Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge....Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge.We present a microwave-assisted approach for its continuous,large-scale production which enables synthesis at a rate of 0.6 g/h,with a yield of up to 90%.The synthesized GDY nanosheets have an average diameter of 246 nm and a thickness of 4 nm.We used GDY as a stable coating for potassium(K)metal anodes(K@GDY),taking advantage of its unique molecular structure to provide favorable paths for K-ion transport.This modification significantly inhibited dendrite formation and improved the cycling stability of K metal batteries.Full-cells with perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA)cathodes showed the clear superiority of the K@GDY anodes over bare K anodes in terms of performance,stability,and cycle life.The K@GDY maintained a stable voltage plateau and gave an excellent capacity retention after 600 cycles with nearly 100%Coulombic efficiency.This work not only provides a scalable and efficient way for GDY synthesis but also opens new possibilities for its use in energy storage and other advanced technologies.展开更多
Graphdiyne(GDY)and its derivatives have been considered ideal supporting materials for nanoscale active particles because of their unique atomic and electronic structure.An efficient bi-metal Cu-Pd catalyst was added ...Graphdiyne(GDY)and its derivatives have been considered ideal supporting materials for nanoscale active particles because of their unique atomic and electronic structure.An efficient bi-metal Cu-Pd catalyst was added to produce the uniform deposition of Pd nano-clusters with an average size of~0.95 nm on hydrogen-substituted GDY(HGDY)nanosheets.With the assistance of NaBH4,the resulting Pd/H-GDY was very effective in the degradation of 4-nitrophenol(4-NP),whose conversion was sharply increased to 97.21%in 100 s with a rate constant per unit mass(k`)of 8.97×10^(5)min−1 g^(−1).Additionally,dyes such as methyl orange(MO)and Congo red(CR)were completely degraded within 180 and 90 s,respectively.The Pd/H-GDY maintained this activity after 5 reduction cycles.These results highlight the promising performance of Pd/H-GDY in catalyzing the degradation of various pollutants,which is attributed to the combined effect of the largeπ-conjugated structure of the H-GDY nanosheets and the evenly distributed Pd nanoclusters.展开更多
A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with ...A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy‑like porous Pyr‑GDY.The catalyst exhibited a good electrocatalytic activity for N_(2)reduction in a nitrogen‑saturated electrolyte,with an ammonia yield of 32.1μg·h^(-1)·mg_(cat)^(-1)at-0.3 V(vs RHE),3.5 times higher than that of Au/C(Au NPs anchored on carbon black).In addition,Au/Pyr‑GDY showed a Faraday efficiency(FE)of 26.9%for eNRR,and a good catalysis durability for over 22 h.展开更多
The activity of photocatalysts can be significantly regulated by designing micro-scale interfacial heterojunctions. The present study demonstrates the skillful construction of a graphdiyne/Sr_(2)Co_(2)O_(5) S-scheme h...The activity of photocatalysts can be significantly regulated by designing micro-scale interfacial heterojunctions. The present study demonstrates the skillful construction of a graphdiyne/Sr_(2)Co_(2)O_(5) S-scheme heterojunction, exhibiting exceptional stability, excellent proton adsorption, and remarkable photocatalytic activity. On the basis of in-situ XPS and calculation of work function, it is proved that the electron migration path between the interface of graphdiyne and Sr_(2)Co_(2)O_(5) conforms to the S-scheme heterojunction mechanism. The recombination rate of photogenerated carriers is significantly reduced by virtue of the synergistic effect of the internal electric field and band edge bending while preserving the inherent redox ability of the materials. The strong coupling between layered graphdiyne and hierarchical flower-like Sr_(2)Co_(2)O_(5) effectively enhances the specific surface area of graphdiyne/Sr_(2)Co_(2)O_(5) heterojunction, thereby facilitating H2O pre-adsorption. Combined with experiments and DFT calculations, it was found that both graphdiyne and Sr_(2)Co_(2)O_(5) have a direct band gap, which makes their electronic transitions without the assistance of phonons, thus improving the efficiency of solar energy conversion. This study offers insights into the potential application of graphdiyne and metal oxides in the field of photocatalytic hydrogen evolution.展开更多
Dual-atom catalysts(DACs),a natural extension of single-atom catalysts(SACs),have emerged as a prominent focal point in the field of heterogeneous catalysis,particularly in the context of chemical and energy conversio...Dual-atom catalysts(DACs),a natural extension of single-atom catalysts(SACs),have emerged as a prominent focal point in the field of heterogeneous catalysis,particularly in the context of chemical and energy conversion processes.Despite the fact that the catalytic activity of DACs is significantly modulated by the electronic structure of the catalyst,understanding how electron spin states are affected by variations in topology and geometric structure remains challenging and relatively unexplored.Herein,we propose the rational design of stable DACs composed of two iron atoms anchored on pristine graphdiyne(GDY),Fe_(2)-GDYn.A comprehensive and systematic investigation was carried out to elucidate the electronic configuration and spin states involved in the deliberate convergence towards the magnetic ground state,with the aim of uncovering the structure-spin relationship.Through an in-depth analysis of spin populations,electronic localization/delocalization,and the chemical bonding characteristics of the central metal atoms and the GDY skeleton,it was revealed that the spin coupling between the two iron atoms is preponderantly dictated by adjacent short-range Fe-Fe interactions.Conversely,spin decoupling can be attributed to the long-rangeπ-bond component within the linkage.Moreover,geometric and chemical bonding asymmetries were found to induce orbital and spin splitting in iron atoms possessing an electronic configuration of d8.These findings provide important insights into the relationship between topology and spin,thereby presenting novel strategies for the rational design of spin-manipulated DACs.展开更多
Finding ways to produce dense and smooth perovskite films with negligible defects is vital for achieving high-efficiency perovskite solar cells(PSCs).Herein,we aim to enhance the quality of the perovskite films throug...Finding ways to produce dense and smooth perovskite films with negligible defects is vital for achieving high-efficiency perovskite solar cells(PSCs).Herein,we aim to enhance the quality of the perovskite films through the utilization of a multifunctional additive in the perovskite anti-solvent,a strategy referred to as anti-solvent additive engineering.Specifically,we introduce ortho-substituted-4′-(4,4″-di-tertbutyl-1,1′:3′,1″-terphenyl)-graphdiyne(o-TB-GDY)as an AAE additive,characterized by its sp/sp^2-cohybridized and highlyπ-conjugated structure,into the anti-solvent.o-TB-GDY not only significantly passivates undercoordinated lead defects(through potent coordination originating from specific highπ–electron conjugation),but also serves as nucleation seeds to effectively enhance the nucleation and growth of perovskite crystals.This markedly reduces defects and non-radiative recombination,thereby increasing the power conversion efficiency(PCE)to 25.62%(certified as 25.01%).Meanwhile,the PSCs exhibit largely enhanced stability,maintaining 92.6%of their initial PCEs after 500 h continuous 1-sun illumination at~23°C in a nitrogen-filled glove box.展开更多
Low ionic conductivity is a major obstacle for polymer solid-state electrolytes.In response to this issue,a design concept of enhanced regional electric potential difference(EREPD)is proposed to modulate the interacti...Low ionic conductivity is a major obstacle for polymer solid-state electrolytes.In response to this issue,a design concept of enhanced regional electric potential difference(EREPD)is proposed to modulate the interaction of nanofillers with other components in the composite polymer solid-state electrolytes(CPSEs).While ensuring the periodic structure of the graphdiyne(GDY)backbone,methoxysubstituted GDY(OGDY)is prepared by an asymmetric substitution strategy,which increases the electric potential differences within each repeating unit of GDY.The staggered distributed electron-rich regions and electron-deficient regions on the two-dimensional plane of OGDY increase the free Li^(+)concentration through Lewis acid-base pair interaction.The adjacent ERRs and EDRs form uniformly distributed EREPDs,creating a continuous potential gradient that synergistically facilitates the efficient migration of Li^(+).Impressively,the OGDY/poly(ethylene oxide)(PEO)exhibits a high ionic conductivity(1.1×10^(-3)S cm^(−1))and ion mobility number(0.71).In addition,the accelerated Li^(+)migration promotes the formation of uniform and dense SEI layers and inhibits the growth of lithium dendrites.As a proof of concept,Li||Li symmetric cell and Li||LiFePO_(4)full cell and pouch cell assembled with OGDY/PEO exhibit good performance,highlighting the effectiveness of our EREPD design strategy for improving CPSEs performance.展开更多
Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Here...Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.展开更多
Based on the in-situ self-reduction and chemical stability,graphdiyne(GDY)and graphdiyne oxide(GDYO)are used as trapping agents to investigate the ability for recovering Au^(3+),Ag^+,and Pd^(2+)under different pH valu...Based on the in-situ self-reduction and chemical stability,graphdiyne(GDY)and graphdiyne oxide(GDYO)are used as trapping agents to investigate the ability for recovering Au^(3+),Ag^+,and Pd^(2+)under different pH values and interfering ions.Under strong acidity at pH=1,these two agents demonstrate high select recovery towards the three precious metal ions,which could be insitu reduced to nanoparticles(NPs).In addition,superparamagnetic Fe_(3)O_(4)NPs are deposited on the surfaces of GDY and GDYO.The magnetic responses enable GDYFe_(3)O_(4)to recover precious metals conveniently and efficiently by the aid of an external magnetic field.This study also confirms the antibacterial activity of the as-recovered NPs deposited on GDY and GDYO against Escherichia coli and Staphylococcus aureus(1×10^(5)colony-forming unit(CFU)·mL^(-1)),and the antibacterial rates are 100%.This strategy of recovering precious metals and subsequently reusing to combat pathogens will be of great significance for environmental remediation and biomedical applications.展开更多
The nitrate reduction reaction(NtRR)has been demonstrated to be a promising way for obtaining ammonia(NH_(3))by converting NO3-to NH3.Here we report the controlled synthesis of cobalt tetroxide/graphdiyne heterostruct...The nitrate reduction reaction(NtRR)has been demonstrated to be a promising way for obtaining ammonia(NH_(3))by converting NO3-to NH3.Here we report the controlled synthesis of cobalt tetroxide/graphdiyne heterostructured nanowires(Co_(3)O_(4)/GDY NWs)by a simple two-step process including the synthesis of Co_(3)O_(4)NWs and the following growth of GDY using hex-aethynylbenzene as the precursor at 110°C for 10 h.Detailed scanning electron microscopy,high resolution transmission electron microscopy,X-ray photoelectron spectroscopy,and Raman characterization confirmed the synthesis of a Co_(3)O_(4)/GDY heterointerface with the formation of sp-C-Co bonds at the interface and incomplete charge transfer between GDY and Co,which provide a con-tinuous supply of electrons for the catalytic reaction and ensure a rapid NtRR.Because of these advantages,Co_(3)O_(4)/GDY NWs had an excellent NtRR performance with a high NH3 yield rate(YNH3)of 0.78 mmol h^(-1)cm^(-2)and a Faraday efficiency(FE)of 92.45%at-1.05 V(vs.RHE).This work provides a general approach for synthesizing heterostructures that can drive high-performance ammo-nia production from wastewater under ambient conditions.展开更多
In the process of photocatalytic water cracking,the migration rate and utilization rate of photogenerated charges determine the hydrogen evolution performance of the catalyst.In this paper,a carbon isotope superconduc...In the process of photocatalytic water cracking,the migration rate and utilization rate of photogenerated charges determine the hydrogen evolution performance of the catalyst.In this paper,a carbon isotope superconducting material graphdiyne(GDY)is prepared by mechanical ball milling and introduced into the S-scheme heterojunction Zn_(0.5)Co_(0.5)S/MoS_(2)inorganic system.In terms of hydrogen evolution kinetics,GDY acts as an electron bridge,not only accelerating the migration of photogenerated carriers but also improving the utilization of photogenerated charges.Morphologically,the large twodimensional layer provides more loading and anchoring points for Zn_(0.5)Co_(0.5)S/MoS_(2),which increases the number of active sites.The ternary composite catalyst 20%GDY/Zn_(0.5)Co_(0.5)S/MoS_(2)(20-GCSM)generates 69.94μmol of hydrogen(5 h)in triethanolamine solution.It is 2.97 and1.80 times higher than Zn_(0.5)Co_(0.5)S and Zn_(0.5)Co_(0.5)S/MoS_(2),respectively.After the cyclic experiment,it still has stable hydrogen evolution performance after standing for24 h(under dark conditions).In addition,the potential mechanism of photocatalytic hydrogen evolution is demonstrated through in-situ X-ray photoelectron spectroscopy.This work provides a reference for further research in the field of introducing carbon materials into photocatalytic systems and improving the utilization of photogenerated charges.展开更多
Subnanometer metal clusters play an increasingly important role in heterogeneous catalysis due to their high catalytic activity and selectivity.In this work,by means of the density functional theory(DFT) calculations,...Subnanometer metal clusters play an increasingly important role in heterogeneous catalysis due to their high catalytic activity and selectivity.In this work,by means of the density functional theory(DFT) calculations,the catalytic activities of transition metal clusters with precise numbers of atoms supported on graphdiyne(TM_(1-4)@GDY,TM=V,Cr,Mn,Fe,Co,Ni,Cu,Ru,Rh,Pd,Ir,Pt) were investigated for oxygen evolution reactions(OER),oxygen reduction reactions(ORR) and hydrogen evolution reactions(HER).The computed results reveal that the Pd_(2),Pd_(4) and Pt_(1) anchored graphdiyne can serve as trifunctional catalysts for OER/ORR/HER with the overpotentials of 0.49/0.37/0.06,0.45/0.33/0.12 and 0.37/0.43/0.01 V,respectively,while Pd_(1) and Pt_(2)@graphdiyne can exhibit excellent catalytic performance for water splitting(OER/HER) with the overpotentials of 0.55/0.17 and 0.43/0.03 V.In addition,Ni_(1) and Pd_(3) anchored GDY can perform as bifunctional catalysts for metal-air cells(OER/ORR) and fuels cells(ORR/HER) with the overpotentials of 0.34/0.32 and 0.42/0.04 V,respectively.Thus,by precisely controlling the numbers of atoms in clusters,the TM_(1-4) anchored graphdiyne can serve as promising multifunctional electrocatalysts for OER/ORR/HER,which may provide an instructive strategy to design catalysts for the energy conversation and storage devices.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
Recently,there has been a growing prevalence in the utilization of graphdiyne(GDY)in the field of biomedicine,attributed to its distinctive physical structure and chemical properties.Additionally,its biocompatibility ...Recently,there has been a growing prevalence in the utilization of graphdiyne(GDY)in the field of biomedicine,attributed to its distinctive physical structure and chemical properties.Additionally,its biocompatibility has garnered increasing attention.However,there is a lack of research on the biological effects and physical mechanisms of GDYprotein interactions at the molecular scale.In this study,the villin headpiece subdomain(HP35)served as a representative protein model.Molecular dynamics simulations were employed to investigate the interaction process between the HP35 protein and GDY,as well as the structural evolution of the protein.The data presented in our study demonstrate that GDY can rapidly adsorb HP35 protein and induce denaturation to one of the a-helix structures of HP35 protein.This implies a potential cytotoxicity concern of GDY for biological systems.Compared to graphene,GDY induced less disruption to HP35 protein.This can be attributed to the presence of natural triangular vacancies in GDY,which prevents p–p stacking action and the limited interaction of GDY with HP35 protein is not conducive to the expansion of protein structures.These findings unveil the biological effects of GDY at the molecular level and provide valuable insights for the application of GDY in biomedicine.展开更多
The effective separation ability of photogenerated carriers plays a crucial role in catalytic hydrogen production.Establishing a heterojunction structure is an effective means to overcome the limited carrier separatio...The effective separation ability of photogenerated carriers plays a crucial role in catalytic hydrogen production.Establishing a heterojunction structure is an effective means to overcome the limited carrier separation ability of some single catalysts.In this paper,Cu,graphdiyne(GDY)and NiCoMoO_(4)are successfully coupled to construct a composite photocatalyst NCY-15%.The addition of sheet GDY effectively prevents the aggregation of NiCoMoO_(4),increases the number of active sites,and enhances the light-trapping ability of the composite catalyst.The synergistic interaction of S-scheme heterojunction and Ohmic junction heterojunction between Cu,GDY and NiCoMoO_(4)provides a unique transfer pathway for electrons,facilitating the rapid separation of photogenerated carriers and accelerating electron transfer,while retaining electrons with strong reducing capacity to participate in hydrogen production,thereby increasing the hydrogen evolution rate.This provides a new way for the development of GDY based photocatalysts.展开更多
The permselectivity of H2/O2, H2/N2, H2/CO, and H2/CH4 mixtures passing a graphdiyne membrane is studied by molecular dynamics simulations. At pressure range of 0.047-4.5 GPa, H2 can pass the graphdiyen membrane quick...The permselectivity of H2/O2, H2/N2, H2/CO, and H2/CH4 mixtures passing a graphdiyne membrane is studied by molecular dynamics simulations. At pressure range of 0.047-4.5 GPa, H2 can pass the graphdiyen membrane quickly, while all the O2, N2, CO, and CH4 molecules are blocked. At pressure of 47 kPa, the hydrogen flow is 7 mol/m^2s. With increase of pressure, the hydrogen flow goes up, and reaches maximum of 6×10^5 mol/m^2s at 1.5 GPa. Compared to other known membranes, graphdiyne can be used for means of hydrogen purification with the best balance of high selectivity and high permeance.展开更多
Ammonia synthesis by electrochemical nitrogen reduction technique is an attractive alternative to traditional Haber-Bosch process.Currently,development of an efficient and effective electrocatalyst is one of the remai...Ammonia synthesis by electrochemical nitrogen reduction technique is an attractive alternative to traditional Haber-Bosch process.Currently,development of an efficient and effective electrocatalyst is one of the remaining key challenges.In this work,density functional theory(DFT)computations were systematically employed on double transition metal atoms(Fe,Co,Ni,Cu and Mo)anchored Graphdiyne(GDY)for nitrogen reduction reaction(NRR).The Co-Ni heteronuclear complex and Mo-Mo homonuclear complex showed the highest NRR activity while demonstrating synergistic effect of double atomic catalytic sites towards the promising NRR activity.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
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
Graphdiyne(GDY,g-C_(n)H_(2n-2)),a novel two-dimensional carbon hybrid material,has attracted significant attention owing to its unique and excellent properties.As a new type of carbon material,GDY has a layered struct...Graphdiyne(GDY,g-C_(n)H_(2n-2)),a novel two-dimensional carbon hybrid material,has attracted significant attention owing to its unique and excellent properties.As a new type of carbon material,GDY has a layered structure and can be used in the field of photocatalytic water splitting.Therefore,herein,new progress in the preparation of graphene using Cu I powder as a catalytic material and the combination of a facile hydrothermal method to prepare a new composite material,Co_(9)S_(8)-GDY-Cu I,is reported.The hydrogen production activity of Co9S8-GDY-Cu I in the sensitization system reached 1411.82μmol g^(-1) h^(-1),which is 10.29 times that of pure GDY.A series of characterization techniques were used to provide evidence for the successful preparation of the material and its superior photocatalytic activity.Raman spectroscopy showed that the material contains acetylenic bonds,and the X-ray photoelectron spectroscopy carbon fitting peaks indicated the presence of C-C(sp^(2))and C-C(sp),further demonstrating that GDY was successfully prepared.A possible reaction mechanism was proposed by making use of UV-visible diffuse reflectance and Mott-Schottky analyses.The results showed that a double S-scheme heterojunction was constructed between the samples,which effectively accelerated the separation and transfer of electrons.In addition,the introduction of Co9S8 nanoparticles greatly improved the visible light absorption capacity of Co_(9)S_(8)-GDY-Cu I.Photoluminescence spectroscopy and related electrochemical characterization further proved that recombination of the electron-hole pairs in the composite material was effectively suppressed.展开更多
基金supported by National Natural Science Foundation of China(52302034,52402060,52202201,52021006)Beijing National Laboratory for Molecular Sciences(BNLMS-CXTD202001)+1 种基金Shenzhen Science and Technology Innovation Commission(KQTD20221101115627004)China Postdoctoral Science Foundation(2024T170972)。
文摘Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge.We present a microwave-assisted approach for its continuous,large-scale production which enables synthesis at a rate of 0.6 g/h,with a yield of up to 90%.The synthesized GDY nanosheets have an average diameter of 246 nm and a thickness of 4 nm.We used GDY as a stable coating for potassium(K)metal anodes(K@GDY),taking advantage of its unique molecular structure to provide favorable paths for K-ion transport.This modification significantly inhibited dendrite formation and improved the cycling stability of K metal batteries.Full-cells with perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA)cathodes showed the clear superiority of the K@GDY anodes over bare K anodes in terms of performance,stability,and cycle life.The K@GDY maintained a stable voltage plateau and gave an excellent capacity retention after 600 cycles with nearly 100%Coulombic efficiency.This work not only provides a scalable and efficient way for GDY synthesis but also opens new possibilities for its use in energy storage and other advanced technologies.
基金National Natural Science Foundation of China(52072336,51902285)Zhejiang Provincial Natural Science Foundation(LR23E020002)+1 种基金Fundamental Research Funds for the Central Universities(226-2023-00064,226-2024-00146)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2022SZ-FR001)。
文摘Graphdiyne(GDY)and its derivatives have been considered ideal supporting materials for nanoscale active particles because of their unique atomic and electronic structure.An efficient bi-metal Cu-Pd catalyst was added to produce the uniform deposition of Pd nano-clusters with an average size of~0.95 nm on hydrogen-substituted GDY(HGDY)nanosheets.With the assistance of NaBH4,the resulting Pd/H-GDY was very effective in the degradation of 4-nitrophenol(4-NP),whose conversion was sharply increased to 97.21%in 100 s with a rate constant per unit mass(k`)of 8.97×10^(5)min−1 g^(−1).Additionally,dyes such as methyl orange(MO)and Congo red(CR)were completely degraded within 180 and 90 s,respectively.The Pd/H-GDY maintained this activity after 5 reduction cycles.These results highlight the promising performance of Pd/H-GDY in catalyzing the degradation of various pollutants,which is attributed to the combined effect of the largeπ-conjugated structure of the H-GDY nanosheets and the evenly distributed Pd nanoclusters.
文摘A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy‑like porous Pyr‑GDY.The catalyst exhibited a good electrocatalytic activity for N_(2)reduction in a nitrogen‑saturated electrolyte,with an ammonia yield of 32.1μg·h^(-1)·mg_(cat)^(-1)at-0.3 V(vs RHE),3.5 times higher than that of Au/C(Au NPs anchored on carbon black).In addition,Au/Pyr‑GDY showed a Faraday efficiency(FE)of 26.9%for eNRR,and a good catalysis durability for over 22 h.
基金supported by the Excellent Youth Program,Ningxia Hui Autonomous Region Natural Science Foundation Project(No.2022AAC05034)the Ningxia Low-Grade Resource High-Value Utilization and Environmental Chemical Integration Technology Innovation Team Project of Chinathe Innovative Team for Transforming Waste Cooking Oil into Clean Energy and High Value-Added Chemicals of China.
文摘The activity of photocatalysts can be significantly regulated by designing micro-scale interfacial heterojunctions. The present study demonstrates the skillful construction of a graphdiyne/Sr_(2)Co_(2)O_(5) S-scheme heterojunction, exhibiting exceptional stability, excellent proton adsorption, and remarkable photocatalytic activity. On the basis of in-situ XPS and calculation of work function, it is proved that the electron migration path between the interface of graphdiyne and Sr_(2)Co_(2)O_(5) conforms to the S-scheme heterojunction mechanism. The recombination rate of photogenerated carriers is significantly reduced by virtue of the synergistic effect of the internal electric field and band edge bending while preserving the inherent redox ability of the materials. The strong coupling between layered graphdiyne and hierarchical flower-like Sr_(2)Co_(2)O_(5) effectively enhances the specific surface area of graphdiyne/Sr_(2)Co_(2)O_(5) heterojunction, thereby facilitating H2O pre-adsorption. Combined with experiments and DFT calculations, it was found that both graphdiyne and Sr_(2)Co_(2)O_(5) have a direct band gap, which makes their electronic transitions without the assistance of phonons, thus improving the efficiency of solar energy conversion. This study offers insights into the potential application of graphdiyne and metal oxides in the field of photocatalytic hydrogen evolution.
文摘Dual-atom catalysts(DACs),a natural extension of single-atom catalysts(SACs),have emerged as a prominent focal point in the field of heterogeneous catalysis,particularly in the context of chemical and energy conversion processes.Despite the fact that the catalytic activity of DACs is significantly modulated by the electronic structure of the catalyst,understanding how electron spin states are affected by variations in topology and geometric structure remains challenging and relatively unexplored.Herein,we propose the rational design of stable DACs composed of two iron atoms anchored on pristine graphdiyne(GDY),Fe_(2)-GDYn.A comprehensive and systematic investigation was carried out to elucidate the electronic configuration and spin states involved in the deliberate convergence towards the magnetic ground state,with the aim of uncovering the structure-spin relationship.Through an in-depth analysis of spin populations,electronic localization/delocalization,and the chemical bonding characteristics of the central metal atoms and the GDY skeleton,it was revealed that the spin coupling between the two iron atoms is preponderantly dictated by adjacent short-range Fe-Fe interactions.Conversely,spin decoupling can be attributed to the long-rangeπ-bond component within the linkage.Moreover,geometric and chemical bonding asymmetries were found to induce orbital and spin splitting in iron atoms possessing an electronic configuration of d8.These findings provide important insights into the relationship between topology and spin,thereby presenting novel strategies for the rational design of spin-manipulated DACs.
基金supported by the National Key Research Program of China(Y91Z0152B4,2018YFA0703501)the National Nature Science Foundation of China(22172173,22021002)。
文摘Finding ways to produce dense and smooth perovskite films with negligible defects is vital for achieving high-efficiency perovskite solar cells(PSCs).Herein,we aim to enhance the quality of the perovskite films through the utilization of a multifunctional additive in the perovskite anti-solvent,a strategy referred to as anti-solvent additive engineering.Specifically,we introduce ortho-substituted-4′-(4,4″-di-tertbutyl-1,1′:3′,1″-terphenyl)-graphdiyne(o-TB-GDY)as an AAE additive,characterized by its sp/sp^2-cohybridized and highlyπ-conjugated structure,into the anti-solvent.o-TB-GDY not only significantly passivates undercoordinated lead defects(through potent coordination originating from specific highπ–electron conjugation),but also serves as nucleation seeds to effectively enhance the nucleation and growth of perovskite crystals.This markedly reduces defects and non-radiative recombination,thereby increasing the power conversion efficiency(PCE)to 25.62%(certified as 25.01%).Meanwhile,the PSCs exhibit largely enhanced stability,maintaining 92.6%of their initial PCEs after 500 h continuous 1-sun illumination at~23°C in a nitrogen-filled glove box.
基金supported by the National Key Research and Development Project of China(2022YFA1204500,2022YFA1204503,2018YFA0703501)the National Natural Science Foundation of China(22275115,21875274,11704024)+4 种基金the Natural Science Foundation of Shandong Province(ZR2024ZD02)Natural Science Foundation of Hebei Province(B2020201006)Hebei Province Innovation Capability Enhancement Plan Project(22567620H)Young Scholarship Funding of Shandong University.Post-graduate Innovation Fund Project of Open Laboratory Project Fund of Hebei University(HBU2025SS010)Basic Research Project of Shandong University-Xin’an Group Silicon-Based High-End New Materials Institute.
文摘Low ionic conductivity is a major obstacle for polymer solid-state electrolytes.In response to this issue,a design concept of enhanced regional electric potential difference(EREPD)is proposed to modulate the interaction of nanofillers with other components in the composite polymer solid-state electrolytes(CPSEs).While ensuring the periodic structure of the graphdiyne(GDY)backbone,methoxysubstituted GDY(OGDY)is prepared by an asymmetric substitution strategy,which increases the electric potential differences within each repeating unit of GDY.The staggered distributed electron-rich regions and electron-deficient regions on the two-dimensional plane of OGDY increase the free Li^(+)concentration through Lewis acid-base pair interaction.The adjacent ERRs and EDRs form uniformly distributed EREPDs,creating a continuous potential gradient that synergistically facilitates the efficient migration of Li^(+).Impressively,the OGDY/poly(ethylene oxide)(PEO)exhibits a high ionic conductivity(1.1×10^(-3)S cm^(−1))and ion mobility number(0.71).In addition,the accelerated Li^(+)migration promotes the formation of uniform and dense SEI layers and inhibits the growth of lithium dendrites.As a proof of concept,Li||Li symmetric cell and Li||LiFePO_(4)full cell and pouch cell assembled with OGDY/PEO exhibit good performance,highlighting the effectiveness of our EREPD design strategy for improving CPSEs performance.
文摘Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.
基金financially supported by the National Natural Science Foundation of China(Nos.22062017 and 22164015)Inner Mongolia Autonomous Region Program for Key Science and Technology(No.2020GG0161)+3 种基金Ordos City Program for Key Science and Technology(No.2022YY003)the Program of Higher-Level Talents of Inner Mongolia University(No.10000-22311201/035)the Research Program of science and technology at Universities of Inner Mongolia Autonomous Region(No.NJZZ23091)the Program for Innovative Research Team in Universities of Inner Mongolia Autonomous Region(No.NMGIRT2210)。
文摘Based on the in-situ self-reduction and chemical stability,graphdiyne(GDY)and graphdiyne oxide(GDYO)are used as trapping agents to investigate the ability for recovering Au^(3+),Ag^+,and Pd^(2+)under different pH values and interfering ions.Under strong acidity at pH=1,these two agents demonstrate high select recovery towards the three precious metal ions,which could be insitu reduced to nanoparticles(NPs).In addition,superparamagnetic Fe_(3)O_(4)NPs are deposited on the surfaces of GDY and GDYO.The magnetic responses enable GDYFe_(3)O_(4)to recover precious metals conveniently and efficiently by the aid of an external magnetic field.This study also confirms the antibacterial activity of the as-recovered NPs deposited on GDY and GDYO against Escherichia coli and Staphylococcus aureus(1×10^(5)colony-forming unit(CFU)·mL^(-1)),and the antibacterial rates are 100%.This strategy of recovering precious metals and subsequently reusing to combat pathogens will be of great significance for environmental remediation and biomedical applications.
文摘The nitrate reduction reaction(NtRR)has been demonstrated to be a promising way for obtaining ammonia(NH_(3))by converting NO3-to NH3.Here we report the controlled synthesis of cobalt tetroxide/graphdiyne heterostructured nanowires(Co_(3)O_(4)/GDY NWs)by a simple two-step process including the synthesis of Co_(3)O_(4)NWs and the following growth of GDY using hex-aethynylbenzene as the precursor at 110°C for 10 h.Detailed scanning electron microscopy,high resolution transmission electron microscopy,X-ray photoelectron spectroscopy,and Raman characterization confirmed the synthesis of a Co_(3)O_(4)/GDY heterointerface with the formation of sp-C-Co bonds at the interface and incomplete charge transfer between GDY and Co,which provide a con-tinuous supply of electrons for the catalytic reaction and ensure a rapid NtRR.Because of these advantages,Co_(3)O_(4)/GDY NWs had an excellent NtRR performance with a high NH3 yield rate(YNH3)of 0.78 mmol h^(-1)cm^(-2)and a Faraday efficiency(FE)of 92.45%at-1.05 V(vs.RHE).This work provides a general approach for synthesizing heterostructures that can drive high-performance ammo-nia production from wastewater under ambient conditions.
基金supported by the National Natural Science Foundation of China(No.22062001)。
文摘In the process of photocatalytic water cracking,the migration rate and utilization rate of photogenerated charges determine the hydrogen evolution performance of the catalyst.In this paper,a carbon isotope superconducting material graphdiyne(GDY)is prepared by mechanical ball milling and introduced into the S-scheme heterojunction Zn_(0.5)Co_(0.5)S/MoS_(2)inorganic system.In terms of hydrogen evolution kinetics,GDY acts as an electron bridge,not only accelerating the migration of photogenerated carriers but also improving the utilization of photogenerated charges.Morphologically,the large twodimensional layer provides more loading and anchoring points for Zn_(0.5)Co_(0.5)S/MoS_(2),which increases the number of active sites.The ternary composite catalyst 20%GDY/Zn_(0.5)Co_(0.5)S/MoS_(2)(20-GCSM)generates 69.94μmol of hydrogen(5 h)in triethanolamine solution.It is 2.97 and1.80 times higher than Zn_(0.5)Co_(0.5)S and Zn_(0.5)Co_(0.5)S/MoS_(2),respectively.After the cyclic experiment,it still has stable hydrogen evolution performance after standing for24 h(under dark conditions).In addition,the potential mechanism of photocatalytic hydrogen evolution is demonstrated through in-situ X-ray photoelectron spectroscopy.This work provides a reference for further research in the field of introducing carbon materials into photocatalytic systems and improving the utilization of photogenerated charges.
基金financially supported by Fundamental Research Funds for Heilongjiang Province universities (No.2021-KYYWF-0184)Harbin Normal University Graduate Student Innovation Project (No.HSDSSCX2023-30)。
文摘Subnanometer metal clusters play an increasingly important role in heterogeneous catalysis due to their high catalytic activity and selectivity.In this work,by means of the density functional theory(DFT) calculations,the catalytic activities of transition metal clusters with precise numbers of atoms supported on graphdiyne(TM_(1-4)@GDY,TM=V,Cr,Mn,Fe,Co,Ni,Cu,Ru,Rh,Pd,Ir,Pt) were investigated for oxygen evolution reactions(OER),oxygen reduction reactions(ORR) and hydrogen evolution reactions(HER).The computed results reveal that the Pd_(2),Pd_(4) and Pt_(1) anchored graphdiyne can serve as trifunctional catalysts for OER/ORR/HER with the overpotentials of 0.49/0.37/0.06,0.45/0.33/0.12 and 0.37/0.43/0.01 V,respectively,while Pd_(1) and Pt_(2)@graphdiyne can exhibit excellent catalytic performance for water splitting(OER/HER) with the overpotentials of 0.55/0.17 and 0.43/0.03 V.In addition,Ni_(1) and Pd_(3) anchored GDY can perform as bifunctional catalysts for metal-air cells(OER/ORR) and fuels cells(ORR/HER) with the overpotentials of 0.34/0.32 and 0.42/0.04 V,respectively.Thus,by precisely controlling the numbers of atoms in clusters,the TM_(1-4) anchored graphdiyne can serve as promising multifunctional electrocatalysts for OER/ORR/HER,which may provide an instructive strategy to design catalysts for the energy conversation and storage devices.
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Project supported by the National Natural Science Foundation of China(Grant No.52072132).
文摘Recently,there has been a growing prevalence in the utilization of graphdiyne(GDY)in the field of biomedicine,attributed to its distinctive physical structure and chemical properties.Additionally,its biocompatibility has garnered increasing attention.However,there is a lack of research on the biological effects and physical mechanisms of GDYprotein interactions at the molecular scale.In this study,the villin headpiece subdomain(HP35)served as a representative protein model.Molecular dynamics simulations were employed to investigate the interaction process between the HP35 protein and GDY,as well as the structural evolution of the protein.The data presented in our study demonstrate that GDY can rapidly adsorb HP35 protein and induce denaturation to one of the a-helix structures of HP35 protein.This implies a potential cytotoxicity concern of GDY for biological systems.Compared to graphene,GDY induced less disruption to HP35 protein.This can be attributed to the presence of natural triangular vacancies in GDY,which prevents p–p stacking action and the limited interaction of GDY with HP35 protein is not conducive to the expansion of protein structures.These findings unveil the biological effects of GDY at the molecular level and provide valuable insights for the application of GDY in biomedicine.
基金supported by the Innovative Team for Transforming Waste Cooking Oil into Clean Energy and High Value-Added Chemicals(2022QCXTD03)Ningxia low-grade resource high value utilization and environmental chemical integration technology innovation team project,and Ningxia Natural Science Foundation of 2022(Outstanding Youth Project),Project number:2022AAC05034.
文摘The effective separation ability of photogenerated carriers plays a crucial role in catalytic hydrogen production.Establishing a heterojunction structure is an effective means to overcome the limited carrier separation ability of some single catalysts.In this paper,Cu,graphdiyne(GDY)and NiCoMoO_(4)are successfully coupled to construct a composite photocatalyst NCY-15%.The addition of sheet GDY effectively prevents the aggregation of NiCoMoO_(4),increases the number of active sites,and enhances the light-trapping ability of the composite catalyst.The synergistic interaction of S-scheme heterojunction and Ohmic junction heterojunction between Cu,GDY and NiCoMoO_(4)provides a unique transfer pathway for electrons,facilitating the rapid separation of photogenerated carriers and accelerating electron transfer,while retaining electrons with strong reducing capacity to participate in hydrogen production,thereby increasing the hydrogen evolution rate.This provides a new way for the development of GDY based photocatalysts.
基金V. ACKNOWLEDGMENTS This work was supported by the National Natu- ral Science Foundation of China （No.20603032 and 20733004）, the National Key Basic Research Program （No.2011CB921400）, the Foundation of National Excellent Doctoral Dissertation of China （No.200736）, the Fundamental Research Funds for the Central Universities （No.WK2340000006 and No.WK2060140005）, and the Shanghai Supercomputer Center, the USTC-HP HPC Project, and the SCCAS.
文摘The permselectivity of H2/O2, H2/N2, H2/CO, and H2/CH4 mixtures passing a graphdiyne membrane is studied by molecular dynamics simulations. At pressure range of 0.047-4.5 GPa, H2 can pass the graphdiyen membrane quickly, while all the O2, N2, CO, and CH4 molecules are blocked. At pressure of 47 kPa, the hydrogen flow is 7 mol/m^2s. With increase of pressure, the hydrogen flow goes up, and reaches maximum of 6×10^5 mol/m^2s at 1.5 GPa. Compared to other known membranes, graphdiyne can be used for means of hydrogen purification with the best balance of high selectivity and high permeance.
基金the financial support by Guangdong Innovation Research Team for Higher Education(2017KCXTD030)High-level Talents Project of Dongguan University of Technology(KCYKYQD2017017)Engineering Research Center of None-food Biomass Efficient Pyrolysis and Utilization Technology of Guangdong Higher Education Institutes(2016GCZX009)。
文摘Ammonia synthesis by electrochemical nitrogen reduction technique is an attractive alternative to traditional Haber-Bosch process.Currently,development of an efficient and effective electrocatalyst is one of the remaining key challenges.In this work,density functional theory(DFT)computations were systematically employed on double transition metal atoms(Fe,Co,Ni,Cu and Mo)anchored Graphdiyne(GDY)for nitrogen reduction reaction(NRR).The Co-Ni heteronuclear complex and Mo-Mo homonuclear complex showed the highest NRR activity while demonstrating synergistic effect of double atomic catalytic sites towards the promising NRR activity.
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.
文摘Graphdiyne(GDY,g-C_(n)H_(2n-2)),a novel two-dimensional carbon hybrid material,has attracted significant attention owing to its unique and excellent properties.As a new type of carbon material,GDY has a layered structure and can be used in the field of photocatalytic water splitting.Therefore,herein,new progress in the preparation of graphene using Cu I powder as a catalytic material and the combination of a facile hydrothermal method to prepare a new composite material,Co_(9)S_(8)-GDY-Cu I,is reported.The hydrogen production activity of Co9S8-GDY-Cu I in the sensitization system reached 1411.82μmol g^(-1) h^(-1),which is 10.29 times that of pure GDY.A series of characterization techniques were used to provide evidence for the successful preparation of the material and its superior photocatalytic activity.Raman spectroscopy showed that the material contains acetylenic bonds,and the X-ray photoelectron spectroscopy carbon fitting peaks indicated the presence of C-C(sp^(2))and C-C(sp),further demonstrating that GDY was successfully prepared.A possible reaction mechanism was proposed by making use of UV-visible diffuse reflectance and Mott-Schottky analyses.The results showed that a double S-scheme heterojunction was constructed between the samples,which effectively accelerated the separation and transfer of electrons.In addition,the introduction of Co9S8 nanoparticles greatly improved the visible light absorption capacity of Co_(9)S_(8)-GDY-Cu I.Photoluminescence spectroscopy and related electrochemical characterization further proved that recombination of the electron-hole pairs in the composite material was effectively suppressed.
