the National Natural Science Foundation of China(Nos.22134002 to L.M.,22125406,22074149,and 21790053 to P.Y.)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB30000000)the National Basic Research Program of China(No.2018YFA0703501).
文摘Modulating electronic structure of metal nanoparticles via metal–support interaction has attracted intense interest in the field of catalytic science.However,the roles of supporting substrates in regulating catalytic properties of nanozymes remain elusive.In this study,we find that the use of graphdiyne oxide(GDYO)as the substrate for self-terminating growth of Ru nanoparticles(Ru@GDYO)endows the peroxidase-like activity of Ru nanoparticles with intrinsic physiological pH preference and natural horseradish peroxidase(HRP)comparable performance.Ru nanoparticles electrolessly deposited onto GDYO possess a partially oxidized electronic structure owing to limited charge transfer between Ru and GDYO,contributing to the intrinsic physiological pH preference of the peroxidase-mimicking nanozyme.More importantly,the substrate GDYO plays an influential factor in enhancing catalytic activity,that is,the activity of Ru@GDYO is much higher than that of Ru nanoparticles deposited on other carbon substrates including graphene oxides and graphdiyne.To demonstrate the application of Ru@GDYO nanozyme in neutral solutions,we employ Ru@GDYO with nicotinamide adenine dinucleotide(NAD+)-dependent dehydrogenases in physiological conditions to realize a sustainable cascade reaction by means of forming continuous NAD^(+)/dihydronicotiamide adenine dinucleotide(NADH)recycling.Our finding represents a promising perspective on designing high-performance peroxidase-mimicking nanozymes with broader applicability,raising fundamental understanding of structure–activity relationship,and investigating new applications of nanozymes in biological systems.
基金supported by the National Natural Science Foundation of China(Nos.21831001,21801014,22171024,and 22202037)the Fundamental Research Funds for the Central Universities(No.2412023QD019).
文摘Polyoxometalate-based nanocomposites with electrocatalytic activity have been applied in hydrogen evolution reactions(HER).Seawater as the main water resource on the earth should be developed as the water electrolysis to prepare high-purity hydrogen.In this paper,we used two synthesis strategies to prepare the nanocomposite Co_(4)-POM@Co-PGDY(Co_(4)-POM:the Kegging-type microcrystals of K_(10)[Co_(4)(PW_(9)O_(3)4)2]and Co-PGDY:cobalt-porphyrin linked graphdiyne)with excellent activity for HER.Co-PGDY as the porous material is applied not only as the protection of microcrystals towards the metal ion in seawater but also as the co-electrocatalyst of Co_(4)-POM.Co_(4)-POM@Co-PGDY exhibits excellent HER performance in seawater electrolytes with low overpotential and high stability at high density.Moreover,we have observed a key H_(3)O+intermediate emergence on the surface of nanocomposite during hydrogen evolution process in seawater by Raman synchrotron radiation-based Fourier transform infrared(SR-FTIR).The results in this paper provide an effective strategy for preparing polyoxometalate-based electrocatalysts with high-performance toward hydrogen evolution reaction.
基金the National Natural Science Foundation of China(Nos.21971132 and 52072197)Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)+7 种基金Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)Major Scientific and Technological Innovation Project(No.2019JZZY020405)Major Basic Research Program of Natural Science Foundation of Shandong Province(No.ZR2020ZD09)Taishan Scholar Young Talent Program(No.tsqn201909114)the Key Laboratory of Resource Chemistry,Ministry of Education(No.KLRC_ME2101)Scientific and Technological Innovation Promotion Project for Small-medium Enterprises of Shandong Province(No.2022TSGC1257)Major Research Program of Jining City(No.2020ZDZP024)The 111 Project of China(No.D20017).
文摘Lithium (Li)-CO_(2) battery is rising as an attractive energy-storage system with the competence of CO_(2) conversion/fixation. However, its practical development is seriously hindered by the high overpotential. Herein, a rational design on a highly catalytic Li-CO_(2) battery electrode built by graphdiyne powder as a multi-functional laminar scaffold with anchored highly dispersed Ru nanoparticles is explored. The strong interaction between the abundant acetylenic bond sites of graphdiyne scaffold and Ru nanoparticles can effectively promote the electrochemical progress and reduce the voltage polarization. The unique channels architecture of the cathodic catalyst with enough space not only accelerates CO_(2) diffusion and electrons/Li+ transport, but also allows a large amount of accommodation for discharged product (Li2CO3) to assure an advanced capacity. The corresponding Li-CO_(2) battery displays an advanced discharged capacity of 15,030 mAh/g at 500 mA/g, great capacity retention of 8873 mAh/g at 2 A/g, high coulombic efficiency of 97.6% at 500 mA/g and superior life span for 120 cycles with voltage gap of 1.67 V under a restricted capacity of 1000 mAh/g at 500 mA/g. Ex/in-situ studies prove that synergy between Ru nanoparticles and acetylene bonds of GDY can boost the round-trip CO_(2)RR and CO_(2)ER kinetics.
基金support from the National Natural Science Foundation of China(grant nos.22021002,22020102005,and 22022705)the CAS-Croucher Funding Scheme for Joint Laboratories.
文摘The direct cleavage of C–NO_(2)bonds for reductive denitration of nitroarenes remains a challenging transformation in synthetic organic chemistry.Herein,we report a biocompatible palladium-deposited graphdiyne nanocatalyst(Pd@GDY/DSPE-PEG)that can catalyze reductive denitration of nitroarenes under ambient physiological conditions.Mechanistic studies support this transformation via the oxidative addition of nitroarenes with Pd(0)and subsequent ligand exchange to form arylpalladium hydride.This one-step reductive denitration via Pd@GDY/DSPE-PEG successfully facilitates the repair of the nitrated proteins arising from endogenic ONOO−and restores their physiological function,including blocking the apoptosis pathway in living cells.Moreover,Pd@GDY/DSPE-PEG was further successfully applied for catalytic denitration to reduce the level of 3-nitrotyrosine residues of proteins located in the mouse brain hippocampus in vivo.This study provides an ideal strategy for designing highly active enzymatic mimicking synthetic catalysts for the regulation of the nitrated protein level and the detoxification of nitrative damage of living cells and tissues.
基金the National Nature Science Foundation of China(grant nos.52072222 and 22279073)the National Key Research and Development Project of China(grant no.2022YFA1200044)+2 种基金the Taishan Scholar Project of Shandong Province of China(grant no.62460082061017)the Natural Science Foundation of Shandong Province(grant no.ZR2022ZD35)the National Nature Science Foundation of China(grant nos.21790050 and 21790051).
文摘The sluggish lithium-ion(Li-ion)transport kinetics in graphite anode hinders its application in fast-charging Li-ion batteries(LIBs).Here,we develop an ionpumping interphase(IPI)on graphdiyne(GDY)/graphite heterojunction anodes to boost the ionic transport kinetics and enable high-performance,fast-charging LIBs.The IPI changed the ion solvation/desolvation environment by covalent/non-covalent interactions with Li ions or solvents to optimize solid-electrolyte interphase(SEI)and regulate Li-ion transport behavior.We studied the in situ growth of few-layer GDY on graphite surface(GDY/graphite)as the IPI and found that the strong interaction between GDY and Li ions enabled surface-induced modification of the ion solvation behavior and surface-assisted desolvation effect to accelerate the Li-ion desolvation process.A functional anion-derived SEI layer with improved Li-ion conductivity was created.Together with the generated built-in electric field at GDY/graphite hetero-interface self-pumping Li ions to intercalate into the graphite,the Li-ion transport kinetics was significantly enhanced to effectively eliminate Li plating and large voltage polarization of the graphite anodes.A fast Li intercalation in GDY/graphite without Li oversaturation at the edge of the graphite was directly observed.The superior performance with high capacity(139.2 mA h g^(-1))and long lifespan(1650 cycles)under extremely fast-charging conditions(20 C,1 C=372 mA g^(-1))was achieved on GDY/graphite anodes.Even at low temperatures(-20℃),a specific capacity of 128.4 mA h g^(-1) was achieved with a capacity retention of 80%after 500 cycles at a 2 C rate.
基金This research was made possible as a result of a generous grant from the National Nature Science Foundation of China(grant nos.21790050,21790051,and 22005310)the National Key Research and Development Project of China(grant no.2018YFA0703501).
文摘After years of development,graphdiyne(GDY)has demonstrated the characteristics of transformative materials in many fields and has promoted great progress in fundamental and applied research.In practice,some important new concepts have been proposed,such as natural surface charge distribution inhomogeneity,multicavity space limiting effect,incomplete charge transfer effect on the atomic level,alkyne-alkene conversion of a chemical bond,in situ induction of constrained growth,reversible transition from high to low valence state,and so on.These characteristics originating from the special electronic structure and chemical structure of GDY have rapidly promoted the development of GDY science in recent years and produced many exciting results in fundamental and applied science.Therefore,we systematically introduce the recent theoretical and experimental progress of GDY in terms of its new structural,electronic,mechanical,thermal,and optical properties and its promising applications in the energy fields of membrane sciences,catalysis,energy storage,and conversion.Specifically,the great breakthrough of GDY zero-valence atomic catalysts,quantum dots catalysts,and heterostructure catalysts for catalytic applications are discussed in detail.We believe this review will provide some significant guidelines for the design and development of GDYbased high-performance materials and devices in energy fields.
基金financially supported by the Innovative team for transforming waste cooking oil into clean energy and high valueadded chemicals,China and Ningxia lowgrade resource high value utilization and environmental chemical integration technology innovation team project.
文摘The photocatalytic performance can be significantly improved by constructing suitable heterojunction photocatalysts.It is well known that graphdiyne possesses a unique conjugated carbon network nanostructure,which gives it ample active sites on its surface and facilitates the reduction of protons.In this study,a unique new double S-scheme heterojunction photocatalyst was constructed by simple self-assembly of GDY prepared via organic synthesis methods and ZnAl-LDH.According to the study,an internal electric field controlling the transfer direction of the electron hole is formed between the interface of CuI-GDY and ZnAl-LDH,which broadens the light absorption range of the catalyst and improves the redox ability of the photocatalytic system.CuI-GDY and ZnAl-LDH are tightly bound together,which helps to separate the photogenerated carriers while preserving the strong reduction electrons in the GDY conduction band and the strong oxidation holes in the ZnAl-LDH valence band so that they can fully participate in the redox reaction.The charge-transfer paths on the S-scheme heterojunction interface were analyzed by in situ irradiation XPS.This work provides an effective strategy for the construction of double S-scheme heterojunction photocatalysts.
基金by a generous grant from the National Key Research and Development Project of China(no.2018YFA0703501)the National Nature Science Foundation of China(nos.21790050,21790051,and 22021002)the Key Program of the Chinese Academy of Sciences(no.XDPB13).
文摘Here we report an in situ assembly growth method that controls the growth of NiTCNQ on the surface of graphdiyne(GDY).The catalytic system of donor–acceptor–donor(GDY/TCNQ/Ni)structure with multiple charge transfer(CT)was achieved by controlling the growth of NiTCNQ on the surface of GDY.Significantly,a controlled double layer interface of GDY/TCNQ/Ni was formed.This system implemented simultaneously the two elements we expected(1)an incomplete CT,and(2)the infinite distribution of active sites originating from highly asymmetric surface charge distribution.The high conductivity and typical semiconductor characteristics of the catalyst endows it with high catalytic activity.We found that an electrolytic cell consisting of the CT salt as a catalyst provided a 1.40 V ultra-small cell voltage up to 10 mA cm−2 and the outer GDY film effectively prevented the corrosion of the catalyst.Our study is the first to introduce CT complexes to a novel catalytic material platform for high selectivity of catalysts,and undoubtedly demonstrates the high selectivity,stability,and activity of such catalytic systems,which provides a new space for the development of novel conceptual catalysts.
基金This work was financially supported by the National Natural Science Foundation of China(grant no.22033005 to J.L.and grant no.21903047 to H.X.)The support of Guangdong Provincial Key Laboratory of Catalysis(grant no.2020B121201002)is also acknowledged.The calculations were performed using the supercomputers at Tsinghua National Laboratory for Information Science and Technology,the Computational Chemistry Laboratory of the Department of Chemistry under the Tsinghua Xuetang Talents Program,and the Supercomputer Center of the Southern University of Science and Technology.
文摘While heterogeneous single-atom catalysts(SACs)have achieved great success in the past decade,their application is potentially limited by their simplistic single-atom active centers,which make single-cluster catalysts(SCCs)a natural extension in the domain of heterogeneous catalysis.SCCs with precise numbers of atoms and structural configurations possess SAC merits,yet have greater potential for catalyzing complex reactions and/or bulky reactants.Through systematic quantum-chemical studies and computational screening,we report here the rational design of transition metal three-atom clusters anchored on graphdiyne(GDY)as a novel kind of stable SCC with great promise for efficient and atomically precise heterogenous catalysis.By investigating their structure and catalytic performance for the oxygen reduction reaction,the hydrogen evolution reaction,and the CO_(2)reduction reaction,we have provided theoretical guidelines for their potential applications as heterogeneous catalysts.These GDY-supported three-atom SCCs provide an ideal benchmark scaffold for rational design of atomically precise heterogeneous catalysts for industrially important chemical reactions.
基金supported by the National Natural Science Foundation of China(Nos.201972123,U2003307,and 21861037)the National Key Research and Development Program of China(No.2021YFB35006042)+2 种基金the Natural Science Foundation of Xinjiang Uygur Autonomous Region of China(Nos.2021D01C097,2020D01C062,and 2021D01D09)Scientific Research Program of the Higher Education Institution of Xinjiang(XJEDU2021Y005)Open Project of PCOSS(Xiamen University)(2021X20).
文摘Graphdiyne(GDY)is fascinating in the construction of efficient and stable catalysts,but their performance is still somewhat restricted due to GDY’s thicker layers,as well as hydrophobic and relatively chemically inert surfaces.Herein,via oxidationexfoliation-reduction strategy,the self-supported electrode material of CoP nanosheets with ultrathin oxygen-containing GDY wrapping(CoP@RGDYO)for effective HER is constructed.The wrapping of ultrathin oxygen-containing GDY promotes charge transfer,improves the surface property,and enhances the acid and alkali resistance as well as the structural stability of the catalyst.As a result,CoP@RGDYO shows enhanced activity and stability in both acidic and alkaline media.Especially,it exhibits a low overpotential of 86 mV and exceptional stability under a 14000-cycle cyclic voltammetry scanning in alkaline media.This work provides new ideas for the design of GDY hybrid materials and the preparation of high-efficiency catalysts.
基金supprted by the“Fundamental Research Funds for the Central Universities”,North Minzu University(2023XYZHG01)Ningxia low-grade resource high value utilization and environmental chemical integration technology innovation team projectInnovative team for transforming waste cooking oil into clean energy and high value-added chemicals,China
文摘Interface engineering of photocatalysts is an effective way to enhance their photocatalytic activity.In this work,the MOF-on-MOF strategy was used to construct the ZIF-9(Co)/Cu_(3)BTC_(2) photocatalyst in situ.Moreover,graph-diyne,possessing an inherent capability to facilitate rapid electron transfer at the interface,has been introduced into the ZIF-9(Co)/Cu_(3)BTC_(2) interface to regulate the interfacial carrier migration.The photogenerated carrier transfer capability has been significantly enhanced by the interfacial synergy,while retaining the original active sites and high specific surface area.The exceptional efficiency performance of the composite catalyst under identical conditions could be attributed to the following two key factors:(i)The interfacial S-scheme hetero-junction in ZIF-9(Co)/Cu_(3)BTC_(2) provides the composite catalyst with strong reduction activity,facilitating the involvement of additional electrons in the reduction reaction through bended bands and an internal electric field.(ii)Carrier dynamics analysis shows that graphdiyne,as an electron transport layer,accelerates the charge migration rate at the S-scheme heterojunction interface through the electron relay effect.The incorporation of graphdiyne greatly improves the catalytic activity of MOFs and also demonstrates the great potential of graph-diyne in photocatalysis.This work provides a feasible idea for the interface engineering design of graphdiyne in photocatalysts.
基金supported by the National Natural Science Foundation of China(22172090,21790051)the National Key Research and Development Project of China(2022YFA1204500,2022YFA1204501)+2 种基金the Natural Science Foundation of Shan-dong Province(ZR2021MB015)the Open Funds of the State Key Laboratory of Electroanalytical Chemistry(SKLEAC202202)the Young Scholars Program of Shandong University。
文摘Tuning the coordination atoms of central metal is an effective means to improve the electrocatalytic activity of atomic catalysts.Herein,iridium(Ir) is proposed to be asymmetrically anchored by sp-N and pyridinic N of hydrogen-substituted graphdiyne(HsGDY),and coordinated with OH as an Ir atomic catalyst(Ir_(1)-N-HsGDY).The electron structures,especially the d-band center of Ir atom,are optimized by these specific coordination atoms.Thus,the as-synthesized Ir_(1)-N-HsGDY exhibits excellent electrocatalytic performances for oxygen reduction and hydrogen evolution reactions in both acidic and alkaline media.Benefiting from the unique structure of HsGDY,IrN_(2)(OH)_(3) has been developed and demonstrated to act as the active site in these electrochemical reactions.All those indicate the fresh role of the sp-N in graphdiyne in producing a new anchor way and contributing to promote the electrocatalytic activity,showing a new strategy to design novel electrochemical catalysts.
