The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporat...The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporating iridium(Ir)ions on the atomic scale into orthorhombic-CoSe2(Ir-CoSe_(2))was reported.Outstanding hydrogen evolution activity in alkaline media such as a low overpotential of 48.7 mV at a current density of 10 mA cm^(-2)and better performance than commercial Pt/C catalysts at high current densities were found in the Ir-CoSe_(2) samples.In the experiments and theoretical calculations,it was revealed that Ir enabled CoSe_(2)to form multifunctional sites to synergistically catalyze alkaline HER by promoting the adsorption and dissociation of H_(2)O(Ir sites)and optimizing the binding energy for H^(*)on Co sites.It was noticeable that the electrolytic system comprising the Ir-CoSe_(2)electrode not only produced hydrogen efficiently via HER,but also degraded organic pollutants(Methylene blue).The cell voltage of the dual-function electrolytic system was 1.58 V at the benchmark current density of 50 mA cm^(-2),which was significantly lower than the conventional water splitting voltage.It was indicated that this method was a novel strategy for designing advanced HER electrocatalysts by constructing multifunctional catalytic sites for hydrogen production and organic degradation.展开更多
The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional ...The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.展开更多
The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clu...The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.展开更多
Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)...Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)S_(4)(HVs-ZIS)and CoIn_(2)S_(4)(CIS)via a defect-guided heteroepitaxial growth strategy.The strong interface coupling induces adequate carriers exchanging passageway between HVs-ZIS and CIS,enhancing the internal electric field(IEF)in the ZnIn_(2)S_(4)/CoIn_(2)S_(4)(HVs-ZIS/CIS)heterostructure.The defect structure in HVs-ZIS induces an additional defect level,improving the separation efficiency of photocarriers.Moreover,promoted by the IEF and intimate heterointerface,photogenerated electrons trapped by the defect level can migrate to the valence band of CIS,contributing to massive photogenerated electrons with intense reducibility in HVs-ZIS/CIS.Consequently,the HVs-ZIS/CIS heterostructure performs a boosted H_(2)evolution activity of 33.65 mmol g^(-1)h^(-1).This work highlights the synergistic effects of defect and strong interface coupling in regulating carrier transfer and paves a brave avenue for constructing efficient heterostructure photocatalysts.展开更多
Establishing highly effective charge transfer channels in carbon nitride(g-C_(3)N_(4)) to enhance its photocatalytic activity is still a challenging issue.Herein,the delaminated 2D Ti_(3)C_(2) MXene nanosheets were em...Establishing highly effective charge transfer channels in carbon nitride(g-C_(3)N_(4)) to enhance its photocatalytic activity is still a challenging issue.Herein,the delaminated 2D Ti_(3)C_(2) MXene nanosheets were employed to decorate the P-doped tubular g-C_(3)N_(4)(PTCN)for engineering 1D/2D Schottky heterojunction(PTCN/TC)through electrostatic self-assembly.The optimized PTCN/TC exhibited the highest hydrogen evolution rate(565 μmol h^(-1)g^(-1)),which was 4.3 and 2.0-fold higher than pristine bulk g-C_(3)N_(4) and PTCN,respectively.Such enhancement may be primarily attributed to the phosphorus heteroatom doped and unique structure of 1D/2D g-C_(3)N_(4)/Ti_(3)C_(2) Schottky heterojunction,enhancing the light-harvesting and charges’separation.One-dimensional pathway of g-C_(3)N_(4) tube and built-in electric field of interfacial Schottky effect can significantly facilitate the spatial separation of photogenerated charge carriers,and simultaneously inhibit their recombination via Schottky barrier.In this composite,metallic Ti_(3)C_(2) was served as electrons sink and photons collector.Moreover,ultrathin Ti_(3)C_(2) flake with exposed terminal metal sites as a co-catalyst exhibited higher photocatalytic reactivity in H2 evolution compared to carbon materials(such as reduced graphene oxide).This work not only proposed the mechanism of tubular g-C_(3)N_(4)/Ti_(3)C_(2) Schottky junction in photocatalysis,but also provided a feasible way to load ultrathin Ti_(3)C_(2) as a co-catalyst for designing highly efficient photocatalysts.展开更多
Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment...Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).展开更多
ABSTRACT Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a“holy grail”for researchers,but is still a challenging issue.Herein,b...ABSTRACT Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a“holy grail”for researchers,but is still a challenging issue.Herein,based on the common polymeric carbon nitride(PCN),a hybrid co-catalysts system comprising plasmonic Au nanoparticles(NPs)and atomically dispersed Pt single atoms(PtSAs)with different functions was constructed to address this challenge.For the dual co-catalysts decorated PCN(PtSAs–Au_(2.5)/PCN),the PCN is photoexcited to generate electrons under UV and short-wavelength visible light,and the synergetic Au NPs and PtSAs not only accelerate charge separation and transfer though Schottky junctions and metal-support bond but also act as the co-catalysts for H_(2) evolution.Furthermore,the Au NPs absorb long-wavelength visible light owing to its localized surface plasmon resonance,and the adjacent PtSAs trap the plasmonic hot-electrons for H_(2) evolution via direct electron transfer effect.Consequently,the PtSAs–Au_(2.5)/PCN exhibits excellent broad-spectrum photocatalytic H_(2) evolution activity with the H_(2) evolution rate of 8.8 mmol g^(−1) h^(−1) at 420 nm and 264μmol g^(−1) h^(−1) at 550 nm,much higher than that of Au_(2.5)/PCN and PtSAs–PCN,respectively.This work provides a new strategy to design broad-spectrum photocatalysts for energy conversion reaction.展开更多
Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandston...Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.展开更多
The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution r...The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).展开更多
To address the issues of reduced performance and shortened lifespan during the low-carbonizating process of Al_(2)O_(3)-C refractories,nano-crystalline ZrC modified graphite was prepared using Zr powder and flake grap...To address the issues of reduced performance and shortened lifespan during the low-carbonizating process of Al_(2)O_(3)-C refractories,nano-crystalline ZrC modified graphite was prepared using Zr powder and flake graphite as raw materials,with NaCl and NaF mixed salt serving as the medium.The flake graphite was gradually replaced by ZrC modified graphite in the preparation of Al_(2)O_(3)-C refractories,and its impact on the material’s structure and properties was investigated.The results indicate that,compared to samples with only flake graphite,the introduction of 1 mass%to 5 mass%nano-crystalline ZrC modified graphite can significantly enhance the mechanical performance of low-carbon Al_(2)O_(3)-C refractories.When 5 mass%ZrC modified graphite is added,the mechanical properties of the samples are optimal,with the cold modulus of rupture and elastic modulus reaching 22.5 MPa and 65.0 GPa,respectively.展开更多
As typical quarternary copper-based chalcogenides,Cu–Zn–Sn–S nanocrystals(CZTS NCs)have emerged as a newfashioned electrocatalyst in hydrogen evolution reactions(HERs).Oleylamine(OM),a reducing surfactant and solve...As typical quarternary copper-based chalcogenides,Cu–Zn–Sn–S nanocrystals(CZTS NCs)have emerged as a newfashioned electrocatalyst in hydrogen evolution reactions(HERs).Oleylamine(OM),a reducing surfactant and solvent,plays a significant role in the assisting synthesis of CZTS NCs due to the ligand effect.Herein,we adopted a facile one-pot colloidal method for achieving the structure evolution of CZTS NCs from 2D nanosheets to 1D nanorods assisted through the continuous addition of OM.During the process,the mechanism of OM-induced morphology evolution was further discussed.When merely adding pure 1-dodecanethiol(DDT)as the solvent,the CZTS nanosheets were obtained.As OM was gradually added to the reaction,the CZTS NCs began to grow along the sides of the nanosheets and gradually shrink at the top,followed by the formation of stable nanorods.In acidic electrolytic conditions,the CZTS NCs with 1.0 OM addition display the optimal HER activity with a low overpotential of 561 m V at 10 m A/cm^(2) and a small Tafel slope of 157.6 m V/dec compared with other CZTS samples.The enhancement of HER activity could be attributed to the contribution of the synergistic effect of the diverse crystal facets to the reaction.展开更多
The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of ...The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of Ru nanoparticles(NPs) anchored on a two-dimensionally ordered MoSe_(2) nanosheet-embedded mesoporous hollow carbon spheres surface(Ru/MoSe_(2)@MHCS) for the largely boosted hydrogen evolution reaction(HER) performance. The combined advantages from the conductive support, oxyphilic MoSe_(2), and Ru active sites imparted a strong synergistic effect and charge redistribution in the Ru periphery which induced high catalytic activity, stability, and kinetics for HER. Specifically, the obtained Ru/MoSe_(2)@MHCS required a small overpotential of 25.5 and 38.4 mV to drive the kinetic current density of 10 mA cm^(-2)both in acid and alkaline media, respectively, which was comparable to that of the Pt/C catalyst. Experimental and theoretical results demonstrated that the charge transfer from MoSe_(2) to Ru NPs enriched the electronic density of Ru sites and thus facilitated hydrogen adsorption and water dissociation. The current work showed the significant interfacial engineering in Ru-based catalysts development and catalysis promotion effect understanding via the metal-support interaction.展开更多
Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) throu...Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.展开更多
Gibberellin 2-oxidases(GA2ox)are important enzymes that maintain the balance of bioactive GAs in plants.GA2ox genes have been identified and characterized in many plants,but these genes were not investigated in Brassi...Gibberellin 2-oxidases(GA2ox)are important enzymes that maintain the balance of bioactive GAs in plants.GA2ox genes have been identified and characterized in many plants,but these genes were not investigated in Brassica napus.Here,we identified 31 GA2ox genes in B.napus and 15 of these BnaGA2ox genes were distributed in the A and C subgenomes.Subcellular localization predictions suggested that all BnaGA2ox proteins were localized in the cytoplasm,and gene structure analysis showed that the BnaGA2ox genes contained 2–4 exons.Phylogenetic analysis indicated that BnGA2ox family proteins in monocotyledons and dicotyledons can be divided into four groups,including two C_(19)-GA2ox and two C_(20)-GA2ox clades.Group 4 is a C_(20)-GA2ox Class discovered recently.Most BnaGA2ox genes had a syntenic relationship with AtGA2ox genes.BnaGA2ox genes in the C subgenome had experienced stronger selection pressure than genes in the A subgenome.BnaGA2ox genes were highly expressed in specific tissues such as those involved in growth and development,and most of them were mainly involved in abiotic responses,regulation of phytohormones and growth and development.Our study provided a valuable evolutionary analysis of GA2ox genes in monocotyledons and dicotyledons,as well as an insight into the biological functions of GA2ox family genes in B.napus.展开更多
基金the financial support of the Doctoral Research Initiation Foundation of Linyi University(LYDX2020BS016)the National Natural Science Foundation of Shandong Province(ZR2021QB208,ZR2022MB054)+4 种基金the National Natural Science Foundation of China(22305262)SIAT Innovation Program for Excellent Young Researchers(2022)Shenzhen Science and Technology Program Grant(RCJC20200714114435061,ZDSYS20220527171406014)the City University of Hong Kong Donation Research Grants(9220061 and 9229021)City University of Hong Kong Strategic Research Grant(SRG 7005505)。
文摘The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporating iridium(Ir)ions on the atomic scale into orthorhombic-CoSe2(Ir-CoSe_(2))was reported.Outstanding hydrogen evolution activity in alkaline media such as a low overpotential of 48.7 mV at a current density of 10 mA cm^(-2)and better performance than commercial Pt/C catalysts at high current densities were found in the Ir-CoSe_(2) samples.In the experiments and theoretical calculations,it was revealed that Ir enabled CoSe_(2)to form multifunctional sites to synergistically catalyze alkaline HER by promoting the adsorption and dissociation of H_(2)O(Ir sites)and optimizing the binding energy for H^(*)on Co sites.It was noticeable that the electrolytic system comprising the Ir-CoSe_(2)electrode not only produced hydrogen efficiently via HER,but also degraded organic pollutants(Methylene blue).The cell voltage of the dual-function electrolytic system was 1.58 V at the benchmark current density of 50 mA cm^(-2),which was significantly lower than the conventional water splitting voltage.It was indicated that this method was a novel strategy for designing advanced HER electrocatalysts by constructing multifunctional catalytic sites for hydrogen production and organic degradation.
基金financial support from the National Natural Science Foundation of China (52203070)the Open Fund of State Key Laboratory of New Textile Materials and Advanced Processing Technologies (FZ2022005)+2 种基金the Open Fund of Hubei Key Laboratory of Biomass Fiber and Ecological Dyeing and Finishing (STRZ202203)the financial support provided by the China Scholarship Council (CSC)Visiting Scholar Programfinancial support from Institute for Sustainability,Energy and Resources,The University of Adelaide,Future Making Fellowship,Australia。
文摘The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.
基金supported by the National Natural Science Foundation of China(22205209,52202373 and U21A200972)China Postdoctoral Science Foundation(2022M722867)Key Research Project of Higher Education Institutions in Henan Province(23A530001)。
文摘The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.
基金supported by the National Natural Science Foundation of China(52072196,52002200,52102106,52202262,22379081,22379080)the Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09)+1 种基金the Natural Science Foundation of Shandong Province(ZR2020QE063,ZR202108180009,ZR2023QE059)the Project funded by China Postdoctoral Science Foundation(2023M741871)。
文摘Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)S_(4)(HVs-ZIS)and CoIn_(2)S_(4)(CIS)via a defect-guided heteroepitaxial growth strategy.The strong interface coupling induces adequate carriers exchanging passageway between HVs-ZIS and CIS,enhancing the internal electric field(IEF)in the ZnIn_(2)S_(4)/CoIn_(2)S_(4)(HVs-ZIS/CIS)heterostructure.The defect structure in HVs-ZIS induces an additional defect level,improving the separation efficiency of photocarriers.Moreover,promoted by the IEF and intimate heterointerface,photogenerated electrons trapped by the defect level can migrate to the valence band of CIS,contributing to massive photogenerated electrons with intense reducibility in HVs-ZIS/CIS.Consequently,the HVs-ZIS/CIS heterostructure performs a boosted H_(2)evolution activity of 33.65 mmol g^(-1)h^(-1).This work highlights the synergistic effects of defect and strong interface coupling in regulating carrier transfer and paves a brave avenue for constructing efficient heterostructure photocatalysts.
基金the financial supports from the National Natural Science Foundation of China(No.:22002146)Taishan Scholars Foundation of Shandong province(No.:tsqn201909058).
文摘Establishing highly effective charge transfer channels in carbon nitride(g-C_(3)N_(4)) to enhance its photocatalytic activity is still a challenging issue.Herein,the delaminated 2D Ti_(3)C_(2) MXene nanosheets were employed to decorate the P-doped tubular g-C_(3)N_(4)(PTCN)for engineering 1D/2D Schottky heterojunction(PTCN/TC)through electrostatic self-assembly.The optimized PTCN/TC exhibited the highest hydrogen evolution rate(565 μmol h^(-1)g^(-1)),which was 4.3 and 2.0-fold higher than pristine bulk g-C_(3)N_(4) and PTCN,respectively.Such enhancement may be primarily attributed to the phosphorus heteroatom doped and unique structure of 1D/2D g-C_(3)N_(4)/Ti_(3)C_(2) Schottky heterojunction,enhancing the light-harvesting and charges’separation.One-dimensional pathway of g-C_(3)N_(4) tube and built-in electric field of interfacial Schottky effect can significantly facilitate the spatial separation of photogenerated charge carriers,and simultaneously inhibit their recombination via Schottky barrier.In this composite,metallic Ti_(3)C_(2) was served as electrons sink and photons collector.Moreover,ultrathin Ti_(3)C_(2) flake with exposed terminal metal sites as a co-catalyst exhibited higher photocatalytic reactivity in H2 evolution compared to carbon materials(such as reduced graphene oxide).This work not only proposed the mechanism of tubular g-C_(3)N_(4)/Ti_(3)C_(2) Schottky junction in photocatalysis,but also provided a feasible way to load ultrathin Ti_(3)C_(2) as a co-catalyst for designing highly efficient photocatalysts.
基金Funded by the Doctoral Fund of Chengdu University(No.2081919131)the Sichuan Science and Technology Program(No.2023YFG0229)。
文摘Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).
基金supported by the National Natural Science Foundation of China(Grant No.51871078 and 52071119)Interdisciplinary Research Foundation of HIT(Grant No.IR2021208)+1 种基金State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2022TS38)Heilongjiang Science Foundation(No.LH2020B006).
文摘ABSTRACT Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a“holy grail”for researchers,but is still a challenging issue.Herein,based on the common polymeric carbon nitride(PCN),a hybrid co-catalysts system comprising plasmonic Au nanoparticles(NPs)and atomically dispersed Pt single atoms(PtSAs)with different functions was constructed to address this challenge.For the dual co-catalysts decorated PCN(PtSAs–Au_(2.5)/PCN),the PCN is photoexcited to generate electrons under UV and short-wavelength visible light,and the synergetic Au NPs and PtSAs not only accelerate charge separation and transfer though Schottky junctions and metal-support bond but also act as the co-catalysts for H_(2) evolution.Furthermore,the Au NPs absorb long-wavelength visible light owing to its localized surface plasmon resonance,and the adjacent PtSAs trap the plasmonic hot-electrons for H_(2) evolution via direct electron transfer effect.Consequently,the PtSAs–Au_(2.5)/PCN exhibits excellent broad-spectrum photocatalytic H_(2) evolution activity with the H_(2) evolution rate of 8.8 mmol g^(−1) h^(−1) at 420 nm and 264μmol g^(−1) h^(−1) at 550 nm,much higher than that of Au_(2.5)/PCN and PtSAs–PCN,respectively.This work provides a new strategy to design broad-spectrum photocatalysts for energy conversion reaction.
基金supported by the National Natural Science Foundation of China(Nos.42072130,41872152).
文摘Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.
基金This work was financially supported by the National Natural Science Foundation of China (52122308,21905253,51973200)the Natural Science Foundation of Henan (202300410372).
文摘The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).
文摘To address the issues of reduced performance and shortened lifespan during the low-carbonizating process of Al_(2)O_(3)-C refractories,nano-crystalline ZrC modified graphite was prepared using Zr powder and flake graphite as raw materials,with NaCl and NaF mixed salt serving as the medium.The flake graphite was gradually replaced by ZrC modified graphite in the preparation of Al_(2)O_(3)-C refractories,and its impact on the material’s structure and properties was investigated.The results indicate that,compared to samples with only flake graphite,the introduction of 1 mass%to 5 mass%nano-crystalline ZrC modified graphite can significantly enhance the mechanical performance of low-carbon Al_(2)O_(3)-C refractories.When 5 mass%ZrC modified graphite is added,the mechanical properties of the samples are optimal,with the cold modulus of rupture and elastic modulus reaching 22.5 MPa and 65.0 GPa,respectively.
基金partially supported by National Natural Science Foundation of China (12274021 and 62075005)。
文摘As typical quarternary copper-based chalcogenides,Cu–Zn–Sn–S nanocrystals(CZTS NCs)have emerged as a newfashioned electrocatalyst in hydrogen evolution reactions(HERs).Oleylamine(OM),a reducing surfactant and solvent,plays a significant role in the assisting synthesis of CZTS NCs due to the ligand effect.Herein,we adopted a facile one-pot colloidal method for achieving the structure evolution of CZTS NCs from 2D nanosheets to 1D nanorods assisted through the continuous addition of OM.During the process,the mechanism of OM-induced morphology evolution was further discussed.When merely adding pure 1-dodecanethiol(DDT)as the solvent,the CZTS nanosheets were obtained.As OM was gradually added to the reaction,the CZTS NCs began to grow along the sides of the nanosheets and gradually shrink at the top,followed by the formation of stable nanorods.In acidic electrolytic conditions,the CZTS NCs with 1.0 OM addition display the optimal HER activity with a low overpotential of 561 m V at 10 m A/cm^(2) and a small Tafel slope of 157.6 m V/dec compared with other CZTS samples.The enhancement of HER activity could be attributed to the contribution of the synergistic effect of the diverse crystal facets to the reaction.
基金supported by the National Natural Science Foundation of China (21972124, 22272148)the Priority Academic Program Development of Jiangsu Higher Education Institution。
文摘The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of Ru nanoparticles(NPs) anchored on a two-dimensionally ordered MoSe_(2) nanosheet-embedded mesoporous hollow carbon spheres surface(Ru/MoSe_(2)@MHCS) for the largely boosted hydrogen evolution reaction(HER) performance. The combined advantages from the conductive support, oxyphilic MoSe_(2), and Ru active sites imparted a strong synergistic effect and charge redistribution in the Ru periphery which induced high catalytic activity, stability, and kinetics for HER. Specifically, the obtained Ru/MoSe_(2)@MHCS required a small overpotential of 25.5 and 38.4 mV to drive the kinetic current density of 10 mA cm^(-2)both in acid and alkaline media, respectively, which was comparable to that of the Pt/C catalyst. Experimental and theoretical results demonstrated that the charge transfer from MoSe_(2) to Ru NPs enriched the electronic density of Ru sites and thus facilitated hydrogen adsorption and water dissociation. The current work showed the significant interfacial engineering in Ru-based catalysts development and catalysis promotion effect understanding via the metal-support interaction.
基金supported by the financial support from the National Natural Science Foundation of China (21871065, 22071038, 22209129)the Heilongjiang Touyan Team (HITTY20190033)the Interdisciplinary Research Foundation of HIT (IR2021205)。
文摘Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.
基金supported by the Chongqing Academy of Agricultural Sciences Youth Innovation Team Project(NKY-2018QC01)Chongqing Finance Special Project(NKY-2022AC002)+2 种基金the Natural Science Foundation Project of Yongchuan(2021yc-jckx20013)the Technology Innovation and Application Development(Surface)Project of Yongchuan(2021yc-cxfz30007)the National Oilseed Rape Industrial Technology System Sanxia Comprehensive Experiment Station Project(CARS-13).
文摘Gibberellin 2-oxidases(GA2ox)are important enzymes that maintain the balance of bioactive GAs in plants.GA2ox genes have been identified and characterized in many plants,but these genes were not investigated in Brassica napus.Here,we identified 31 GA2ox genes in B.napus and 15 of these BnaGA2ox genes were distributed in the A and C subgenomes.Subcellular localization predictions suggested that all BnaGA2ox proteins were localized in the cytoplasm,and gene structure analysis showed that the BnaGA2ox genes contained 2–4 exons.Phylogenetic analysis indicated that BnGA2ox family proteins in monocotyledons and dicotyledons can be divided into four groups,including two C_(19)-GA2ox and two C_(20)-GA2ox clades.Group 4 is a C_(20)-GA2ox Class discovered recently.Most BnaGA2ox genes had a syntenic relationship with AtGA2ox genes.BnaGA2ox genes in the C subgenome had experienced stronger selection pressure than genes in the A subgenome.BnaGA2ox genes were highly expressed in specific tissues such as those involved in growth and development,and most of them were mainly involved in abiotic responses,regulation of phytohormones and growth and development.Our study provided a valuable evolutionary analysis of GA2ox genes in monocotyledons and dicotyledons,as well as an insight into the biological functions of GA2ox family genes in B.napus.
