Photocatalytic transfer hydrogenation using water as the proton source has emerged as an attractive and green approach for the catalytic reduction of unsaturated bonds.Herein,we report an oxygen-defective TiO_(2)-supp...Photocatalytic transfer hydrogenation using water as the proton source has emerged as an attractive and green approach for the catalytic reduction of unsaturated bonds.Herein,we report an oxygen-defective TiO_(2)-supported palladium catalyst(Pd-TiO_(2)-Ov)for efficient photocatalytic water-donating transfer hydrogenation of anethole towards 4-n-propylanisole in a high yield of 99.9%,which is significantly higher compared to the pristine TiO_(2)-supported palladium catalyst(Pd-TiO_(2),74%).The enhanced performance is ascribed to the presence of oxygen vacancies,which facilitate light absorption and suppress the recombination of photogenerated electron-hole pairs.Furthermore,the Pd-TiO_(2)-Ov is versatile in hydrogenating various alkene substrates including those with hydroxyl,ether,fluoride,and chloride functional groups in full conversion,thus offering a green method for transfer hydrogenation of alkenes.This study provides new insights and advances in current hydrogenation technology with water as the proton source.展开更多
Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames w...Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames within the pre-chamber is explored.This study performed numerical simulations on a large-bore marine ammonia/hydrogen pre-chamber engine prototype,considering pre-chamber volume,throat diameter,the distance between the hydrogen injector and the spark plug,and the hydrogen injector angle.Compared with the original engine,when the pre-chamber volume is 73.4 ml,the throat diameter is 14 mm,the distance ratio is 0.92,and the hydrogen injector angle is 80°.Moreover,the peak pressure in the pre-chamber increased by 23.1%,and that in the main chamber increased by 46.3%.The results indicate that the performance of the original engine is greatly enhanced by altering its fuel and pre-chamber structure.展开更多
The inherent oxygen sensitivity of hydrogenases has limited their biomedical use.We report a hybrid peptide-nanocluster hydrogel that establishes a self-sustained anaerobic microenvironment,enabling hydrogenase-cataly...The inherent oxygen sensitivity of hydrogenases has limited their biomedical use.We report a hybrid peptide-nanocluster hydrogel that establishes a self-sustained anaerobic microenvironment,enabling hydrogenase-catalyzed hydrogen therapy under aerobic conditions.The Fmoc-KYF peptide network traps O_(2) in hydrophobic pockets,while photoexcited silver nanoclusters rapidly scavenge residual oxygen,ensuring stable hydrogen evolution.In vitro,the generated hydrogen mitigates oxidative stress and inflammation.In diabetic mice,the light-activated system accelerates wound closure,promotes angiogenesis,and drives macrophage polarization toward a reparative phenotype.This study introduces a bioengineering strategy that integrates material design,enzyme catalysis,and photodynamics to overcome oxygen limitation and advance hydrogenase-based therapeutic applications.展开更多
In general,metal carbides are synthesized via high-temperature-programmed solid-gas reactions using methane under an inert atmosphere.However,fabricating single-atom(SA)catalysts on such carbide supports typically inh...In general,metal carbides are synthesized via high-temperature-programmed solid-gas reactions using methane under an inert atmosphere.However,fabricating single-atom(SA)catalysts on such carbide supports typically inherits these demanding conditions,requiring multiple chemical reagents and prolonged processing.To overcome these synthetic limitations,we introduced a pulsed laser-driven strategy that integrates pulsed laser ablation and liquid-phase irradiation to construct atomically dispersed Pt sites on molybdenum carbide(Pt/MoC)nanospheres with tunable loading densities.These catalysts exhibit improved hydrogen evolution reaction(HER)activity in alkaline media,despite HER conventionally favoring acidic conditions.To enhance the hydrogen production efficiency of the electrolyzer while reducing energy consumption,we strategically replaced the conventional oxygen evolution reaction with the hydrazine oxidation reaction(HzOR)at the anode.Strong metal-support interactions between Pt atoms and MoC modulate the local electronic structure,thereby optimizing the adsorption energies of key intermediates for HzOR.In situ Raman spectroelectrochemistry and theoretical calculations elucidate the reaction mechanism,highlighting the role of Pt SA sites in lowering activation barriers for N2 and H2 evolution.The optimized Pt/MoC catalyst achieves enhanced HER performance in overall hydrazine splitting compared with conventional overall water splitting,maintaining structural integrity and outstanding stability over 100 h at 30 mA cm^(-2).This study establishes a pulsed laser-based strategy for atomic-engineered Pt/MoC as a promising platform for energy-effective and hydrazine-fueled hydrogen generation in alkaline conditions.展开更多
Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous s...Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.展开更多
The development of dual functional material for cyclic CO_(2)capture and hydrogenation is of great significance for converting diluted CO_(2)into valuable fuels,but suffers from kinetic limitation and deactivation of ...The development of dual functional material for cyclic CO_(2)capture and hydrogenation is of great significance for converting diluted CO_(2)into valuable fuels,but suffers from kinetic limitation and deactivation of adsorbent and catalyst.Herein,we engineered a series of RuNa/γ-Al_(2)O_(3)materials,varying the size of ruthenium from single atoms to clusters/nanoparticles.The coordination environment and structure sensitivity of ruthenium were quantitatively investigated at atomic scale.Our findings reveal that the reduced Ru nanoparticles,approximately 7.1 nm in diameter with a Ru-Ru coordination number of 5.9,exhibit high methane formation activity and selectivity at 340°C.The Ru-Na interfacial sites facilitate CO_(2)migration through a deoxygenation pathway,involving carbonate dissociation,carbonyl formation,and hydrogenation.In-situ experiments and theoretical calculations show that stable carbonyl intermediates on metallic Ru nanoparticles facilitate heterolytic C–O scission and C–H bonding,significantly lowering the energy barrier for activating stored CO_(2).展开更多
As a versatile and environmentally benign oxidant,hydrogen peroxide(H_(2)O_(2))is highly desired in sanitation,disinfection,environmental remediation,and the chemical industry.Compared with the conventional anthraquin...As a versatile and environmentally benign oxidant,hydrogen peroxide(H_(2)O_(2))is highly desired in sanitation,disinfection,environmental remediation,and the chemical industry.Compared with the conventional anthraquinone process,the electrosynthesis of H_(2)O_(2)through the two-electron oxygen reduction reaction(2e^(−)ORR)is an efficient,competitive,and promising avenue.Electrocatalysts and devices are two core factors in 2e^(−)ORR,but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear.To this end,this review adopts a multiscale perspective to summarize recent advancements in the design principles,catalytic mechanisms,and application prospects of 2e^(−)ORR catalysts,with a particular focus on the influence of pH conditions,aiming at providing guidance for the selective design of advanced 2e^(−)ORR catalysts for highly-efficient H_(2)O_(2)production.Moreover,in response to diverse on-site application demands,we elaborate on the evolution of H_(2)O_(2)electrosynthesis devices,from rotating ring-disk electrodes and H-type cells to diverse flow-type cells.We elaborate on their characteristics and shortcomings,which can be beneficial for their further upgrades and customized applications.These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.展开更多
The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multip...The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multiple kinetic steps during hydrogen production.To address this challenge,a heterogeneous catalyst comprising metal Co,CoO and carbon-doped Mo_(2)N(Co–CoO–C/Mo_(2)N/CC)was synthesized by heat treatment of carbon cloth-supported CoMoO_(4) microrods in a mixed reduction atmosphere.The resulting catalyst has rich interfaces,exhibiting excellent initial HER activity with an overpotential of 27 mV at 10 mA·cm^(−2) and a Tafel slope of 37 mV·dec^(−1).Further studies show that the activity and stability of the catalyst can be tailored by the dynamic surface reconfiguration and doping effects.The carbon doping and high crystallinity in Mo_(2)N help to reduce the dissolution of Mo and the surface metal Co is preferentially converted into stable Co(OH)2,thus stabilizing the structure of the catalyst and coordinating various reaction kinetics.In an electrolyzer comprising a heterogeneous Co–CoO–C/Mo_(2)N cathode and NiFe layered double hydroxides(LDH)anode,only 1.58 V is required to achieve a current density of 50 mA·cm^(−2),outperforming Pt/RuO catalysts.After continuous electrolysis for 100 h,the potential increases by merely 19 mV from the initial 1.58 V,indicating excellent stability.This study presents a novel strategy for developing highly active and stable heterogeneous catalysts,offering insights into the dynamic evolution of catalyst structures and laying the groundwork for designing efficient and stable composite catalysts for energy conversion applications.展开更多
Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/mo...Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/molybdenum nitride rod-shaped structures(denoted Co/Mo_(2)N)via ammonia-assisted reduction,which effectively modulating the HER performance.The optimized Co/Mo_(2)N-500,characterized by 3%tensile lattice strain,demonstrates exceptional HER activity with lower overpotentials of140 mV and 184 mV at high current density of 1000 mA cm^(-2)in alkaline freshwater and seawater electrolytes,respectively.Co/Mo_(2)N also exhibits excellent long-term durability even at a high current density of 300 mA cm^(-2),surpassing its counterparts and benchmark Pt/C catalyst.Density functional theory calculations validate that the tensile strain optimizes the d-band states,water dissociation,and hydrogen adsorption kinetics of the strained Mo_(2)N in Co/Mo_(2)N,thereby improving its catalytic efficacy.This work provides valuable insights into controlling lattice strain to develop highly efficient electrocatalysts towards advanced electrocatalytic applications.展开更多
Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention...Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention.CLHP demands redox catalysts with high oxygen capacity,regulatable reactivity,and structural integrity even under harsh operational conditions.Currently,sintering,agglomeration,and inactivation of redox catalysts during cyclic lattice oxygen release and restoration are challenging,hindering the wide industrialization of the chemical looping(CL)process.Moreover,the precise control of activity and reaction rate of the redox catalysts to flexibly accommodate the demands of various reaction substrates remains unclear.This paper introduces the design of a nano-scaled redox catalyst featuring a unique core-shell structure.By precisely controlling the shell thickness,a series of hierarchical Fe_(2)O_(3)@SiO_(2)redox catalysts were successfully synthesized.Building on this achievement,an in-depth investigation was conducted into the impact of the thickness and spatial structure of the inert support on the stability and mass transfer rate of the redox catalyst,aiming to achieve a perfect balance between these two factors during the CLHP process.A thin shell(70 nm)exhibits excellent cyclic stability,maintaining consistent performance in 30 consecutive redox cycles,while a thicker shell(200 nm)undergoes rapid deactivation due to the formation of a substantial amount of iron silicate.In-situ transmission electron microscopy(TEM)reveals that the SiO_(2)shell effectively restricts the agglomeration of Fe_(2)O_(3).The unique core-shell structure and controllable shell thickness offer novel insights into the flexible design of efficient and durable hierarchical redox catalysts with spatial structure.展开更多
A growing global population and the increasing prevalence of diet-related health issues such as“hidden hunger”,obesity,hypertension,and diabetes necessitate a fundamental rethinking of crop design and breeding.Synth...A growing global population and the increasing prevalence of diet-related health issues such as“hidden hunger”,obesity,hypertension,and diabetes necessitate a fundamental rethinking of crop design and breeding.Synthetic metabolic engineering offers a method to modify and redesign metabolic pathways to increase the nutritional value of crops.We summarize recent advances in the biofortification of key nutrients including provitamin A,vitamin C,vitamin B9,iron,zinc,anthocyanins,flavonoids,and unsaturated fatty acids.We discuss the potential of multi-gene stacking,gene editing,enzyme engineering,and artificial intelligence in synthetic metabolic engineering.We propose future research directions and potential solutions centered on leveraging AI-driven systems biology,precision gene editing,enzyme engineering,agrobacterium-mediated genotype-independent transformation,and modular metabolic engineering strategies to develop next-generation nutritionally enhanced super crops and transform global food systems.展开更多
This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess a...This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess amorphous carbon.X-ray absorption near-edge structure(XANES)analysis confirmed that Co and Ni predominantly exist in the+2 oxidation state,whereas extended X-ray absorption fine structure(EXAFS)analysis revealed shortened Co-O and Co-Co bond lengths,indicating lattice distortions.Rietveld refinement and electron microscopy confirmed the formation of a homogeneous solid solution(NixCo_(2-x)(O,F)_(3))rather than a simple CoO/NiO composite.The optimized material(AH-2)exhibited the lowest overpotential(145 mV at 10 mA cm^(-1))and the smallest Tafel slope(98 mV dec^(-1)),attributed to its balanced phase composition,enhanced electronic conductivity,and synergistic effects of carbon and fluorine incorporation.Electrochemical impedance spectroscopy(EIS)confirmed improved charge transfer efficiency,correlating with enhanced catalytic activity.These findings provide critical insights into the tunability of transition metal oxide catalysts via controlled lattice modifications,offering a promising avenue for developing cost-effective and efficient electrocatalysts for sustainable hydrogen production.展开更多
Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains...Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.展开更多
Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomat...Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomaterials under diverse electrochemical operations remain limited.Here,exemplified by three electrochemical operations,including cyclic voltammetry(CV),squarewave potential(SWP)and chronoamperometry(CA),we reveal the structural evolution behavior and the corresponding electrocatalytic activity of bimetallic telluride hollow nanorods(Ir_(1-x)Ru_(x)0Te_(2)HNRs).It was found that the surface Te atoms in Ir_(1-x)Ru_(x)0Te_(2)HNRs undergo preferential leaching during the CV and SWP processes,ultimately leading to the formation of a metal alloy shell.In contrast,during the CA process,the surface reconstruction induced by Te leaching was suppressed by the adsorption of anions on the electrode surface.Electrocatalytic tests show that the CV activated Ir_(0.75)Ru_(0.25)Te_(2)HNRs exhibit excellent activity for the hydrogen oxidation reaction in 0.1 M KOH,with a mass activity of 686 Ag^(-1)at an overpotential of50 mV,which is 2.9 times higher than that of commercialPt/C catalyst.Density functional theory(DFT)computation reveals that the incorporation of Ru optimizes the hydroxyl binding energy of IrRu alloy,thus resulting in the reduced reaction energy barrier of hydrogen oxidation reaction.This work provides a new insight into the design of efficient catalysts through electrochemical surface engineering.展开更多
Birefringent materials play a crucial role in light polarization, with important applications in fiber-optic com-munications. However, developing such materials for the solar-blind region and shorter wavelengths remai...Birefringent materials play a crucial role in light polarization, with important applications in fiber-optic com-munications. However, developing such materials for the solar-blind region and shorter wavelengths remains challenging due to the inherent trade-off between birefringence and bandgap. In this work, we introduce a strategic assembly of cyanuric rings with biuret units-the latter identified for the first time as a birefringence-active motif-resulting in two neW compounds: [H_(5)C_(2)N_(3)O_(2)][H_(3)C_(3)N_(3)O_(3)] (1) and [H_(5)C_(2)N_(3)O_(2)][H_(3)C_(3)N_(3)O_(3)]·xH_(2)O (x ≈ 0.43) (2). Through hydrogen bonding-driven structural optimization, compound 2 achieves a 50% increase in birefringence (Δn = 0.403 @ 546 nm) compared to 1, while retaining a short cutoff edge of 208 nm. This advancement demonstrates that hydrogen-bond-guided structural design, combined with novel functional units, can overcome the traditional birefringence-bandgap conflict, opening new possibilities for short-wavelength birefringent materials with strong optical anisotropy.展开更多
Understanding the role of cations within the catalysts in the interfacial water behavior at the electrolyte/catalyst interface is of pivotal importance for designing advanced catalysts toward hydrogen evolution reacti...Understanding the role of cations within the catalysts in the interfacial water behavior at the electrolyte/catalyst interface is of pivotal importance for designing advanced catalysts toward hydrogen evolution reaction(HER),which remains obscure and requires deep probing.Herein,we demonstrate the first investigation of interfacial water behavior on the surface of a series of sodium tungsten bronzes(Na_(x)WO_(3),0_(x)WO_(3)/electrolyte interface.Our integrated studies indicate that the Na ions significantly enrich the electronic state of WO_(6)octahedrons in Na_(x)WO_(3),which leads to the regulated electronic and atomic structures,endowing Na_(x)WO_(3)with disordered interfacial water network containing more isolated H_(3)O^(+)and subsequently moderate H^(*)adsorption to speed the Volmer step at the Na_(x)WO_(3)surface,thus boosting the HER.Consequently,the intrinsic HER activities achieved on those Na_(x)WO_(3)are tens of times higher than those on WO_(3).Particularly,it is found that Na concentration x=0.69 endows Na_(x)WO_(3)with the highest intrinsic HER activity,and the resultant Na_(0.69)WO_(3)with a unique porous octahedral structure exhibits a low overpotential of only 64 mV at current density of 10 mA cm^(-2)in acidic electrolyte.This study provides the first insight into the cation-dependent interfacial water behavior induced by the cations within the catalyst and establishes the interfacial water-activity relationship of HER,thus allowing for the design of a more advanced catalyst with efficient interfacial structu res towa rds HER.展开更多
Perovskite oxides have shown great potential application in fuel cells due to the unique crystal structures and tunable composition as well as effective capability toward the oxygen reduction reaction(ORR),whereas the...Perovskite oxides have shown great potential application in fuel cells due to the unique crystal structures and tunable composition as well as effective capability toward the oxygen reduction reaction(ORR),whereas the investigation on the electrocatalytic performance of perovskite oxides toward the two-electron ORR to H_(2)O_(2)production remains very limited.Herein,a facile synthetic method has been developed to prepare La_(2)Sn_(2)O_(7)@La-doped ZnSnO_(3)heterostructures comprising of amorphous La_(2)Sn_(2)O_(7)and crystalline La-doped ZnSnO_(3).The optimal La_(2)Sn_(2)O_(7)@Ladoped ZnSnO_(3)heterostructures catalyst exhibits a significantly improved two-electron ORR performance to H_(2)O_(2)production with onset potential of 0.77 V and large current density of 2.51 m A.cm^(-2)at 0.1 V compared to ZnSnO_(3)(0.75 V,1.80 m A.cm^(-2),0.11 m A) as well as maintains high H_(2)O_(2)selectivity of 80%,which has been theoretically demonstrated to be contributed to the synergistic effect of amorphous La_(2)Sn_(2)O_(7)and crystalline La-doped ZnSnO_(3).Moreover,high H_(2)O_(2)yield rate of 2.9 m M.h^(-1)at 0.1 V can be achieved with a superior turnover frequency(TOF) of3.31 × 10^(-2)s^(-1)compared to the ZnSnO_(3)catalyst(2.10 × 10^(-2)s^(-1)).This work reveals the great potential of perovskite oxide as promising candidates for the environmentally friendly synthesis of hydrogen peroxide.展开更多
Structural engineering enhances plasmonic stability and amplifies localized electric fields,yet the limited intrinsic activity of plasmonic materials necessitates integrating catalytic active sites.Herein,we design a ...Structural engineering enhances plasmonic stability and amplifies localized electric fields,yet the limited intrinsic activity of plasmonic materials necessitates integrating catalytic active sites.Herein,we design a yolk@shell nanoreactor featuring dual-plasmonic Au@CuS core-shell structures encapsulated by sulfur vacancy-rich ZnIn2S4(Sv-ZIS).The electromagnetic“hotspots”from Au and CuS near-field coupling concentrate incident light to boost hot-carrier generation and migration while sulfur vacancies in Sv-ZIS promote hydrogen evolution.This dual mechanism synergistically achieves 86.3 mmol g^(-1)h-1of H2production(65.6%quantum efficiency at 420 nm),maintaining 48.3 mmol g^(-1)h-1at 6℃.Density functional theory(DFT)simulations demonstrate that sulfur vacancies not only reduce the H*adsorption energy barrier from 0.87 to 0.11 eV but also amplify the interfacial electric field strength by 9%.Vacancy-redirected fields favor proton reduction pathways,accelerating charge transfer kinetics.Comparative studies confirm the universal superiority of dual-plasmonic architecture,while Sv-ZIS shells exhibit optimized activity through defect-mediated electronic interactions.This work provides a blueprint for bridging plasmonic field enhancement and defect engineering in multi-component photocatalysts.展开更多
基金supported by the National Key Research and Development Program of China(2023YFD2200505)National Natural Science Foundation of China(22202105),Natural Science Foundation of Jiangsu Higher Education Institutions of China(21KJA150003)the Innovation and Entrepreneurship Team Program of Jiangsu Province(JSSCTD202345).
文摘Photocatalytic transfer hydrogenation using water as the proton source has emerged as an attractive and green approach for the catalytic reduction of unsaturated bonds.Herein,we report an oxygen-defective TiO_(2)-supported palladium catalyst(Pd-TiO_(2)-Ov)for efficient photocatalytic water-donating transfer hydrogenation of anethole towards 4-n-propylanisole in a high yield of 99.9%,which is significantly higher compared to the pristine TiO_(2)-supported palladium catalyst(Pd-TiO_(2),74%).The enhanced performance is ascribed to the presence of oxygen vacancies,which facilitate light absorption and suppress the recombination of photogenerated electron-hole pairs.Furthermore,the Pd-TiO_(2)-Ov is versatile in hydrogenating various alkene substrates including those with hydroxyl,ether,fluoride,and chloride functional groups in full conversion,thus offering a green method for transfer hydrogenation of alkenes.This study provides new insights and advances in current hydrogenation technology with water as the proton source.
基金Supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions under Grant No.014000319/2018-00391.
文摘Pre-chamber ignition technology can address the issue of uneven in-cylinder mixture combustion in large-bore marine engines.The impact of various pre-chamber structures on the formation of the mixture and jet flames within the pre-chamber is explored.This study performed numerical simulations on a large-bore marine ammonia/hydrogen pre-chamber engine prototype,considering pre-chamber volume,throat diameter,the distance between the hydrogen injector and the spark plug,and the hydrogen injector angle.Compared with the original engine,when the pre-chamber volume is 73.4 ml,the throat diameter is 14 mm,the distance ratio is 0.92,and the hydrogen injector angle is 80°.Moreover,the peak pressure in the pre-chamber increased by 23.1%,and that in the main chamber increased by 46.3%.The results indicate that the performance of the original engine is greatly enhanced by altering its fuel and pre-chamber structure.
基金supported by the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(No.2019R1A6C1010042,RS-2024-00434932,and RS-2025-12872968)by the Korea government(MSIT)(PG2025039-02)+3 种基金support from the National Research Foundation of Korea(NRF),(2022R1A2C2010686,RS-2025-02634080,RS-2021-NR060090,and RS-2024-00405324)the Core-Facility Center for Photochemistry&Nanomaterials,Gyeongsang National University,In-situ Cryo X-ray Absorption Spectrometer,IC-XAS(NFEC-2025-07-307201)supported by the Glocal University 30 Project Fund of Gyeongsang National University in 2025the Odisha State Higher Education Council,Department of Higher Education,Government of Odisha for financial support under MRI(23EM/PH/123).
文摘In general,metal carbides are synthesized via high-temperature-programmed solid-gas reactions using methane under an inert atmosphere.However,fabricating single-atom(SA)catalysts on such carbide supports typically inherits these demanding conditions,requiring multiple chemical reagents and prolonged processing.To overcome these synthetic limitations,we introduced a pulsed laser-driven strategy that integrates pulsed laser ablation and liquid-phase irradiation to construct atomically dispersed Pt sites on molybdenum carbide(Pt/MoC)nanospheres with tunable loading densities.These catalysts exhibit improved hydrogen evolution reaction(HER)activity in alkaline media,despite HER conventionally favoring acidic conditions.To enhance the hydrogen production efficiency of the electrolyzer while reducing energy consumption,we strategically replaced the conventional oxygen evolution reaction with the hydrazine oxidation reaction(HzOR)at the anode.Strong metal-support interactions between Pt atoms and MoC modulate the local electronic structure,thereby optimizing the adsorption energies of key intermediates for HzOR.In situ Raman spectroelectrochemistry and theoretical calculations elucidate the reaction mechanism,highlighting the role of Pt SA sites in lowering activation barriers for N2 and H2 evolution.The optimized Pt/MoC catalyst achieves enhanced HER performance in overall hydrazine splitting compared with conventional overall water splitting,maintaining structural integrity and outstanding stability over 100 h at 30 mA cm^(-2).This study establishes a pulsed laser-based strategy for atomic-engineered Pt/MoC as a promising platform for energy-effective and hydrazine-fueled hydrogen generation in alkaline conditions.
文摘Traditional polymeric photocatalysts are typically constructed using aromatic building blocks to enhanceπ-conjugation.However,their inherent hydrophobicity and rigid structure lead to poor dispersibility in aqueous solutions,resulting in significant optical losses and exciton recombination.In this study,two series of six novel polymer photocatalysts(FLUSO,FLUSO-PEG10,FLUSO-PEG30;CPDTSO,CPDTSO-PEG10,CPDTSO-PEG30)are designed and synthesized by incorporating the hydrophilic,non-conjugated polyethylene glycol(PEG)chain,into both the main and side chains of polymers.By precisely optimizing the ratio of hydrophilic PEG segments,the water dispersibility is significantly improved while the light absorption capability of the polymer photocatalysts is well maintained.The experimental results confirm that the optimized FLUSO-PEG10 exhibits excellent photocatalytic hydrogen evolution rate,reaching up to 33.9 mmol/(g·h),which is nearly three times higher than that of fullyπ-conjugated counterparts.Water contact angles and particle size analyses reveal that incorporating non-conjugated segments into the main chains enhances the capacitance of the polymer/water interface and reduces particle aggregation,leading to improved photocatalyst dispersion and enhanced charge generation.
基金National Key R&D Program of China(2022YFE0105900)National Natural Science Foundation of China(52306179)+1 种基金Science and Technology Innovation Program of Hunan Province(2021RC4006)High Performance Computing Center of Central South University。
文摘The development of dual functional material for cyclic CO_(2)capture and hydrogenation is of great significance for converting diluted CO_(2)into valuable fuels,but suffers from kinetic limitation and deactivation of adsorbent and catalyst.Herein,we engineered a series of RuNa/γ-Al_(2)O_(3)materials,varying the size of ruthenium from single atoms to clusters/nanoparticles.The coordination environment and structure sensitivity of ruthenium were quantitatively investigated at atomic scale.Our findings reveal that the reduced Ru nanoparticles,approximately 7.1 nm in diameter with a Ru-Ru coordination number of 5.9,exhibit high methane formation activity and selectivity at 340°C.The Ru-Na interfacial sites facilitate CO_(2)migration through a deoxygenation pathway,involving carbonate dissociation,carbonyl formation,and hydrogenation.In-situ experiments and theoretical calculations show that stable carbonyl intermediates on metallic Ru nanoparticles facilitate heterolytic C–O scission and C–H bonding,significantly lowering the energy barrier for activating stored CO_(2).
基金supported by the National Natural Science Foundation of China(Nos.22102073,22075147).
文摘As a versatile and environmentally benign oxidant,hydrogen peroxide(H_(2)O_(2))is highly desired in sanitation,disinfection,environmental remediation,and the chemical industry.Compared with the conventional anthraquinone process,the electrosynthesis of H_(2)O_(2)through the two-electron oxygen reduction reaction(2e^(−)ORR)is an efficient,competitive,and promising avenue.Electrocatalysts and devices are two core factors in 2e^(−)ORR,but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear.To this end,this review adopts a multiscale perspective to summarize recent advancements in the design principles,catalytic mechanisms,and application prospects of 2e^(−)ORR catalysts,with a particular focus on the influence of pH conditions,aiming at providing guidance for the selective design of advanced 2e^(−)ORR catalysts for highly-efficient H_(2)O_(2)production.Moreover,in response to diverse on-site application demands,we elaborate on the evolution of H_(2)O_(2)electrosynthesis devices,from rotating ring-disk electrodes and H-type cells to diverse flow-type cells.We elaborate on their characteristics and shortcomings,which can be beneficial for their further upgrades and customized applications.These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
基金supported by the National Natural Science Foundation of China(Nos.22379116,U2003130 and U2004210)the Outstanding Youth Foundation of Natural Science Foundation of Hubei Province(No.2020CFA099)+1 种基金the Foundation of Science Research Program from Hubei Provincial Department of Education(No.Q20221101)the Innovation group of Key Research and Development Program of Hubei Province(Nos.2021BAA208 and 2022BCA061).
文摘The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multiple kinetic steps during hydrogen production.To address this challenge,a heterogeneous catalyst comprising metal Co,CoO and carbon-doped Mo_(2)N(Co–CoO–C/Mo_(2)N/CC)was synthesized by heat treatment of carbon cloth-supported CoMoO_(4) microrods in a mixed reduction atmosphere.The resulting catalyst has rich interfaces,exhibiting excellent initial HER activity with an overpotential of 27 mV at 10 mA·cm^(−2) and a Tafel slope of 37 mV·dec^(−1).Further studies show that the activity and stability of the catalyst can be tailored by the dynamic surface reconfiguration and doping effects.The carbon doping and high crystallinity in Mo_(2)N help to reduce the dissolution of Mo and the surface metal Co is preferentially converted into stable Co(OH)2,thus stabilizing the structure of the catalyst and coordinating various reaction kinetics.In an electrolyzer comprising a heterogeneous Co–CoO–C/Mo_(2)N cathode and NiFe layered double hydroxides(LDH)anode,only 1.58 V is required to achieve a current density of 50 mA·cm^(−2),outperforming Pt/RuO catalysts.After continuous electrolysis for 100 h,the potential increases by merely 19 mV from the initial 1.58 V,indicating excellent stability.This study presents a novel strategy for developing highly active and stable heterogeneous catalysts,offering insights into the dynamic evolution of catalyst structures and laying the groundwork for designing efficient and stable composite catalysts for energy conversion applications.
基金supported by the Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy(2020CB1007)Fundamental Research Funds for the Central Universities and Guangxi Key Laboratory of Information Materials and Guilin University of Electronic Technology,China(231002-K)+4 种基金Natural Science Foundation of Guangxi Zhuang Autonomous Region(2022GXNSFAA035467)Guangxi Science and Technology Program(Guike AD21220067)National Natural Science Foundation of China(22369002)Nationally Funded Postdoctoral Researcher Program(GZC20230756)China Postdoctoral Science Foundation(2024M750858)。
文摘Lattice-strain engineering has demonstrated its capability to influence the electronic structure and catalytic performance of electrocatalysts.Herein,we present a facile method for inducing thermal strain in cobalt/molybdenum nitride rod-shaped structures(denoted Co/Mo_(2)N)via ammonia-assisted reduction,which effectively modulating the HER performance.The optimized Co/Mo_(2)N-500,characterized by 3%tensile lattice strain,demonstrates exceptional HER activity with lower overpotentials of140 mV and 184 mV at high current density of 1000 mA cm^(-2)in alkaline freshwater and seawater electrolytes,respectively.Co/Mo_(2)N also exhibits excellent long-term durability even at a high current density of 300 mA cm^(-2),surpassing its counterparts and benchmark Pt/C catalyst.Density functional theory calculations validate that the tensile strain optimizes the d-band states,water dissociation,and hydrogen adsorption kinetics of the strained Mo_(2)N in Co/Mo_(2)N,thereby improving its catalytic efficacy.This work provides valuable insights into controlling lattice strain to develop highly efficient electrocatalysts towards advanced electrocatalytic applications.
基金financial support from the National Natural Science Foundation of China(52076209,22179027,22469006)the Foundation and Applied Foundation Research of Guangdong Province(2022B1515020045)the Heilongjiang Key Research and Development Project of China(JD22A026)。
文摘Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention.CLHP demands redox catalysts with high oxygen capacity,regulatable reactivity,and structural integrity even under harsh operational conditions.Currently,sintering,agglomeration,and inactivation of redox catalysts during cyclic lattice oxygen release and restoration are challenging,hindering the wide industrialization of the chemical looping(CL)process.Moreover,the precise control of activity and reaction rate of the redox catalysts to flexibly accommodate the demands of various reaction substrates remains unclear.This paper introduces the design of a nano-scaled redox catalyst featuring a unique core-shell structure.By precisely controlling the shell thickness,a series of hierarchical Fe_(2)O_(3)@SiO_(2)redox catalysts were successfully synthesized.Building on this achievement,an in-depth investigation was conducted into the impact of the thickness and spatial structure of the inert support on the stability and mass transfer rate of the redox catalyst,aiming to achieve a perfect balance between these two factors during the CLHP process.A thin shell(70 nm)exhibits excellent cyclic stability,maintaining consistent performance in 30 consecutive redox cycles,while a thicker shell(200 nm)undergoes rapid deactivation due to the formation of a substantial amount of iron silicate.In-situ transmission electron microscopy(TEM)reveals that the SiO_(2)shell effectively restricts the agglomeration of Fe_(2)O_(3).The unique core-shell structure and controllable shell thickness offer novel insights into the flexible design of efficient and durable hierarchical redox catalysts with spatial structure.
基金supported by grants from the Guangxi Science and Technology Major Project(GKAA24206023)the Biological Breeding-National Science and Technology Major Project(2024ZD04077)+2 种基金the National Natural Science Foundation of China(32272120)the National Key Research and Development Program of China(2024YFF1000800)the Guangdong Basic Research Center of Excellence for Precise Breeding of Future Crops Major Project(FCBRCE-202502,FCBRCE-202504).
文摘A growing global population and the increasing prevalence of diet-related health issues such as“hidden hunger”,obesity,hypertension,and diabetes necessitate a fundamental rethinking of crop design and breeding.Synthetic metabolic engineering offers a method to modify and redesign metabolic pathways to increase the nutritional value of crops.We summarize recent advances in the biofortification of key nutrients including provitamin A,vitamin C,vitamin B9,iron,zinc,anthocyanins,flavonoids,and unsaturated fatty acids.We discuss the potential of multi-gene stacking,gene editing,enzyme engineering,and artificial intelligence in synthetic metabolic engineering.We propose future research directions and potential solutions centered on leveraging AI-driven systems biology,precision gene editing,enzyme engineering,agrobacterium-mediated genotype-independent transformation,and modular metabolic engineering strategies to develop next-generation nutritionally enhanced super crops and transform global food systems.
基金supported by the Russian Science Foundation(project No.24-43-00215,http://rscf.ru/project/24-43-00215/).
文摘This study explores a novel strategy to enhance the hydrogen evolution reaction(HER)activity of carbon-supported rock salt-type NiCo_(2)(O,F)_(3) nanorods through lattice modifications induced by fluorine and excess amorphous carbon.X-ray absorption near-edge structure(XANES)analysis confirmed that Co and Ni predominantly exist in the+2 oxidation state,whereas extended X-ray absorption fine structure(EXAFS)analysis revealed shortened Co-O and Co-Co bond lengths,indicating lattice distortions.Rietveld refinement and electron microscopy confirmed the formation of a homogeneous solid solution(NixCo_(2-x)(O,F)_(3))rather than a simple CoO/NiO composite.The optimized material(AH-2)exhibited the lowest overpotential(145 mV at 10 mA cm^(-1))and the smallest Tafel slope(98 mV dec^(-1)),attributed to its balanced phase composition,enhanced electronic conductivity,and synergistic effects of carbon and fluorine incorporation.Electrochemical impedance spectroscopy(EIS)confirmed improved charge transfer efficiency,correlating with enhanced catalytic activity.These findings provide critical insights into the tunability of transition metal oxide catalysts via controlled lattice modifications,offering a promising avenue for developing cost-effective and efficient electrocatalysts for sustainable hydrogen production.
基金financially supported by the National Natural Science Foundation of China(Nos.22272118,22172111,and 22309134)the Science and Technology Commission of Shanghai Municipality,China(Nos.22ZR1464100,20ZR1460300,and 19DZ2271500)+2 种基金the China Postdoctoral Science Foundation(2022M712402),the Shanghai Rising-Star Program(23YF1449200)the Zhejiang Provincial Science and Technology Project(2022C01182)the Fundamental Research Funds for the Central Universities(2023-3-YB-07)。
文摘Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.
基金financially supported by the National Natural Science Foundation of China(Nos.22205196 and U1904215)the Natural Science Foundation of Jiangsu Province(No.BK20210790)the start-up fundings from Yangzhou University
文摘Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomaterials under diverse electrochemical operations remain limited.Here,exemplified by three electrochemical operations,including cyclic voltammetry(CV),squarewave potential(SWP)and chronoamperometry(CA),we reveal the structural evolution behavior and the corresponding electrocatalytic activity of bimetallic telluride hollow nanorods(Ir_(1-x)Ru_(x)0Te_(2)HNRs).It was found that the surface Te atoms in Ir_(1-x)Ru_(x)0Te_(2)HNRs undergo preferential leaching during the CV and SWP processes,ultimately leading to the formation of a metal alloy shell.In contrast,during the CA process,the surface reconstruction induced by Te leaching was suppressed by the adsorption of anions on the electrode surface.Electrocatalytic tests show that the CV activated Ir_(0.75)Ru_(0.25)Te_(2)HNRs exhibit excellent activity for the hydrogen oxidation reaction in 0.1 M KOH,with a mass activity of 686 Ag^(-1)at an overpotential of50 mV,which is 2.9 times higher than that of commercialPt/C catalyst.Density functional theory(DFT)computation reveals that the incorporation of Ru optimizes the hydroxyl binding energy of IrRu alloy,thus resulting in the reduced reaction energy barrier of hydrogen oxidation reaction.This work provides a new insight into the design of efficient catalysts through electrochemical surface engineering.
基金the National Key R&D Pro-gram of China(2021YFA0717800)National Natural Science Founda-tion of China(22322510)+3 种基金West Light Foundation of CAS(XBZG-ZDSYS 202201)Natural Science Foundation of Xinjiang Uygur Autonomous Region(2022D01E87)Science and Technology Program of Xinjiang Uyghur Autonomous Region(2025E01008)Tianshan Talent Training Program(2022TSYCCX0071).
文摘Birefringent materials play a crucial role in light polarization, with important applications in fiber-optic com-munications. However, developing such materials for the solar-blind region and shorter wavelengths remains challenging due to the inherent trade-off between birefringence and bandgap. In this work, we introduce a strategic assembly of cyanuric rings with biuret units-the latter identified for the first time as a birefringence-active motif-resulting in two neW compounds: [H_(5)C_(2)N_(3)O_(2)][H_(3)C_(3)N_(3)O_(3)] (1) and [H_(5)C_(2)N_(3)O_(2)][H_(3)C_(3)N_(3)O_(3)]·xH_(2)O (x ≈ 0.43) (2). Through hydrogen bonding-driven structural optimization, compound 2 achieves a 50% increase in birefringence (Δn = 0.403 @ 546 nm) compared to 1, while retaining a short cutoff edge of 208 nm. This advancement demonstrates that hydrogen-bond-guided structural design, combined with novel functional units, can overcome the traditional birefringence-bandgap conflict, opening new possibilities for short-wavelength birefringent materials with strong optical anisotropy.
基金financially supported by the National Natural Science Foundation of China(22279069,22179067,22478211 and 22372017)the Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10)。
文摘Understanding the role of cations within the catalysts in the interfacial water behavior at the electrolyte/catalyst interface is of pivotal importance for designing advanced catalysts toward hydrogen evolution reaction(HER),which remains obscure and requires deep probing.Herein,we demonstrate the first investigation of interfacial water behavior on the surface of a series of sodium tungsten bronzes(Na_(x)WO_(3),0_(x)WO_(3)/electrolyte interface.Our integrated studies indicate that the Na ions significantly enrich the electronic state of WO_(6)octahedrons in Na_(x)WO_(3),which leads to the regulated electronic and atomic structures,endowing Na_(x)WO_(3)with disordered interfacial water network containing more isolated H_(3)O^(+)and subsequently moderate H^(*)adsorption to speed the Volmer step at the Na_(x)WO_(3)surface,thus boosting the HER.Consequently,the intrinsic HER activities achieved on those Na_(x)WO_(3)are tens of times higher than those on WO_(3).Particularly,it is found that Na concentration x=0.69 endows Na_(x)WO_(3)with the highest intrinsic HER activity,and the resultant Na_(0.69)WO_(3)with a unique porous octahedral structure exhibits a low overpotential of only 64 mV at current density of 10 mA cm^(-2)in acidic electrolyte.This study provides the first insight into the cation-dependent interfacial water behavior induced by the cations within the catalyst and establishes the interfacial water-activity relationship of HER,thus allowing for the design of a more advanced catalyst with efficient interfacial structu res towa rds HER.
基金financially supported by the National Natural Science Foundation of China (No.22372057)Yunnan Fundamental Research Projects (No.202301AT070059)+2 种基金the Natural Science Foundation of Hunan Province (No.2023JJ30121)the Natural Science Foundation of Changsha (No.KQ2208259)the Fundamental Research Funds for the Central Universities (No.202044011)。
文摘Perovskite oxides have shown great potential application in fuel cells due to the unique crystal structures and tunable composition as well as effective capability toward the oxygen reduction reaction(ORR),whereas the investigation on the electrocatalytic performance of perovskite oxides toward the two-electron ORR to H_(2)O_(2)production remains very limited.Herein,a facile synthetic method has been developed to prepare La_(2)Sn_(2)O_(7)@La-doped ZnSnO_(3)heterostructures comprising of amorphous La_(2)Sn_(2)O_(7)and crystalline La-doped ZnSnO_(3).The optimal La_(2)Sn_(2)O_(7)@Ladoped ZnSnO_(3)heterostructures catalyst exhibits a significantly improved two-electron ORR performance to H_(2)O_(2)production with onset potential of 0.77 V and large current density of 2.51 m A.cm^(-2)at 0.1 V compared to ZnSnO_(3)(0.75 V,1.80 m A.cm^(-2),0.11 m A) as well as maintains high H_(2)O_(2)selectivity of 80%,which has been theoretically demonstrated to be contributed to the synergistic effect of amorphous La_(2)Sn_(2)O_(7)and crystalline La-doped ZnSnO_(3).Moreover,high H_(2)O_(2)yield rate of 2.9 m M.h^(-1)at 0.1 V can be achieved with a superior turnover frequency(TOF) of3.31 × 10^(-2)s^(-1)compared to the ZnSnO_(3)catalyst(2.10 × 10^(-2)s^(-1)).This work reveals the great potential of perovskite oxide as promising candidates for the environmentally friendly synthesis of hydrogen peroxide.
基金supported by the National Natural Science Foundation of China(22162007)the Science and Technology Supporting Project of Guizhou Province([2021]480)+1 种基金the Science and Technology Supporting Project of Guizhou Province([2023)379)the Project from Guizhou Institute of Innovation and development of dual-carbon and new energy technologies(DCRE-2023-05)。
文摘Structural engineering enhances plasmonic stability and amplifies localized electric fields,yet the limited intrinsic activity of plasmonic materials necessitates integrating catalytic active sites.Herein,we design a yolk@shell nanoreactor featuring dual-plasmonic Au@CuS core-shell structures encapsulated by sulfur vacancy-rich ZnIn2S4(Sv-ZIS).The electromagnetic“hotspots”from Au and CuS near-field coupling concentrate incident light to boost hot-carrier generation and migration while sulfur vacancies in Sv-ZIS promote hydrogen evolution.This dual mechanism synergistically achieves 86.3 mmol g^(-1)h-1of H2production(65.6%quantum efficiency at 420 nm),maintaining 48.3 mmol g^(-1)h-1at 6℃.Density functional theory(DFT)simulations demonstrate that sulfur vacancies not only reduce the H*adsorption energy barrier from 0.87 to 0.11 eV but also amplify the interfacial electric field strength by 9%.Vacancy-redirected fields favor proton reduction pathways,accelerating charge transfer kinetics.Comparative studies confirm the universal superiority of dual-plasmonic architecture,while Sv-ZIS shells exhibit optimized activity through defect-mediated electronic interactions.This work provides a blueprint for bridging plasmonic field enhancement and defect engineering in multi-component photocatalysts.
