The discovery of graphene in 2004 brings a new era of two-dimensional(2D)materials research[1].Together with previous carbon nanotubes and fullerene,the carbon series nanostructures seem an endless story that always a...The discovery of graphene in 2004 brings a new era of two-dimensional(2D)materials research[1].Together with previous carbon nanotubes and fullerene,the carbon series nanostructures seem an endless story that always astonishes the world.In this means,the first chemical synthesis of graphdiynes by Chinese chemists Yuliang Li et al.continues the brilliant age of carbon research[2].Proposed by Haley and coworkers,graphdiyne(GD)展开更多
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
Building anion-derived solid electrolyte interphase(SEI)with enriched LiF is considered the most promising strategy to address inferior safety features and poor cyclability of lithium-metal batteries(LMBs).Herein,we d...Building anion-derived solid electrolyte interphase(SEI)with enriched LiF is considered the most promising strategy to address inferior safety features and poor cyclability of lithium-metal batteries(LMBs).Herein,we discover that,instead of direct electron transfer from surface polar groups to bis(trifluoromethanesulfonyl)imide(TFSI-)for inducing a LiF-rich SEI,the dipole-induced fluorinated-anion decomposition reaction begins with the adsorption of Li ions and is highly dependent on their mobility on the polar surface.To demonstrate this,a single-layer graphdiyne on MXene(sGDY@MXene)heterostructure has been successfully fabricated and integrated into polypropylene separators.It is found that the adsorbed Li ions connect electron-donating sGDY@MXene to TFSI-,facilitating interfacial charge transfer for TFSI-decomposition.However,this does not capture the entire picture.The sGDY@MXene also renders the adsorbed Li ions with high mobility,enabling them to reach optimal reaction sites and expedite their coordination processes with O on O=S=O and F on the broken–CF_3~-,facilitating bond cleavage.In contrast,immobilized Li ions on the more lithiophilic pristine MXene retard these cleavage processes.Consequently,the decomposition reaction is accelerated on sGDY@MXene.This work highlights the dedicate balance between lithiophilicity and Li-ion mobility in effectively promoting a LiF-rich SEI for the long-term stability of LMBs.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
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
Developing highly active catalysts for photo/electrocatalytic water splitting is an attractive strategy to produce H2 as a renewable energy source.In this study,a new nickel boron oxide/graphdiyne(NiBi/GDY)hybrid cata...Developing highly active catalysts for photo/electrocatalytic water splitting is an attractive strategy to produce H2 as a renewable energy source.In this study,a new nickel boron oxide/graphdiyne(NiBi/GDY)hybrid catalyst was prepared by a facile synthetic approach.Benefitting from the strong electron donating ability of graphdiyne,NiBi/GDY showed an optimized electronic structure containing lower valence nickel atoms and demonstrated improved catalytic performance.As expected,NiBi/GDY displayed a high photocatalytic H2 evolution rate of 4.54 mmol g^(-1)h^(-1),2.9 and 4.5 times higher than those of NiBi/graphene and NiBi,respectively.NiBi/GDY also displayed outstanding electrocatalytic H2 evolution activity in 1.0 M KOH solution,with a current density of 400 mA/cm^(2)at an overpotential of 478.0 mV,which is lower than that of commercial Pt/C(505.3 mV@400 mA/cm^(2)).This work demonstrates that GDY is an ideal support for the development of highly active catalysts for photo/electrocatalytic H2 evolution.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
The inherent shortcomings of a zinc anode in aqueous zinc‐ion batteries(ZIBs)such as zinc dendrites and side reactions severely limit their practical application.Herein,to address these issues,an ion‐oriented transp...The inherent shortcomings of a zinc anode in aqueous zinc‐ion batteries(ZIBs)such as zinc dendrites and side reactions severely limit their practical application.Herein,to address these issues,an ion‐oriented transport channel constructed by graphdiyne(GDY)nanowalls is designed and grown in situ on the surface of a zinc electrode.The vertically stacked GDY nanowalls with a unique hierarchical porous structure and mechanical properties form a nanomesh‐like interface on the zinc electrode,acting as an ion‐oriented channel,which can efficiently confine the segmented growth of zinc metal in microscopic regions of hundreds of nanometers.In those microscopic regions,the uniform domain current density is effortlessly maintained compared with a large surface area,thereby inhibiting zinc dendrites effectively.Besides,due to the presence of the ion‐oriented channel,the modified zinc anode demonstrates long‐term stable zinc plating/stripping performance for more than 600 h at 1 mAh cm^(−2)in an aqueous electrolyte.In addition,full‐cells coupled with MnO2 show high specific capacity and power density,as well as excellent cycling stability with a capacity retention of 82%after 5000 cycles at 1 A g^(−1).This work provides a feasible and accessible surface engineering approach to modify the electrode interface for confined and dendrite‐free zinc deposition in aqueous ZIBs.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
Graphdiyne(GDY)has attracted considerable attention as a new two-dimensional(2D)carbon hybrid material because of its good conductivity,adjustable electronic structure,and special electron transfer enhancement propert...Graphdiyne(GDY)has attracted considerable attention as a new two-dimensional(2D)carbon hybrid material because of its good conductivity,adjustable electronic structure,and special electron transfer enhancement properties.GDY has great potential in the field of photocatalytic water splitting for hydrogen evolution,owing to its unique properties.In this study,GDY was successfully prepared by the mechanochemical coupling of precursors C_(6)Br_(6) and CaC_(2) using a ball-milling approach.The prepared GDY,especially its microstructure and composition,was well characterized using different techniques such as X-ray diffraction,scanning electron microscopy,transmission electron microscopy,X-ray photoelectron spectroscopy(XPS),Fourier-transform infrared,and Raman characterization techniques.By exploiting the unique two-dimensional(2D)structure and outstanding light absorption properties of GDY,GDY/CdSe 2D/0D heterojunctions were successfully established and applied to photocatalytic hydrogen evolution.The hydrogen evolution activity of GDY/CdSe-20,a type of composite material,reached 6470μmol g^(-1) h^(-1),which is 461 and 40 times higher than that of GDY and CdSe,respectively.Moreover,the fine electrical conductivity of GDY enabled rapid and effective transfer of the photogenerated electrons in CdSe into the hydrogen evolution reaction.The transfer path of the photogenerated electrons was studied through XPS with in situ irradiation,and a reasonable mechanism for the hydrogen evolution reaction was proposed.This study provides a feasible approach for the large-scale preparation of GDY and demonstrates the prospects of GDY in the field of photocatalysis.展开更多
文摘The discovery of graphene in 2004 brings a new era of two-dimensional(2D)materials research[1].Together with previous carbon nanotubes and fullerene,the carbon series nanostructures seem an endless story that always astonishes the world.In this means,the first chemical synthesis of graphdiynes by Chinese chemists Yuliang Li et al.continues the brilliant age of carbon research[2].Proposed by Haley and coworkers,graphdiyne(GD)
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the financial support from the National Natural Science Foundation of China(Nos.52272242,52174387,and 52403339)Key Research and Development Program of Henan Province(No.231111240600)。
文摘Building anion-derived solid electrolyte interphase(SEI)with enriched LiF is considered the most promising strategy to address inferior safety features and poor cyclability of lithium-metal batteries(LMBs).Herein,we discover that,instead of direct electron transfer from surface polar groups to bis(trifluoromethanesulfonyl)imide(TFSI-)for inducing a LiF-rich SEI,the dipole-induced fluorinated-anion decomposition reaction begins with the adsorption of Li ions and is highly dependent on their mobility on the polar surface.To demonstrate this,a single-layer graphdiyne on MXene(sGDY@MXene)heterostructure has been successfully fabricated and integrated into polypropylene separators.It is found that the adsorbed Li ions connect electron-donating sGDY@MXene to TFSI-,facilitating interfacial charge transfer for TFSI-decomposition.However,this does not capture the entire picture.The sGDY@MXene also renders the adsorbed Li ions with high mobility,enabling them to reach optimal reaction sites and expedite their coordination processes with O on O=S=O and F on the broken–CF_3~-,facilitating bond cleavage.In contrast,immobilized Li ions on the more lithiophilic pristine MXene retard these cleavage processes.Consequently,the decomposition reaction is accelerated on sGDY@MXene.This work highlights the dedicate balance between lithiophilicity and Li-ion mobility in effectively promoting a LiF-rich SEI for the long-term stability of LMBs.
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.
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.
文摘Developing highly active catalysts for photo/electrocatalytic water splitting is an attractive strategy to produce H2 as a renewable energy source.In this study,a new nickel boron oxide/graphdiyne(NiBi/GDY)hybrid catalyst was prepared by a facile synthetic approach.Benefitting from the strong electron donating ability of graphdiyne,NiBi/GDY showed an optimized electronic structure containing lower valence nickel atoms and demonstrated improved catalytic performance.As expected,NiBi/GDY displayed a high photocatalytic H2 evolution rate of 4.54 mmol g^(-1)h^(-1),2.9 and 4.5 times higher than those of NiBi/graphene and NiBi,respectively.NiBi/GDY also displayed outstanding electrocatalytic H2 evolution activity in 1.0 M KOH solution,with a current density of 400 mA/cm^(2)at an overpotential of 478.0 mV,which is lower than that of commercial Pt/C(505.3 mV@400 mA/cm^(2)).This work demonstrates that GDY is an ideal support for the development of highly active catalysts for photo/electrocatalytic H2 evolution.
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National Natural Science Foundation of China,Grant/Award Numbers:21701182,21771187,21790050,21790051,22005323Frontier Science Research Project of the Chinese Academy of Sciences,Grant/Award Number:QYZDB‐SSWJSC052+1 种基金Taishan Scholars Program of Shandong Province,Grant/Award Number:tsqn201812111ICCAS Institute Research Project。
文摘The inherent shortcomings of a zinc anode in aqueous zinc‐ion batteries(ZIBs)such as zinc dendrites and side reactions severely limit their practical application.Herein,to address these issues,an ion‐oriented transport channel constructed by graphdiyne(GDY)nanowalls is designed and grown in situ on the surface of a zinc electrode.The vertically stacked GDY nanowalls with a unique hierarchical porous structure and mechanical properties form a nanomesh‐like interface on the zinc electrode,acting as an ion‐oriented channel,which can efficiently confine the segmented growth of zinc metal in microscopic regions of hundreds of nanometers.In those microscopic regions,the uniform domain current density is effortlessly maintained compared with a large surface area,thereby inhibiting zinc dendrites effectively.Besides,due to the presence of the ion‐oriented channel,the modified zinc anode demonstrates long‐term stable zinc plating/stripping performance for more than 600 h at 1 mAh cm^(−2)in an aqueous electrolyte.In addition,full‐cells coupled with MnO2 show high specific capacity and power density,as well as excellent cycling stability with a capacity retention of 82%after 5000 cycles at 1 A g^(−1).This work provides a feasible and accessible surface engineering approach to modify the electrode interface for confined and dendrite‐free zinc deposition in aqueous ZIBs.
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.
文摘Graphdiyne(GDY)has attracted considerable attention as a new two-dimensional(2D)carbon hybrid material because of its good conductivity,adjustable electronic structure,and special electron transfer enhancement properties.GDY has great potential in the field of photocatalytic water splitting for hydrogen evolution,owing to its unique properties.In this study,GDY was successfully prepared by the mechanochemical coupling of precursors C_(6)Br_(6) and CaC_(2) using a ball-milling approach.The prepared GDY,especially its microstructure and composition,was well characterized using different techniques such as X-ray diffraction,scanning electron microscopy,transmission electron microscopy,X-ray photoelectron spectroscopy(XPS),Fourier-transform infrared,and Raman characterization techniques.By exploiting the unique two-dimensional(2D)structure and outstanding light absorption properties of GDY,GDY/CdSe 2D/0D heterojunctions were successfully established and applied to photocatalytic hydrogen evolution.The hydrogen evolution activity of GDY/CdSe-20,a type of composite material,reached 6470μmol g^(-1) h^(-1),which is 461 and 40 times higher than that of GDY and CdSe,respectively.Moreover,the fine electrical conductivity of GDY enabled rapid and effective transfer of the photogenerated electrons in CdSe into the hydrogen evolution reaction.The transfer path of the photogenerated electrons was studied through XPS with in situ irradiation,and a reasonable mechanism for the hydrogen evolution reaction was proposed.This study provides a feasible approach for the large-scale preparation of GDY and demonstrates the prospects of GDY in the field of photocatalysis.
