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
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
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
Rational design of electrochemical sulfide oxidation reaction(SOR)catalysts is a prerequisite to fully recycling hydrogen(H_(2))and elemental sulfur(S0)resources,realizing the bridge between environment and energy fie...Rational design of electrochemical sulfide oxidation reaction(SOR)catalysts is a prerequisite to fully recycling hydrogen(H_(2))and elemental sulfur(S0)resources,realizing the bridge between environment and energy fields,as well as enlightening the optimization of metal‒sulfur battery applications.While transition metal catalysts often suffer from sulfur poisoning,single-atom catalysts(SACs)offer a promising solution,where the precise coordination environment of metal centers becomes a critical determinant of catalytic performance.Herein,for the first time,we develop a Ni single-atom catalyst for SOR with unique Ni-N_(3)O_(1) coordination anchored on hierarchically porous carbon(Ni1@HPC),which demonstrates remarkable advantages over conventional Ni-N_(4) or Ni-O4 configurations,exhibiting a superior SOR activity(0.37 V vs.RHE at 100 mA·cm^(-2))that surpasses reported carbon-based catalysts and is comparable to most metal-based catalysts.In situ Raman and density functional theory(DFT)results reveal that the HPC facilitates rapid product S0 desorption while the Ni-N3O1 coordination enables appropriate reactant sulfide(S^(2-))adsorption,striking a critical balance between activity and stability that other coordination geometries fail to achieve.Additionally,the practical application of coupling hydrogen evolution reaction(HER)and SOR is realized on Ni1@HPC with low power consumption,which is a promising alternative to the traditional overall water splitting(OWS)process.This work not only establishes a structure–activity relationship for single-atom catalysts in SOR but also provides a general strategy for optimizing metal coordination in electrocatalytic systems.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
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
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
Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous ...Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.展开更多
The rational construction of heterogeneous interfacial engineering presents a critical strategy for advancing efficient electrochemical water-splitting development.Here,a bimetallic sulfide-coupled MoNi alloy heterost...The rational construction of heterogeneous interfacial engineering presents a critical strategy for advancing efficient electrochemical water-splitting development.Here,a bimetallic sulfide-coupled MoNi alloy heterostructure catalyst(VMoS/MoNi)is synthesized via hydrothermal and sulfidation methods for high-performance alkaline water electrolysis.Benefiting from interfacial coupling within the VMoS/MoNi catalyst,the active sites are enriched,and electron transfer is promoted,leading to enhanced synergy and collaboration in electrocatalytic reactions.As a result,at 10 mA·cm^(-2),the VMoS/MoNi catalyst demonstrates excellent HER(26 mV)and OER(223 mV)performance.VMoS/MoNi catalysts used as double electrode in an alkaline electrolytic assembly are noteworthy for achieving a cell voltage of 1.56 V at 10 mA·cm^(-2),a significant improvement above most previously reported bifunctional electrocatalysts.This result provides further momentum for the design of heterostructure electrocatalysts,advancing the study of renewable energy conversion and storage.展开更多
Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prep...Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.展开更多
CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synerg...CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.展开更多
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.
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 National Key Technologies R&D Program of China(Nos.2018YFA0209301 and 2018YFA0209303)the National Natural Science Foundation of China(Nos.22272027,U21A20326,U1905214,21425309,21761132002,21961142019,and 21861130353)+1 种基金the Chang Jiang Scholars Program of China(No.T2016147)the 111 Project(No.D16008).
文摘Rational design of electrochemical sulfide oxidation reaction(SOR)catalysts is a prerequisite to fully recycling hydrogen(H_(2))and elemental sulfur(S0)resources,realizing the bridge between environment and energy fields,as well as enlightening the optimization of metal‒sulfur battery applications.While transition metal catalysts often suffer from sulfur poisoning,single-atom catalysts(SACs)offer a promising solution,where the precise coordination environment of metal centers becomes a critical determinant of catalytic performance.Herein,for the first time,we develop a Ni single-atom catalyst for SOR with unique Ni-N_(3)O_(1) coordination anchored on hierarchically porous carbon(Ni1@HPC),which demonstrates remarkable advantages over conventional Ni-N_(4) or Ni-O4 configurations,exhibiting a superior SOR activity(0.37 V vs.RHE at 100 mA·cm^(-2))that surpasses reported carbon-based catalysts and is comparable to most metal-based catalysts.In situ Raman and density functional theory(DFT)results reveal that the HPC facilitates rapid product S0 desorption while the Ni-N3O1 coordination enables appropriate reactant sulfide(S^(2-))adsorption,striking a critical balance between activity and stability that other coordination geometries fail to achieve.Additionally,the practical application of coupling hydrogen evolution reaction(HER)and SOR is realized on Ni1@HPC with low power consumption,which is a promising alternative to the traditional overall water splitting(OWS)process.This work not only establishes a structure–activity relationship for single-atom catalysts in SOR but also provides a general strategy for optimizing metal coordination in electrocatalytic systems.
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 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.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.
基金Financial supports from the National Natural Science Foundation(No.21991104 and No.22,278,235)。
文摘Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.
基金supported by the National Natural Science Foundation of China(No.22369025)Yunnan Applied Basic Research Projects(Nos.202201AT070095,202301AT070098,202301AT070107,202401AT070438,and 202401AT070433)+2 种基金Education Reform Research Project of Yunnan University(No.2021Z06)Yunnan University Graduate Student Practice and Innovation Program(Nos.ZC-23234269,ZC-23235291,KC-23236398,and KC-23234063)Yunnan Revitalization Talent Support Program。
文摘The rational construction of heterogeneous interfacial engineering presents a critical strategy for advancing efficient electrochemical water-splitting development.Here,a bimetallic sulfide-coupled MoNi alloy heterostructure catalyst(VMoS/MoNi)is synthesized via hydrothermal and sulfidation methods for high-performance alkaline water electrolysis.Benefiting from interfacial coupling within the VMoS/MoNi catalyst,the active sites are enriched,and electron transfer is promoted,leading to enhanced synergy and collaboration in electrocatalytic reactions.As a result,at 10 mA·cm^(-2),the VMoS/MoNi catalyst demonstrates excellent HER(26 mV)and OER(223 mV)performance.VMoS/MoNi catalysts used as double electrode in an alkaline electrolytic assembly are noteworthy for achieving a cell voltage of 1.56 V at 10 mA·cm^(-2),a significant improvement above most previously reported bifunctional electrocatalysts.This result provides further momentum for the design of heterostructure electrocatalysts,advancing the study of renewable energy conversion and storage.
基金Supported by National Key R&D Program of China(2022YFA1503400)。
文摘Aiming at the problems of insufficient activity and selectivity of Cu-based catalysts in CO_(2)hydrogenation to methanol,Al_(2)O_(3),ZrO_(2)and CeO_(2)modified Cu-ZnO catalysts by the co-precipitation method were prepared,and the influence mechanism of additives on the structure-performance relationship of the catalysts was systematically explored.Through a variety of characterization methods such as XRD,N2 physical adsorption-desorption,TEM,H_(2)-TPR,CO_(2)-TPD and XPS,combined with catalytic performance evaluation experiments,the correlation between the microstructure of catalysts and the reaction performance of CO_(2)hydrogenation to methanol was analyzed in depth.The results show that metal additives significantly improve the performance of catalysts.After the introduction of additives,the specific surface area and pore volume of the catalysts increase,the grain size of Cu decreases,and its dispersion improves.The Ce-modified CZC catalyst exhibited the best performance,with the grain size of CuO as small as 11.41 nm,and the surface oxygen vacancy concentration(OⅡ/OⅠ=3.15)was significantly higher than that of other samples.The reaction performance test shows that under the conditions of 2.8 MPa,8000 h−1 and 280℃,the CO_(2)conversion of the CZC catalyst reached 18.83%,the methanol selectivity was 68.40%,and the methanol yield was 12.88%,all of which are superior to other catalysts.Its excellent performance can be attributed to the fact that CeO_(2)enhances the metal-support interaction,increases the surface basicity,promotes the adsorption and activation of CO_(2),and simultaneously inhibits the reverse water-gas shift side reaction.This study clarifies the structure-activity regulation mechanism of additive modification on Cu-ZnO catalysts,providing a theoretical basis and technical reference for the development of efficient catalysts for CO_(2)hydrogenation to methanol.
文摘CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.
