The sluggish lithium-ion(Li-ion)transport kinetics in graphite anode hinders its application in fast-charging Li-ion batteries(LIBs).Here,we develop an ionpumping interphase(IPI)on graphdiyne(GDY)/graphite heterojunct...The sluggish lithium-ion(Li-ion)transport kinetics in graphite anode hinders its application in fast-charging Li-ion batteries(LIBs).Here,we develop an ionpumping interphase(IPI)on graphdiyne(GDY)/graphite heterojunction anodes to boost the ionic transport kinetics and enable high-performance,fast-charging LIBs.The IPI changed the ion solvation/desolvation environment by covalent/non-covalent interactions with Li ions or solvents to optimize solid-electrolyte interphase(SEI)and regulate Li-ion transport behavior.We studied the in situ growth of few-layer GDY on graphite surface(GDY/graphite)as the IPI and found that the strong interaction between GDY and Li ions enabled surface-induced modification of the ion solvation behavior and surface-assisted desolvation effect to accelerate the Li-ion desolvation process.A functional anion-derived SEI layer with improved Li-ion conductivity was created.Together with the generated built-in electric field at GDY/graphite hetero-interface self-pumping Li ions to intercalate into the graphite,the Li-ion transport kinetics was significantly enhanced to effectively eliminate Li plating and large voltage polarization of the graphite anodes.A fast Li intercalation in GDY/graphite without Li oversaturation at the edge of the graphite was directly observed.The superior performance with high capacity(139.2 mA h g^(-1))and long lifespan(1650 cycles)under extremely fast-charging conditions(20 C,1 C=372 mA g^(-1))was achieved on GDY/graphite anodes.Even at low temperatures(-20℃),a specific capacity of 128.4 mA h g^(-1) was achieved with a capacity retention of 80%after 500 cycles at a 2 C rate.展开更多
Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon ...Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon neutrality,LIBs are expected to play a pivotal role in reducing CO_(2)emissions by decreasing reliance on fossil fuels and enabling the integration of renewable energy sources.Owing to their technological maturity and exceptional electrochemical performance,the global production of graphite and graphene for LIBs is projected to continue expanding.Over the past decades,numerous researchers have concentrated on reducing the material and energy input whilst optimising the electrochemical performance of graphite and graphene,through novel synthesis methods and various modifications at the laboratory scale.This review provides a comprehensive examination of the manufacturing methods,environmental impact,research progress,and challenges associated with graphite and graphene in LIBs from an industrial perspective,with a particular focus on the carbon footprint of production processes.Additionally,it considers emerging challenges and future development directions of graphite and graphene,offering significant insights for ongoing and future research in the field of green LIBs.展开更多
Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,...Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,understanding the oxidation behavior of nuclear graphite is essential for reactor safety.The influence of oxidation involves multiple factors,including temperature,sample size,oxidant,impurities,filler type and size,etc.The size of the filler particles plays a crucial role in this study.Five ultrafine-and superfine-grained nuclear graphite samples(5.9-34.4μm)are manufactured using identical raw materials and manufacturing processes.Isothermal oxidation tests conducted at 650℃-750℃ are used to study the oxidation behavior.Additionally,comprehensive characterization is performed to analyze the crystal structure,surface morphology,and nanoscale to microscale pore structure of the samples.Results indicate that oxidation behavior cannot be predicted solely based on filler grain size.Reactive site concentration,characterized by active surface area,dominates the chemical reaction kinetics,whereas pore tortuosity,quantified by the structural parameterΨ,plays a key role in regulating oxidant diffusion.These findings clarify the dual role of microstructure in oxidation mechanisms and establish a theoretical and experimental basis for the design of high-performance nuclear graphite capable of long-term service in high-temperature gas-cooled reactors.展开更多
Laser-induced periodic surface structures(LIPSS)have gained increasing attention in the field of micro/nano fabrication,although achieving sub-100-nm period LIPSS with high uniformity remains a significant challenge.I...Laser-induced periodic surface structures(LIPSS)have gained increasing attention in the field of micro/nano fabrication,although achieving sub-100-nm period LIPSS with high uniformity remains a significant challenge.In this work,towards deep-subwavelength LIPSS on highly oriented pyrolytic graphite(HOPG),we demonstrate that ultra-uniform nanogratings of sub-50-nm periods and near-10-nm groove widths can be stably prepared via 800-nm femtosecond laser scanning irradiation with a high-NA objective lens under water immersion.The resulting nanogratings of strong polarization dependence,exhibiting exceptional surface flatness,period stability,and structural integrity,tend to appear at near-damage-threshold fluence regime with an appropriate effective pulse number.It turns out that the water immersion condition can significantly reduce the thermal effects of femtosecond laser ablation on HOPG,and thus via a mild,incubation-like scanning ablation process occurring in the nanogrooves with a continuous or jumping manner,this deep-subwavelength grating can achieve robust elongation growth,ensuring its long-range uniformity as well as minimal deposited debris and structural defects.Interestingly,the different incubation extension mechanisms for the mutually perpendicular and parallel settings between scanning direction and laser polarization bring not only distinct effective-pulse-number windows and somewhat different grating qualities,but also different extension stabilities in nanograting stitching via overlapping scanning lines and thus the optimal scanning strategy of parallel setting for large-area processing.In short,this study presents a convenient laser-processing approach for high precision fabrication of sub-50-nm gratings on HOPG,which would provide new insights into micro/nano-fabrication for optoelectronic metasurfaces and physics of the interaction between ultrafast laser and graphite.展开更多
To enhance the electrochemical performance of lithium-ion battery anodes with higher silicon content,it is essential to engineer their microstructure for better lithium-ion transport and mitigated volume change as wel...To enhance the electrochemical performance of lithium-ion battery anodes with higher silicon content,it is essential to engineer their microstructure for better lithium-ion transport and mitigated volume change as well.Herein,we suggest an effective approach to control the micropore structure of silicon oxide(SiO_(x))/artificial graphite(AG)composite electrodes using a perforated current collector.The electrode features a unique pore structure,where alternating high-porosity domains and low-porosity domains markedly reduce overall electrode resistance,leading to a 20%improvement in rate capability at a 5C-rate discharge condition.Using microstructure-resolved modeling and simulations,we demonstrate that the patterned micropore structure enhances lithium-ion transport,mitigating the electrolyte concentration gradient of lithium-ion.Additionally,perforating current collector with a chemical etching process increases the number of hydrogen bonding sites and enlarges the interface with the SiO_(x)/AG composite electrode,significantly improving adhesion strength.This,in turn,suppresses mechanical degradation and leads to a 50%higher capacity retention.Thus,regularly arranged micropore structure enabled by the perforated current collector successfully improves both rate capability and cycle life in SiO_(x)/AG composite electrodes,providing valuable insights into electrode engineering.展开更多
In order to effectively prevent the contamination of carbon particle volatiles during high-purity SiC crystals are prepared using the physical vapor transport(PVT)method in ultra-high temperature environments(T³2...In order to effectively prevent the contamination of carbon particle volatiles during high-purity SiC crystals are prepared using the physical vapor transport(PVT)method in ultra-high temperature environments(T³2000℃),this study innovatively attempts to protect graphite materials with SiC reinforced pyrolytic graphite(PyG)coating.It is discovered by preparing the SiC particle layer,the degree of graphitization and stability of PyG coating can be improved.The corrosion test results demonstrated that the SiC reinforced PyG coating can maintain an intact coating with a high graphitization degree after the SiC vapour corrosion test of 2050℃-120 h.Conversely,the samples with and without PyG coating reveal porous and eroded surfaces.Furthermore,following the SiC vapour corrosion test,the PyG coating sample’s integral ratio of D-band and G-band(I_(D)/I_(G))of Raman spectrum test data,reduced by 6.5%,while the SiC reinforced PyG coating decreased by 17.2%,indicating its excellent corrosion resistance.The application of SiC reinforced pyrolytic graphite coating in preparing the SiC single crystal might received a theoretical foundation according to this work.展开更多
Waste graphitization cathode carbon blocks are a type of hazardous solid waste generated during the aluminum electrolysis process,and their proper disposal is a key step in the resource utilization of discarded graphi...Waste graphitization cathode carbon blocks are a type of hazardous solid waste generated during the aluminum electrolysis process,and their proper disposal is a key step in the resource utilization of discarded graphite.This study utilizes the porous“defect advantage”of a cathode carbon block matrix to prepare silicon-doped and asphalt-coated detoxified and purified waste graphitization cathode carbon blocks for use as high-performance silicon/carbon composite anode materials.The results show that the uniformly silicondoped silicon/carbon composite material features a unique amorphous carbon-encapsulated“locked silicon”structure,which effectively addresses issues such as cathode volume expansion,excessive growth of the solid electrolyte interphase(SEI)film,and poor electrical contact between active materials.Consequently,electrochemical performance is enhanced.After assembly in a half-cell,the PSCC/10%Si@C(purified waste graphitization cathode carbon/10%Si@C)material exhibits optimal electrochemical stability,with an initial charging specific capacity of 514.5 mAh/g at 0.1 C(1 C=170 mA/g)and a capacity retention rate of 95.1%after 100 cycles.At a charge rate of 2.0 C,a specific capacity of 216.9 mAh/g is achieved.This technology provides a new pathway for the economical and high-value utilization of waste cathode carbon blocks and the development of low-cost,high-performance anode materials.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
Lithium-ion batteries(LIBs)are an electrochemical energy storage technology that has been widely used for portable electrical devices,electric vehicles,and grid storage,etc.To satisfy the demand for user convenience e...Lithium-ion batteries(LIBs)are an electrochemical energy storage technology that has been widely used for portable electrical devices,electric vehicles,and grid storage,etc.To satisfy the demand for user convenience especially for electric vehicles,the development of a fast-charging technology for LIBs has become a critical focus.In commercial LIBs,the slow kinetics of Li+intercalation into the graphite anode from the electrolyte solution is known as the main restriction for fast-charging.We summarize the recent advances in obtaining fast-charging graphite-based anodes,mainly involving modifications of the electrolyte solution and graphite anode.Specifically,strategies for increasing the ionic conductivity and regulating the Li+solvation/desolvation state in the electrolyte solution,as well as optimizing the fabrication and the intrinsic activity of graphite-based anodes are discussed in detail.This review considers practical ways to obtain fast Li+intercalation kinetics into a graphite anode from the electrolyte as well as analysing progress in the commercialization of fast-charging LIBs.展开更多
Although graphite(G)materials dominate the commercial lithium-ion battery(LIBs)anode market due to their excellent overall performance,their limited rate performance and cycle life hinder applications in highperforman...Although graphite(G)materials dominate the commercial lithium-ion battery(LIBs)anode market due to their excellent overall performance,their limited rate performance and cycle life hinder applications in highperformance fields.To improve the cycling and rate performance of graphite anodes,this study first employed economical and eco-friendly tannic acid(TA)as a carbon coating precursor to coat graphite surfaces viaπ-πstacking interactions.In an oxygen-rich alkaline environment,tannic acid undergoes oxidation polymerization and crosslinks with formaldehyde to form a polymer matrix that coats the graphite surface.After subsequent carbonization,carbon-coated graphite material(G@C)was successfully synthesized.Carbon coatings on graphite effectively lower LIB resistance,enhance lithium-ion diffusion,and prevent exfoliation during cycling,thereby significantly boosting rate performance and prolonging the cycle life of graphite.After 500 cycles at 2C,the specific capacity of G@C was 103.7 mAh g^(-1),with a retention of 89%.However,G exhibited only 68.7 mAh g^(-1) and 85%retention under identical conditions.This carbon-coated graphite modification strategy offers a novel,green,and economical approach for designing and tailoring graphite anode materials for lithium-ion batteries with long cycle life and high rate.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
We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) change...We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) changed from 0.5:1 to 4:1,and the impregnation time changed from 1 to 7 h.The typical composite phase change thermal storage materials doped with the as-treated graphite were fabricated using form-stable technique.To investigate the oxidation and anti-oxidation behavior of the impregnated graphite at high temperatures,the samples were put into a muffle furnace for a cyclic heat test.Based on SEM,EDS,DSC techniques,analyses on the impregnated technique suggested an optimized processing conditions of a 3 h impregnation time with the ratio of graphite:Al(H_(2)PO_(4))_(3) as 1:3 for graphite impregnation treatment.Further investigations on high-temperature phase change heat storage materials doped by the treated graphite suggested excellent oxidation resistance and thermal cycling performance.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
Magnesium potassium phosphate cement(MKPC)coatings exhibit potential for carbon steel protection but face challenges in practical application due to the preparation process and properties.This study develops flake gra...Magnesium potassium phosphate cement(MKPC)coatings exhibit potential for carbon steel protection but face challenges in practical application due to the preparation process and properties.This study develops flake graphite(FG)-modified MKPC coatings via spraying process,investigating the effects of FG size and dosage on phase composition,microstructure,mechanical properties,corrosion protection,and thermal conductivity.Results show that a low FG dosage(5 wt%)synergistically optimizes multifunctional performance.Compared to unmodified MKPC,FG2-1 exhibited exceptional impact resistance,associated with a 57%reduction in corrosion current density(icorr),a 356.3% increase in low-frequency impedance modulus(Z_(0.01 Hz))and a 37% increase in thermal conductivity.However,the coating with a high FG dosage(15 wt%)degraded performance due to defect accumulation and reduced crystallinity of KMgPO_(4)·6H_(2)O.This work advances the rational design of multifunctional inorganic coatings for extreme service environments requiring coupled corrosion protection and thermal management.展开更多
High-performance graphite materials have important roles in aerospace and nuclear reactor technologies because of their outstanding chemical stability and high-temperature performance.Their traditional production meth...High-performance graphite materials have important roles in aerospace and nuclear reactor technologies because of their outstanding chemical stability and high-temperature performance.Their traditional production method relies on repeated impregnation-carbonization and graphitization,and is plagued by lengthy preparation cycles and high energy consumption.Phase transition-assisted self-pressurized selfsintering technology can rapidly produce high-strength graphite materials,but the fracture strain of the graphite materials produced is poor.To solve this problem,this study used a two-step sintering method to uniformly introduce micro-nano pores into natural graphite-based bulk graphite,achieving improved fracture strain of the samples without reducing their density and mechanical properties.Using natural graphite powder,micron-diamond,and nano-diamond as raw materials,and by precisely controlling the staged pressure release process,the degree of diamond phase transition expansion was effectively regulated.The strain-to-failure of the graphite samples reached 1.2%,a 35%increase compared to samples produced by fullpressure sintering.Meanwhile,their flexural strength exceeded 110 MPa,and their density was over 1.9 g/cm^(3).The process therefore produced both a high strength and a high fracture strain.The interface evolution and toughening mechanism during the two-step sintering process were investigated.It is believed that the micro-nano pores formed have two roles:as stress concentrators they induce yielding by shear and as multi-crack propagation paths they significantly lengthen the crack propagation path.The two-step sintering phase transition strategy introduces pores and provides a new approach for increasing the fracture strain of brittle materials.展开更多
CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed gra...CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed graphite-CeO_(2) interfaces to enhance solar-driven photothermal catalytic DRM.Compared with carbon nanotubes-modified CeO_(2)(CeO_(2)-CNT),graphite-modified CeO_(2)(CeO_(2)-GRA)constructed graphite-CeO_(2) interfaces with distortion in CeO_(2),leading to the formation abundant oxygen vacancies.These graphite-CeO_(2) interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers.The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3℃,boosting light-to-thermal conversion.The synergy between photogenerated carriers and localized heat enabled Ni/CeO_(2)-GRA to achieve a CO production rate of 9985.6 mmol/(g·h)(vs 7192.4 mmol/(g·h)for Ni/CeO_(2))and a light-to-fuel efficiency of 21.8%(vs 13.8%for Ni/CeO_(2)).This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.展开更多
Based on the service characteristics of fuel elements for molten salt reactors,they need to have a high power density,resistance to coolant infiltration,and excellent thermodynamic properties.To solve the problem of t...Based on the service characteristics of fuel elements for molten salt reactors,they need to have a high power density,resistance to coolant infiltration,and excellent thermodynamic properties.To solve the problem of the graphite used in the fuel element for these reactors being susceptible to molten salt infiltration,carbon black(CB)was added to increase the density of the graphite,and a fuel element(TRISO(tri-structural isotropic)fuel particles were randomly distributed in the modified graphite matrix)was prepared by cold isostatic pressing process.An out-of-pile performance study shows that the densification and pore structure of the modified graphite matrix were improved,as was the resistance to molten salt infiltration.The median pore size of the modified graphite was reduced from 673 to 433 nm and the threshold pressure for molten salt(FLiBe,66%(molar fraction)LiF and 34%BeF_(2))infiltration was increased from 0.88 to 1.37 MPa.The isotropic CB made the graphite matrix less anisotropic,while its thermal conductivity and compressive strength were reduced due to the difficult graphitization of CB.Fuel elements containing 20%(volume fraction)TRISO particles were prepared.Numerical simulations show that the power and temperature distribution of the fuel were in line with the design requirements.The modified graphite matrix had a higher density,smaller pores,a lower anisotropy and a greater resistance to FLiBe infiltration.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
The stability of matrix graphite under neutron irradiation and in corrosive environments is crucial for the safe operation of molten salt reactors(MSRs).Raman spectroscopy and a slow positron beam were employed to inv...The stability of matrix graphite under neutron irradiation and in corrosive environments is crucial for the safe operation of molten salt reactors(MSRs).Raman spectroscopy and a slow positron beam were employed to investigate the effects of He ion irradiation fluences and subsequent annealing on the microstructure and defects of the matrix graphite.He ions with 500 keV energy and fluences ranging from 1.1×10^(15)ions∕cm^(2)to 3.5×10^(17)ions∕cm^(2)were used to simulate neutron irradiation at 300 K.The samples with an irradiation fluence of 3.5×10^(16)ions∕cm^(2)were subjected to isochronal annealing at different temperatures(573 K,873 K and 1173 K)for 3 h.The Raman results revealed that the D peak gradually increased,whereas the intrinsic G peak decreased with increasing irradiation fluence.At the same irradiation fluence,the D peak gradually decreased,whereas the intrinsic G peak increased with increasing annealing temperature.Slow positron beam analysis demonstrated that the density or size of irradiation defects(vacancy type)increased with higher irradiation fluence,but decreased rapidly with increasing annealing temperature.The Raman spectral analysis of sample cross sections subjected to high irradiation fluences revealed the emergence of amorphization precisely at the depth where ion damage was most pronounced,whereas the surface retained its crystalline structure.Raman and positron annihilation analyses indicated that the matrix graphite exhibited good irradiation resistance to He ions at 300 K.However,vacancy-type defects induced by He ion irradiation exhibit poor thermal stability and can be easily removed during annealing.展开更多
基金the National Nature Science Foundation of China(grant nos.52072222 and 22279073)the National Key Research and Development Project of China(grant no.2022YFA1200044)+2 种基金the Taishan Scholar Project of Shandong Province of China(grant no.62460082061017)the Natural Science Foundation of Shandong Province(grant no.ZR2022ZD35)the National Nature Science Foundation of China(grant nos.21790050 and 21790051).
文摘The sluggish lithium-ion(Li-ion)transport kinetics in graphite anode hinders its application in fast-charging Li-ion batteries(LIBs).Here,we develop an ionpumping interphase(IPI)on graphdiyne(GDY)/graphite heterojunction anodes to boost the ionic transport kinetics and enable high-performance,fast-charging LIBs.The IPI changed the ion solvation/desolvation environment by covalent/non-covalent interactions with Li ions or solvents to optimize solid-electrolyte interphase(SEI)and regulate Li-ion transport behavior.We studied the in situ growth of few-layer GDY on graphite surface(GDY/graphite)as the IPI and found that the strong interaction between GDY and Li ions enabled surface-induced modification of the ion solvation behavior and surface-assisted desolvation effect to accelerate the Li-ion desolvation process.A functional anion-derived SEI layer with improved Li-ion conductivity was created.Together with the generated built-in electric field at GDY/graphite hetero-interface self-pumping Li ions to intercalate into the graphite,the Li-ion transport kinetics was significantly enhanced to effectively eliminate Li plating and large voltage polarization of the graphite anodes.A fast Li intercalation in GDY/graphite without Li oversaturation at the edge of the graphite was directly observed.The superior performance with high capacity(139.2 mA h g^(-1))and long lifespan(1650 cycles)under extremely fast-charging conditions(20 C,1 C=372 mA g^(-1))was achieved on GDY/graphite anodes.Even at low temperatures(-20℃),a specific capacity of 128.4 mA h g^(-1) was achieved with a capacity retention of 80%after 500 cycles at a 2 C rate.
基金supported by European Union's Horizon Europe,UK Research and Innovation(UKRI).
文摘Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon neutrality,LIBs are expected to play a pivotal role in reducing CO_(2)emissions by decreasing reliance on fossil fuels and enabling the integration of renewable energy sources.Owing to their technological maturity and exceptional electrochemical performance,the global production of graphite and graphene for LIBs is projected to continue expanding.Over the past decades,numerous researchers have concentrated on reducing the material and energy input whilst optimising the electrochemical performance of graphite and graphene,through novel synthesis methods and various modifications at the laboratory scale.This review provides a comprehensive examination of the manufacturing methods,environmental impact,research progress,and challenges associated with graphite and graphene in LIBs from an industrial perspective,with a particular focus on the carbon footprint of production processes.Additionally,it considers emerging challenges and future development directions of graphite and graphene,offering significant insights for ongoing and future research in the field of green LIBs.
基金supported by the National Key Research and Development Program of China(2024YFA1612900)the National Natural Science Foundation of China(Grant No.52103365 and No.12375270)the Guangdong Innovative and Entrepreneurial Research Team Program,China(Grant No.2021ZT09L227).
文摘Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,understanding the oxidation behavior of nuclear graphite is essential for reactor safety.The influence of oxidation involves multiple factors,including temperature,sample size,oxidant,impurities,filler type and size,etc.The size of the filler particles plays a crucial role in this study.Five ultrafine-and superfine-grained nuclear graphite samples(5.9-34.4μm)are manufactured using identical raw materials and manufacturing processes.Isothermal oxidation tests conducted at 650℃-750℃ are used to study the oxidation behavior.Additionally,comprehensive characterization is performed to analyze the crystal structure,surface morphology,and nanoscale to microscale pore structure of the samples.Results indicate that oxidation behavior cannot be predicted solely based on filler grain size.Reactive site concentration,characterized by active surface area,dominates the chemical reaction kinetics,whereas pore tortuosity,quantified by the structural parameterΨ,plays a key role in regulating oxidant diffusion.These findings clarify the dual role of microstructure in oxidation mechanisms and establish a theoretical and experimental basis for the design of high-performance nuclear graphite capable of long-term service in high-temperature gas-cooled reactors.
基金supported by grants from Natural Science Foundation of Guangdong Province(Grant No.2021A1515012335)National Natural Science Foundation of China(NSFC)(Grant No.11274400)+2 种基金Pearl River S&T Nova Program of Guangzhou(Grant No.201506010059)State Key Laboratory of Optoelectronic Materials and Technologies(Sun Yat-Sen University)(Grant No.OEMT-2024-ZTS-01)State Key Laboratory of High Field Laser Physics(Shanghai Institute of Optics and Fine Mechanics)。
文摘Laser-induced periodic surface structures(LIPSS)have gained increasing attention in the field of micro/nano fabrication,although achieving sub-100-nm period LIPSS with high uniformity remains a significant challenge.In this work,towards deep-subwavelength LIPSS on highly oriented pyrolytic graphite(HOPG),we demonstrate that ultra-uniform nanogratings of sub-50-nm periods and near-10-nm groove widths can be stably prepared via 800-nm femtosecond laser scanning irradiation with a high-NA objective lens under water immersion.The resulting nanogratings of strong polarization dependence,exhibiting exceptional surface flatness,period stability,and structural integrity,tend to appear at near-damage-threshold fluence regime with an appropriate effective pulse number.It turns out that the water immersion condition can significantly reduce the thermal effects of femtosecond laser ablation on HOPG,and thus via a mild,incubation-like scanning ablation process occurring in the nanogrooves with a continuous or jumping manner,this deep-subwavelength grating can achieve robust elongation growth,ensuring its long-range uniformity as well as minimal deposited debris and structural defects.Interestingly,the different incubation extension mechanisms for the mutually perpendicular and parallel settings between scanning direction and laser polarization bring not only distinct effective-pulse-number windows and somewhat different grating qualities,but also different extension stabilities in nanograting stitching via overlapping scanning lines and thus the optimal scanning strategy of parallel setting for large-area processing.In short,this study presents a convenient laser-processing approach for high precision fabrication of sub-50-nm gratings on HOPG,which would provide new insights into micro/nano-fabrication for optoelectronic metasurfaces and physics of the interaction between ultrafast laser and graphite.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.NRF-2021M3H4A1A02048529)the Ministry of Trade,Industry and Energy(MOTIE)of the Korean government under grant No.RS-2022-00155854support from the DGIST Supercomputing and Big Data Center.
文摘To enhance the electrochemical performance of lithium-ion battery anodes with higher silicon content,it is essential to engineer their microstructure for better lithium-ion transport and mitigated volume change as well.Herein,we suggest an effective approach to control the micropore structure of silicon oxide(SiO_(x))/artificial graphite(AG)composite electrodes using a perforated current collector.The electrode features a unique pore structure,where alternating high-porosity domains and low-porosity domains markedly reduce overall electrode resistance,leading to a 20%improvement in rate capability at a 5C-rate discharge condition.Using microstructure-resolved modeling and simulations,we demonstrate that the patterned micropore structure enhances lithium-ion transport,mitigating the electrolyte concentration gradient of lithium-ion.Additionally,perforating current collector with a chemical etching process increases the number of hydrogen bonding sites and enlarges the interface with the SiO_(x)/AG composite electrode,significantly improving adhesion strength.This,in turn,suppresses mechanical degradation and leads to a 50%higher capacity retention.Thus,regularly arranged micropore structure enabled by the perforated current collector successfully improves both rate capability and cycle life in SiO_(x)/AG composite electrodes,providing valuable insights into electrode engineering.
基金Project(U19A2099)supported by the National Natural Science Foundation of China。
文摘In order to effectively prevent the contamination of carbon particle volatiles during high-purity SiC crystals are prepared using the physical vapor transport(PVT)method in ultra-high temperature environments(T³2000℃),this study innovatively attempts to protect graphite materials with SiC reinforced pyrolytic graphite(PyG)coating.It is discovered by preparing the SiC particle layer,the degree of graphitization and stability of PyG coating can be improved.The corrosion test results demonstrated that the SiC reinforced PyG coating can maintain an intact coating with a high graphitization degree after the SiC vapour corrosion test of 2050℃-120 h.Conversely,the samples with and without PyG coating reveal porous and eroded surfaces.Furthermore,following the SiC vapour corrosion test,the PyG coating sample’s integral ratio of D-band and G-band(I_(D)/I_(G))of Raman spectrum test data,reduced by 6.5%,while the SiC reinforced PyG coating decreased by 17.2%,indicating its excellent corrosion resistance.The application of SiC reinforced pyrolytic graphite coating in preparing the SiC single crystal might received a theoretical foundation according to this work.
基金supported by the National Natural Science Foundation of China(No.52274346).
文摘Waste graphitization cathode carbon blocks are a type of hazardous solid waste generated during the aluminum electrolysis process,and their proper disposal is a key step in the resource utilization of discarded graphite.This study utilizes the porous“defect advantage”of a cathode carbon block matrix to prepare silicon-doped and asphalt-coated detoxified and purified waste graphitization cathode carbon blocks for use as high-performance silicon/carbon composite anode materials.The results show that the uniformly silicondoped silicon/carbon composite material features a unique amorphous carbon-encapsulated“locked silicon”structure,which effectively addresses issues such as cathode volume expansion,excessive growth of the solid electrolyte interphase(SEI)film,and poor electrical contact between active materials.Consequently,electrochemical performance is enhanced.After assembly in a half-cell,the PSCC/10%Si@C(purified waste graphitization cathode carbon/10%Si@C)material exhibits optimal electrochemical stability,with an initial charging specific capacity of 514.5 mAh/g at 0.1 C(1 C=170 mA/g)and a capacity retention rate of 95.1%after 100 cycles.At a charge rate of 2.0 C,a specific capacity of 216.9 mAh/g is achieved.This technology provides a new pathway for the economical and high-value utilization of waste cathode carbon blocks and the development of low-cost,high-performance anode materials.
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.
文摘Lithium-ion batteries(LIBs)are an electrochemical energy storage technology that has been widely used for portable electrical devices,electric vehicles,and grid storage,etc.To satisfy the demand for user convenience especially for electric vehicles,the development of a fast-charging technology for LIBs has become a critical focus.In commercial LIBs,the slow kinetics of Li+intercalation into the graphite anode from the electrolyte solution is known as the main restriction for fast-charging.We summarize the recent advances in obtaining fast-charging graphite-based anodes,mainly involving modifications of the electrolyte solution and graphite anode.Specifically,strategies for increasing the ionic conductivity and regulating the Li+solvation/desolvation state in the electrolyte solution,as well as optimizing the fabrication and the intrinsic activity of graphite-based anodes are discussed in detail.This review considers practical ways to obtain fast Li+intercalation kinetics into a graphite anode from the electrolyte as well as analysing progress in the commercialization of fast-charging LIBs.
基金supported by the Science and Technology Projects of the State Grid Corporation of China(5500-202323102A-1-1-ZN).
文摘Although graphite(G)materials dominate the commercial lithium-ion battery(LIBs)anode market due to their excellent overall performance,their limited rate performance and cycle life hinder applications in highperformance fields.To improve the cycling and rate performance of graphite anodes,this study first employed economical and eco-friendly tannic acid(TA)as a carbon coating precursor to coat graphite surfaces viaπ-πstacking interactions.In an oxygen-rich alkaline environment,tannic acid undergoes oxidation polymerization and crosslinks with formaldehyde to form a polymer matrix that coats the graphite surface.After subsequent carbonization,carbon-coated graphite material(G@C)was successfully synthesized.Carbon coatings on graphite effectively lower LIB resistance,enhance lithium-ion diffusion,and prevent exfoliation during cycling,thereby significantly boosting rate performance and prolonging the cycle life of graphite.After 500 cycles at 2C,the specific capacity of G@C was 103.7 mAh g^(-1),with a retention of 89%.However,G exhibited only 68.7 mAh g^(-1) and 85%retention under identical conditions.This carbon-coated graphite modification strategy offers a novel,green,and economical approach for designing and tailoring graphite anode materials for lithium-ion batteries with long cycle life and high rate.
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.
基金Funded by Scientific and Technological Innovation Project of Carbon Emission Peak and Carbon Neutrality of Jiangsu Province(No.BE2022028-4)。
文摘We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite substrate.The mass ratio of graphite to Al(H_(2)PO_(4))_(3) changed from 0.5:1 to 4:1,and the impregnation time changed from 1 to 7 h.The typical composite phase change thermal storage materials doped with the as-treated graphite were fabricated using form-stable technique.To investigate the oxidation and anti-oxidation behavior of the impregnated graphite at high temperatures,the samples were put into a muffle furnace for a cyclic heat test.Based on SEM,EDS,DSC techniques,analyses on the impregnated technique suggested an optimized processing conditions of a 3 h impregnation time with the ratio of graphite:Al(H_(2)PO_(4))_(3) as 1:3 for graphite impregnation treatment.Further investigations on high-temperature phase change heat storage materials doped by the treated graphite suggested excellent oxidation resistance and thermal cycling performance.
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National Key Research and Development Program of China(2024YFB3714804)National Natural Science Foundation of China(52171277)+1 种基金Baima Lake Laboratory Joint Funds of the Zhejiang Provincial Natural Science Foundation of China(LBMHZ24E020001)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2022SZ-TD006).
文摘Magnesium potassium phosphate cement(MKPC)coatings exhibit potential for carbon steel protection but face challenges in practical application due to the preparation process and properties.This study develops flake graphite(FG)-modified MKPC coatings via spraying process,investigating the effects of FG size and dosage on phase composition,microstructure,mechanical properties,corrosion protection,and thermal conductivity.Results show that a low FG dosage(5 wt%)synergistically optimizes multifunctional performance.Compared to unmodified MKPC,FG2-1 exhibited exceptional impact resistance,associated with a 57%reduction in corrosion current density(icorr),a 356.3% increase in low-frequency impedance modulus(Z_(0.01 Hz))and a 37% increase in thermal conductivity.However,the coating with a high FG dosage(15 wt%)degraded performance due to defect accumulation and reduced crystallinity of KMgPO_(4)·6H_(2)O.This work advances the rational design of multifunctional inorganic coatings for extreme service environments requiring coupled corrosion protection and thermal management.
基金Natural Science Foundation of Shanghai(24ZR1400800)he Natural Science Foundation of China(U23A20685,52073058,91963204)+1 种基金the National Key R&D Program of China(2021YFB3701400)Shanghai Sailing Program(23YF1400200)。
文摘High-performance graphite materials have important roles in aerospace and nuclear reactor technologies because of their outstanding chemical stability and high-temperature performance.Their traditional production method relies on repeated impregnation-carbonization and graphitization,and is plagued by lengthy preparation cycles and high energy consumption.Phase transition-assisted self-pressurized selfsintering technology can rapidly produce high-strength graphite materials,but the fracture strain of the graphite materials produced is poor.To solve this problem,this study used a two-step sintering method to uniformly introduce micro-nano pores into natural graphite-based bulk graphite,achieving improved fracture strain of the samples without reducing their density and mechanical properties.Using natural graphite powder,micron-diamond,and nano-diamond as raw materials,and by precisely controlling the staged pressure release process,the degree of diamond phase transition expansion was effectively regulated.The strain-to-failure of the graphite samples reached 1.2%,a 35%increase compared to samples produced by fullpressure sintering.Meanwhile,their flexural strength exceeded 110 MPa,and their density was over 1.9 g/cm^(3).The process therefore produced both a high strength and a high fracture strain.The interface evolution and toughening mechanism during the two-step sintering process were investigated.It is believed that the micro-nano pores formed have two roles:as stress concentrators they induce yielding by shear and as multi-crack propagation paths they significantly lengthen the crack propagation path.The two-step sintering phase transition strategy introduces pores and provides a new approach for increasing the fracture strain of brittle materials.
文摘CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed graphite-CeO_(2) interfaces to enhance solar-driven photothermal catalytic DRM.Compared with carbon nanotubes-modified CeO_(2)(CeO_(2)-CNT),graphite-modified CeO_(2)(CeO_(2)-GRA)constructed graphite-CeO_(2) interfaces with distortion in CeO_(2),leading to the formation abundant oxygen vacancies.These graphite-CeO_(2) interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers.The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3℃,boosting light-to-thermal conversion.The synergy between photogenerated carriers and localized heat enabled Ni/CeO_(2)-GRA to achieve a CO production rate of 9985.6 mmol/(g·h)(vs 7192.4 mmol/(g·h)for Ni/CeO_(2))and a light-to-fuel efficiency of 21.8%(vs 13.8%for Ni/CeO_(2)).This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.
文摘Based on the service characteristics of fuel elements for molten salt reactors,they need to have a high power density,resistance to coolant infiltration,and excellent thermodynamic properties.To solve the problem of the graphite used in the fuel element for these reactors being susceptible to molten salt infiltration,carbon black(CB)was added to increase the density of the graphite,and a fuel element(TRISO(tri-structural isotropic)fuel particles were randomly distributed in the modified graphite matrix)was prepared by cold isostatic pressing process.An out-of-pile performance study shows that the densification and pore structure of the modified graphite matrix were improved,as was the resistance to molten salt infiltration.The median pore size of the modified graphite was reduced from 673 to 433 nm and the threshold pressure for molten salt(FLiBe,66%(molar fraction)LiF and 34%BeF_(2))infiltration was increased from 0.88 to 1.37 MPa.The isotropic CB made the graphite matrix less anisotropic,while its thermal conductivity and compressive strength were reduced due to the difficult graphitization of CB.Fuel elements containing 20%(volume fraction)TRISO particles were prepared.Numerical simulations show that the power and temperature distribution of the fuel were in line with the design requirements.The modified graphite matrix had a higher density,smaller pores,a lower anisotropy and a greater resistance to FLiBe infiltration.
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 Natural Science Foundation of China(Nos.12005289,52072397)State Key Laboratory of Nuclear Detection and Electronics,University of Science and Technology of China(SKLPDE-KF-202316).
文摘The stability of matrix graphite under neutron irradiation and in corrosive environments is crucial for the safe operation of molten salt reactors(MSRs).Raman spectroscopy and a slow positron beam were employed to investigate the effects of He ion irradiation fluences and subsequent annealing on the microstructure and defects of the matrix graphite.He ions with 500 keV energy and fluences ranging from 1.1×10^(15)ions∕cm^(2)to 3.5×10^(17)ions∕cm^(2)were used to simulate neutron irradiation at 300 K.The samples with an irradiation fluence of 3.5×10^(16)ions∕cm^(2)were subjected to isochronal annealing at different temperatures(573 K,873 K and 1173 K)for 3 h.The Raman results revealed that the D peak gradually increased,whereas the intrinsic G peak decreased with increasing irradiation fluence.At the same irradiation fluence,the D peak gradually decreased,whereas the intrinsic G peak increased with increasing annealing temperature.Slow positron beam analysis demonstrated that the density or size of irradiation defects(vacancy type)increased with higher irradiation fluence,but decreased rapidly with increasing annealing temperature.The Raman spectral analysis of sample cross sections subjected to high irradiation fluences revealed the emergence of amorphization precisely at the depth where ion damage was most pronounced,whereas the surface retained its crystalline structure.Raman and positron annihilation analyses indicated that the matrix graphite exhibited good irradiation resistance to He ions at 300 K.However,vacancy-type defects induced by He ion irradiation exhibit poor thermal stability and can be easily removed during annealing.
