Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a fo...Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.展开更多
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and ma...Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and magnetic field enhanced-electrochemical activity remains to be fully elucidated.Herein,single-domain CoFe_(2)O_(4) catalysts with tunable oxygen vacancies(CFO-V_(O)) were synthesized to probe how V_(O) mediates magnetism and OER activity under magnetic field.The introduction of V_(O) can simultaneously modulate saturation magnetization(M_(s)) and coercivity(H_(c)),where the increased M_(s) dominates the magnetic field-enhanced OER activity.Under a 14,000 G magnetic field,the optimized CFO-V_(O) exhibits up to 16.1 % reduction in overpotential and 365 % enhancement in magnetocurrent(MC).Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction,magnetohydrodynamic effect,and spin charge transfer effect.Importantly,the magnetic field promotes additional Co^(3+) generation to compensate for charge imbalance caused by V_(O) filling,maintaining dynamic equilibrium of V_(O) and effective reactant adsorption-conversion processes.This work unveils the synergistic mechanism of V_(O) and magnetic parameters for enhancing OER performance under the magnetic field,providing new insights into the design of high-efficiency spinregulated OER catalysts.展开更多
Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied ...Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.展开更多
The escalating pace of industrialization has significantly intensified water pollution challenges,for instance,the persistent organic pollutants like methyl orange(MO).Conventional remediation techniques,such as adsor...The escalating pace of industrialization has significantly intensified water pollution challenges,for instance,the persistent organic pollutants like methyl orange(MO).Conventional remediation techniques,such as adsorption and biological degradation,are often hampered by low efficiency and the risk of secondary pollution.Photocatalysis emerges as a promising sustainable alternative;however,the benchmark material titanium dioxide(TiO_(2))suffers from its intrinsic limitations,notably its wide bandgap energy(≥3.4 eV)restricting its activity to the region of the ultraviolet light and its rapid recombination of photogenerated charge carriers.To overcome these constraints,this research focused on synthesizing novel TiO_(2)/Sn_(3)O_(4) heterojunction composite photocatalysts via a solvothermal approach.Comprehensive characterization techniques confirmed the successful formation of the composite,which revealed that ultrathin Sn3O4 nanosheets uniformly coated TiO_(2) nanospheres.This unique architecture effectively reduced the overall crystallinity and introduced the beneficial oxygen vacancies.Under visible-light irradiation(λ≥420 nm),the optimized TiO_(2)/Sn3O4 composite exhibited the exceptional photocatalytic performance,which achieved 96%degradation of MO within just 60 minutes.The calculated apparent kinetic rate constant(0.103 min^(-1))was remarkably(5.15 times)higher than that of pristine TiO_(2).ESR experiments identified that hydroxyl radicals(·OH)was the predominant active species driving the degradation.Furthermore,cyclic degradation tests demonstrated its excellent material stability,with the composite retaining 85%of its initial efficiency after four consecutive reuse cycles.This work underscored the synergistic effects within the TiO_(2)/Sn_(3)O_(4) heterojunction,which significantly enhanced the visible-light absorption,charge separation,and photocatalytic activity,which provided the valuable insights for designing efficient,stable catalysts for the advanced environmental remediation applications.展开更多
Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer ...Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer from insufficient hole transport capability,which hinders the overall activity.The present study demonstrates that a simple photoetching strategy is able to introduce gradient distributed oxygen vacancies(GO_(V))in the thick FeOOH layer and significantly enhances the photogenerated holes transport dynamics.The incorporation of GO_(V)within FeOOH not only realizes the“relay transport”of photogenerated hole through the progressive upward shift of the valence band in the spatial distribution,but also provides abundant oxidation active sites by efficient hole trapping.These improvements effectively improve the oxygen evolution reaction(OER)activities and mitigate photocorrosion by the instantaneous hole extraction.Consequently,the FeOOH-GO_(V)layer enables the BVO/FeOOH-GO_(V)photoanode to achieve an impressive photocurrent density of 5.37 mA cm^(-2)and a robust operational stability up to 160 h at 1.23 VRHE,setting new benchmarks for current density and stability in FeOOH-based BVO photoanodes.This work provides an effective avenue to optimize OER cocatalysts for constructing highly efficient and stable photoelectrochemical water splitting devices.展开更多
Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hin...Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hinder system integration due to their specific manufacturing processes.Conversely,metal oxide diodes,with their simple fabrication techniques,offer advantages for system integration.The oxygen vacancy defect of oxide semiconductor will greatly affect the electrical performance of the device,so the performance of the diode can be effectively controlled by adjusting the oxygen vacancy concentration.This study centers on optimizing the performance of diodes by modulating the oxygen vacancy concentration within InGaZnO films through control of oxygen flows during the sputtering process.Experimental results demonstrate that the diode exhibits a forward current density of 43.82 A·cm^(−2),with a rectification ratio of 6.94×10^(4),efficiently rectifying input sine signals with 1 kHz frequency and 5 V magnitude.These results demonstrate its potential in energy conversion and management.By adjusting the oxygen vacancy,a methodology is provided for optimizing the performance of rectifying diodes.展开更多
Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting...Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting the reaction.During the reaction,the presence of oxygen vacancies can extract oxygen from NO,thereby facilitating the cleavage of NO on the catalyst surface.Thus,the formation of oxygen vacancies is key to accelerating the CO-SCR reaction,with different types of oxygen vacancies being more conducive to their generation.In this study,Rh/CeCuO_(x) catalysts were synthesized using the co-crystallization and impregnation methods,and asymmetric oxygen vacancies were induced through hydrogen thermal treatment.This structuralmodification was aimed at regulating the behavior of NO on the catalyst surface.The Rh/Ce0.95Cu0.05O_(x)-H_(2) catalyst exhibited the best performance in CO-SCR,achieving above 90%NO conversion at 162℃.Various characterization techniques showed that the H_(2) treatment effectively reduced some of the CuO and Rh_(2)O_(3),creating asymmetric oxygen vacancies that accelerated the cleavage of NO on the catalyst surface,rather than forming difficult-to-decompose nitrates.This study offers a novel approach to constructing oxygen vacancies in new CO-SCR catalysts.展开更多
Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structu...Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structure of the catalysts,external factors such as visible light irradiation can improve the efficiency of hydrogen production as well.In the present study,a Z-scheme heterostructured VO-Cu_(0.5)Ni_(0.5)O catalysts were constructed by introducing a plenteous phase interface and oxygen vacancy(Vo).The catalytic activity of as-prepared VO-Cu_(0.5)Ni_(0.5)O toward AB methanolysis has been improved dramatically with the assistance of visible light irradiation.The turnover frequency(TOF)under visible light irradiation was measured to be 29_(mol)H_(2)·mol_(cat.)^(-1)·min^(-1),which is 1.4 times larger than the TOF in the absence of visible light.Systematic characterization experiments and density functional theory(DFT)calculations were conducted to unveil the causation of enhanced catalytic activity.The results demonstrated that the enhancement of the catalytic activity of VO-Cu_(0.5)Ni_(0.5)O originated from the electronic structure modification induced by the formation of heterojunctions,the introduction of oxygen vacancies,and the assistance of visible light cooperatively.The formation of heterojunction and the introduction of oxygen vacancies provoked the upshift of the d-band center;while the visible light irradiation induced the photogenerated electrons to transfer from Cu to Ni sites at the interface.Such electron structure modulation is beneficial for the construction of abundant active sites,thereby enhancing the adsorption of methanol on the Ni sites,which is considered as the rate-determine step for the methanolysis of AB.The strong interaction between Ni and O weakened the O-H bond of methanol,accelerating the methanolysis of AB.These results demonstrate the utilization of combined heterojunction,oxygen vacancy,and visible light to explore highly active AB methanolysis catalysts,which should shed light on the exploration of more effective catalysts for AB methanolysis.展开更多
On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil ...On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil particles.However,soil particles on the Earth with the similar composition lack such structures and properties.This discrepancy raises a key question whether there is a direct relationship between solar wind irradiation and the alterations in the structure and chemical performance of extraterrestrial materials.To address this question,this work investigates the effects of proton irradiation,simulating solar wind radiation,on the structure and photothermal catalytic properties of the classic catalyst In_(2)O_(3).It reveals that proton irradiation induces structural features in In_(2)O_(3) analogous to those characteristics of solar wind weathering observed in extraterrestrial materials.Furthermore,after proton beam irradiation with an energy of 30 keV and a dose of 3×10^(17) protons·cm^(-2),the methanol production yield of the In_(2)O_(3) catalyst increased to 2.6 times of its preirradiation level,and the methanol selectivity improved to 2.1 times of the original value.This work provides both theoretical and experimental support for the development of high-efficiency,radiation-resistant photothermal catalysts.展开更多
The authors regret<During the submission process,Hongxiang Zhang and Honggen Peng served as the first and the second corresponding author,respectively.The original manuscript submitted for this paper also listed tw...The authors regret<During the submission process,Hongxiang Zhang and Honggen Peng served as the first and the second corresponding author,respectively.The original manuscript submitted for this paper also listed two co-corresponding authors(Hongxiang Zhang and Honggen Peng).But the corresponding author of Honggen Peng was omitted in the final published manuscript.So,we apply to designate Honggen Peng(penghonggen@ncu.edu.cn)as the second co-corresponding author and the corresponding unit is“a,b">.展开更多
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein...The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein,an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy(Co-O_(V))on the Co/BiOCl-O_(V)photocatalyst was developed for photocatalytic degradation of glyphosate(GLP)wastewater of high performance/selectivity.Under full-spectrum-light irradiation,a high GLP degradation rate of 99.8%with over 90%C-P bond-breaking selectivity was achieved within 2 h,while effectively circumventing toxicant residues such as aminomethylphosphonic acid(AMPA).X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-O_(V)carrier and photothermal/pyroelectric effect.The oriented formation of more•O_(2)^(−)on Co/BiOCl-O_(V)could be achieved with the Co-O_(V)coupled center that had excellent O2 adsorption/activation capacity,as demonstrated by quantum calculations.The formed unique Co-O_(V)active sites could largely decrease the C-P bond-breaking energy barrier,thus greatly improving the selectivity toward the initial C-P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP.The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C-X bonds.展开更多
The regulation of peroxymonosulfate(PMS)activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle.This work ...The regulation of peroxymonosulfate(PMS)activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle.This work demonstrates a strategy to constructed ethylene glycol(EG)well-coupled S-scheme heterojunction of NiFe_(2)O_(4-x)/NiS with oxygen vacancy(VO)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation,a 99%PMS decomposition efficiency is achieved.Photoassisted Kelvin probe force microscopy and in-situ electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe_(2)O_(4-x)/NiS with an S-scheme heterojunction,which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation.The S-scheme NiFe_(2)O_(4-x)/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate(0.15 min^(-1))at a low PMS dosage of 0.1 g/L,which is 19 times greater than that of the pristine NiS(0.0077 min^(-1)).Density functional theory calculations confirmed that VO in NiFe_(2)O_(4-x)/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer.Moreover,in-situ experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation,unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe_(2)O_(4-x)/NiS during the reaction.This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation,providing a promising solution the cost-effective and efficient treatment of organic wastewater.展开更多
The synergy of metal/oxygen vacancy(O_(v))pairs is critical in catalyzing activation of C-H,C=C,and C-O bonds.However,gaining fundamental understanding on spatial distance of metallic and O_(v)sites on catalyst surfac...The synergy of metal/oxygen vacancy(O_(v))pairs is critical in catalyzing activation of C-H,C=C,and C-O bonds.However,gaining fundamental understanding on spatial distance of metallic and O_(v)sites on catalyst surface would lead to unexpected chemoselectivity toward important and challenging reactions.In this work,we have proposed and validated unique Ni-O-Ce-O_(v)enriched Ni/CeO_(2)catalysts prepared by a deposition-precipitation method,for the transfer hydrogenation of lignin-derived guaiacol toward cyclohexanol rather than benzene derivatives.The counter-intuitively designed high Ni loading Ni_(2)0/CeO_(2)catalyst(20 wt%Ni content)displays a distance of 0.5 nm for Ni/O_(v)pairs with a remarkable activity(TOF:166.5 h^(-1))and 90%+selectivity for C_(Ar)=C_(Ar)bond saturation,outperforming better metal-dispersed Ni_(5)/CeO_(2)catalyst with limited presence of Ni-O-Ce-O_(v)sites.The high hydrogenation activity against hydrogenolysis reactions on Ni_(2)0/CeO_(2)catalyst is attributed to tunable Ni/O_(v)distances,which constrain the cleavage of CAr-OH bond and deep deoxygenation.Such spatial distribution effect has also facilitated tandem dehydrogenation(O-H bond cleavage)and hydrogenation(C_(Ar)=C_(Ar)hydrogenation)reactions,leading to cyclohexanol as the target product in the absence of externally added H_(2).Insights into spatial distribution of O_(v)sites open an alternative perspective in designing efficient catalysts toward producing value-added cyclic oxygenates through upgrading of lignin compounds.展开更多
Transition metal-based electrocatalysts are a promising alternative to noble metal catalysts for electrochemical upgrading of biomass-derived 5-hydroxymethylfurfural(HMF)into high-value 2,5-furandicarboxylic acid(FDCA...Transition metal-based electrocatalysts are a promising alternative to noble metal catalysts for electrochemical upgrading of biomass-derived 5-hydroxymethylfurfural(HMF)into high-value 2,5-furandicarboxylic acid(FDCA).However,the rational design of efficient electrocatalysts with precisely tailored structure-activity correlations remains a critical challenge.Herein,we report a hierarchically structured self-supporting electrode(Vo-NiCo(OH)_(2)-NF)synthesized through in situ electrochemical reconstruction of NiCo-Prussian blue analogue(NiCo-PBA)precursor,in which oxygen vacancy(Vo)-rich Co-doped Ni(OH)_(2)nanosheet arrays are vertically aligned on nickel foam(NF),creating an interconnected conductive network.When evaluated for the HMF oxidation reaction(HMFOR),Vo-NiCo(OH)_(2)-NF exhibits exceptional electrochemical performance,achieving near-complete HMF conversion(99%),ultrahigh FDCA Faradaic efficiency(97.5%),and remarkable product yield(96.2%)at 1.45 V,outperforming conventional Co-doped Ni(OH)_(2)(NiCo(OH)_(2)-NF)and pristine Ni(OH)_(2)(Ni(OH)_(2)-NF)electrodes.By combining in situ spectroscopic characterization and theoretical calculations,we elucidate that the synergistic effects of Co-doping and oxygen vacancy engineering effectively modulate the electronic structure of Ni active centers,favor the formation of high-valent Ni^(3+)species,and optimize HMF adsorption,thereby improving the HMFOR performance.This work provides valuable mechanistic insights for catalyst design and may inspire the development of advanced transition metal-based electrodes for efficient biomass conversion systems.展开更多
Correction to:Rare Met.https://doi.org/10.1007/s12598-021-01864-4 In the original publication,the affiliation of the 5th author(Corresponding author)was published incorrectly.The correct affiliation is given in this C...Correction to:Rare Met.https://doi.org/10.1007/s12598-021-01864-4 In the original publication,the affiliation of the 5th author(Corresponding author)was published incorrectly.The correct affiliation is given in this Correction.The original publication has been corrected.展开更多
Modulating the adsorption energy of intermediate species via alloying presents a promising approach to enhance the electrocatalytic nitrate reduction to ammonia(NRA).Nonetheless,the synthesis of alloy catalysts that a...Modulating the adsorption energy of intermediate species via alloying presents a promising approach to enhance the electrocatalytic nitrate reduction to ammonia(NRA).Nonetheless,the synthesis of alloy catalysts that are uniformly distributed and structurally stable poses significant challenges.Herein,the CuNi alloy was successfully anchored on oxygen vacancy-rich N-Ti_(3)C_(2)T_(x) through metal-support interactions(MSI).The three-dimensional(3D)wrinkled morphology of N-Ti_(3)C_(2)T_(x) MXene was achieved by employing melamine-formaldehyde spheres(MFs)as self-sacrificial templates,which effectively prevented the restacking of the Ti_(3)C_(2)T_(x) layers,thereby increasing specific surface area and promoting the formation of surface oxygen vacancies.Ti–O–M structure plays a crucial role in inhibiting both particle migration and metal atom diffusion.X-ray photoelectron spectroscopy(XPS)analysis confirms moderate metal-support interactions between the CuNi alloy and N-Ti_(3)C_(2)T_(x),leading to the establishment of stable Ti–O–M bonds and charge redistribution within the Ti-O-M framework.The Cu_(5)Ni_(5)/N-Ti_(3)C_(2)T_(x) sample achieves an impressive Faradaic efficiency(FE)of 97.50%at−0.27 V vs.RHE,alongside the highest NH3 yield rate of 527.44µmol h−1 cm−2.In-situ electrochemical Raman spectroscopy and theoretical calculations reveal that the high intrinsic catalytic activity of NRA can be attributed to the synergistic effects between the CuNi alloy and the interfacial metal-oxygen interactions.This work provides significant perspectives on the design of interfacial metal interactions and the development of durable electrocatalysts.展开更多
The development of efficient and robust non-precious metal electrocatalyst to drive the sluggish hydrogen oxidation reaction(HOR)is the key to the practical application of anion exchange membrane fuel cells(AEMFC),whi...The development of efficient and robust non-precious metal electrocatalyst to drive the sluggish hydrogen oxidation reaction(HOR)is the key to the practical application of anion exchange membrane fuel cells(AEMFC),which relies on the rational regulation of intermediates’binding strength.Herein,we reported a simple strategy to manipulate the adsorption energy of OH^(∗)on electrocatalyst surface via engineering Ni/NbO_(x) heterostructures with manageable oxygen vacancy(Ov).Theoretical calculations confirm that the electronic effect between Ni and NbO_(x) could weaken the hydrogen adsorption on Ni,and the interfacial oxygen vacancy tailor hydroxide binding energy(OHBE).The optimized HBE and OHBE contribute to reduce formation energy of water during the alkaline HOR process.Furthermore,in situ Raman spectroscopy monitor the dynamic process that OH^(∗)adsorbed on oxygen vacancy and react with adjacent H^(∗)adsorbed Ni,confirming the vital role of OH^(∗)for alkaline HOR process.As a result,the optimal Ni/NbO_(x) exhibits a remarkable intrinsic activity with a specific activity of 0.036mA/cm^(2),which is 4-fold than that of pristine Ni counterpart and surpasses most non-precious electrocatalysts ever reported.展开更多
This work presents a hierarchical yolk-shell NiZn-Co_(3)O_(4)sphere with abundant oxygen vacancy by utilizing structure optimization and composition regulation for efficient detection of triethylamine(TEA)gas.A compar...This work presents a hierarchical yolk-shell NiZn-Co_(3)O_(4)sphere with abundant oxygen vacancy by utilizing structure optimization and composition regulation for efficient detection of triethylamine(TEA)gas.A comparative exploration of TEA gas sensing characterization for different Co_(3)O_(4)-based sensors is conducted systematically.The result shows that the sensor based on the NiZn–Co_(3)O_(4)HCSS displays the highest sensing response of 42.5 at a working temperature of 180°C.In particular,the Ni Zn–Co_(3)O_(4)HCSS device possesses a fast responserecovery speed,excellent anti-humidity and outstanding long-term stability of up to 40 days to TEA gas.The improved TEA gas sensing property can be attributed to the intriguing hierarchical core–shell architecture and abundant oxygen vacancy induced by NiZn co-doping.Moreover,to study the sensing mechanism in detail,the adsorption behavior and charge transfer phenomenon between OV–NiZn–Co_(3)O_(4)(110)and TEA molecule is carried out by the density functional theory(DFT).This work demonstrates an outstanding performance of Ni and Zn co-doped hierarchical core–shell Co_(3)O_(4)in TEA detection by combining theoretical and experimental investigations into mechanisms for optimized TEA gas molecule sensing.展开更多
Transition metal oxides(TMOs),thanks to their elevated theoretical capacitance and pseudocapacitive properties,are of particular interest in exploring the advanced supercapacitor electrode materials.The present work r...Transition metal oxides(TMOs),thanks to their elevated theoretical capacitance and pseudocapacitive properties,are of particular interest in exploring the advanced supercapacitor electrode materials.The present work reports the rapid laser-assisted synthesis of SiC@-Fe_(2)O_(3-x)anode materials with engineered oxygen vacancies in seconds,which improve the charge transport,redox activity,and structural stability,thus facilitating a substantial enhancement in electrochemical performance.As a result,the resultant SiC@Fe_(2)O_(3-x)nanowires exhibit excellent performances with an areal capacitance of 1082.16 at 5 mA cm^(-2),and retain 86.7%capacitance over 10,000 cycles.Furthermore,the assembled asymmetric supercapacitors(ASC),employing SiC@Fe_(2)O_(3-x)as the negative electrode and Ni(OH)2as the positive electrode,delivers a 1.5 V operating voltage,an energy density of 197μWh cm^(-2),and 80.6%capacitance retention after 14,000cycles,representing their promise toward the applications in next-generation energy storage materials.展开更多
Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consum...Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consumption and greenhouse gas emissions.Therefore,achieving ammonia synthesis under milder conditions has been a long-standing goal.In this study,we design and synthesize a series of CeO_(2)-modified Fe/carbon-based catalysts with varying amounts of CeO_(2)(Ce_(x)Fe_(y)/C).The catalyst Ce_(2)Fe_(5)/C demonstrates an ammonia yield rate of 3.5 mmol/(g·h),which is 44 times greater than that of Fe/C and 8 times greater than that of commercial Fe-based catalysts at 300℃and 1 MPa.Temperature-programmed desorption experiments show that Ce_(2)Fe_(5)/C has enhanced nitrogen adsorption capabilities.Multiple analyses confirm that the CeO_(2)in Ce_(2)Fe_(5)/C is rich in oxygen vacancies,which can provide electrons to Fe,facilitating nitrogen adsorption,dissociation,and activity in low-temperature ammonia synthesis.展开更多
基金support from the National Natural Science Foundation of China(Nos.12305373 and 52276220)the Guangzhou Basic Research Program(No.SL2024A04J00234).
文摘Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.
基金supported by the “Climbing Plan” of Harbin Normal University (No.XKB202301)National Natural Science Foundation of China (Nos.21871065 and 22071038)。
文摘Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and magnetic field enhanced-electrochemical activity remains to be fully elucidated.Herein,single-domain CoFe_(2)O_(4) catalysts with tunable oxygen vacancies(CFO-V_(O)) were synthesized to probe how V_(O) mediates magnetism and OER activity under magnetic field.The introduction of V_(O) can simultaneously modulate saturation magnetization(M_(s)) and coercivity(H_(c)),where the increased M_(s) dominates the magnetic field-enhanced OER activity.Under a 14,000 G magnetic field,the optimized CFO-V_(O) exhibits up to 16.1 % reduction in overpotential and 365 % enhancement in magnetocurrent(MC).Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction,magnetohydrodynamic effect,and spin charge transfer effect.Importantly,the magnetic field promotes additional Co^(3+) generation to compensate for charge imbalance caused by V_(O) filling,maintaining dynamic equilibrium of V_(O) and effective reactant adsorption-conversion processes.This work unveils the synergistic mechanism of V_(O) and magnetic parameters for enhancing OER performance under the magnetic field,providing new insights into the design of high-efficiency spinregulated OER catalysts.
基金financially supported by the National Natural Science Foundation of China(No.22172144 and 22272151)Key Research and Development Program of Zhejiang Province(2023C03148).
文摘Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.
文摘The escalating pace of industrialization has significantly intensified water pollution challenges,for instance,the persistent organic pollutants like methyl orange(MO).Conventional remediation techniques,such as adsorption and biological degradation,are often hampered by low efficiency and the risk of secondary pollution.Photocatalysis emerges as a promising sustainable alternative;however,the benchmark material titanium dioxide(TiO_(2))suffers from its intrinsic limitations,notably its wide bandgap energy(≥3.4 eV)restricting its activity to the region of the ultraviolet light and its rapid recombination of photogenerated charge carriers.To overcome these constraints,this research focused on synthesizing novel TiO_(2)/Sn_(3)O_(4) heterojunction composite photocatalysts via a solvothermal approach.Comprehensive characterization techniques confirmed the successful formation of the composite,which revealed that ultrathin Sn3O4 nanosheets uniformly coated TiO_(2) nanospheres.This unique architecture effectively reduced the overall crystallinity and introduced the beneficial oxygen vacancies.Under visible-light irradiation(λ≥420 nm),the optimized TiO_(2)/Sn3O4 composite exhibited the exceptional photocatalytic performance,which achieved 96%degradation of MO within just 60 minutes.The calculated apparent kinetic rate constant(0.103 min^(-1))was remarkably(5.15 times)higher than that of pristine TiO_(2).ESR experiments identified that hydroxyl radicals(·OH)was the predominant active species driving the degradation.Furthermore,cyclic degradation tests demonstrated its excellent material stability,with the composite retaining 85%of its initial efficiency after four consecutive reuse cycles.This work underscored the synergistic effects within the TiO_(2)/Sn_(3)O_(4) heterojunction,which significantly enhanced the visible-light absorption,charge separation,and photocatalytic activity,which provided the valuable insights for designing efficient,stable catalysts for the advanced environmental remediation applications.
基金supported by the State Key Laboratory of Solidification Processing in NWPU(SKLSP202407)the National Natural Science Foundation of China(52402130)+2 种基金the Natural Science Basis Research Plan in Shaanxi Province of China(2024JC-YBQN-0384)the Shaanxi Science and Technology Innovation Team(2023-CX-TD-44)the National Natural Science Foundation of China(52301015).
文摘Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer from insufficient hole transport capability,which hinders the overall activity.The present study demonstrates that a simple photoetching strategy is able to introduce gradient distributed oxygen vacancies(GO_(V))in the thick FeOOH layer and significantly enhances the photogenerated holes transport dynamics.The incorporation of GO_(V)within FeOOH not only realizes the“relay transport”of photogenerated hole through the progressive upward shift of the valence band in the spatial distribution,but also provides abundant oxidation active sites by efficient hole trapping.These improvements effectively improve the oxygen evolution reaction(OER)activities and mitigate photocorrosion by the instantaneous hole extraction.Consequently,the FeOOH-GO_(V)layer enables the BVO/FeOOH-GO_(V)photoanode to achieve an impressive photocurrent density of 5.37 mA cm^(-2)and a robust operational stability up to 160 h at 1.23 VRHE,setting new benchmarks for current density and stability in FeOOH-based BVO photoanodes.This work provides an effective avenue to optimize OER cocatalysts for constructing highly efficient and stable photoelectrochemical water splitting devices.
文摘Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hinder system integration due to their specific manufacturing processes.Conversely,metal oxide diodes,with their simple fabrication techniques,offer advantages for system integration.The oxygen vacancy defect of oxide semiconductor will greatly affect the electrical performance of the device,so the performance of the diode can be effectively controlled by adjusting the oxygen vacancy concentration.This study centers on optimizing the performance of diodes by modulating the oxygen vacancy concentration within InGaZnO films through control of oxygen flows during the sputtering process.Experimental results demonstrate that the diode exhibits a forward current density of 43.82 A·cm^(−2),with a rectification ratio of 6.94×10^(4),efficiently rectifying input sine signals with 1 kHz frequency and 5 V magnitude.These results demonstrate its potential in energy conversion and management.By adjusting the oxygen vacancy,a methodology is provided for optimizing the performance of rectifying diodes.
基金supported by the support of the National Natural Science Foundation of China(Nos.22072141,22176185 and 52304429)the National Key Research and Development Program of China(Nos.2022YFB3504200,2021YFB3501900)+4 种基金the Natural Science Foundation of Jiangxi Province for Distinguished Young Scholars(No.20232ACB213004)Jiangxi Provincial Key Research and Development Program(No.20232BBG70012)Jiangxi Provincial Natural Science Foundation(No.20212BAB213032)the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.2018263)the Research Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(No.E355C001).
文摘Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting the reaction.During the reaction,the presence of oxygen vacancies can extract oxygen from NO,thereby facilitating the cleavage of NO on the catalyst surface.Thus,the formation of oxygen vacancies is key to accelerating the CO-SCR reaction,with different types of oxygen vacancies being more conducive to their generation.In this study,Rh/CeCuO_(x) catalysts were synthesized using the co-crystallization and impregnation methods,and asymmetric oxygen vacancies were induced through hydrogen thermal treatment.This structuralmodification was aimed at regulating the behavior of NO on the catalyst surface.The Rh/Ce0.95Cu0.05O_(x)-H_(2) catalyst exhibited the best performance in CO-SCR,achieving above 90%NO conversion at 162℃.Various characterization techniques showed that the H_(2) treatment effectively reduced some of the CuO and Rh_(2)O_(3),creating asymmetric oxygen vacancies that accelerated the cleavage of NO on the catalyst surface,rather than forming difficult-to-decompose nitrates.This study offers a novel approach to constructing oxygen vacancies in new CO-SCR catalysts.
基金supported the Natural Science Foundation of Guangdong Province(Nos.2022A1515140085,2022A1515111022 and 2022A1515110275)the Major and Special Project in the Field of Intelligent Manufacturing of the Universities in Guangdong Province(No.2020ZDZX2067)+2 种基金the Natural Science Foundation of Huizhou University(No.HZU202004)the Professorial and Doctoral Scientific Research Foundation of Huizhou University(No.2020JB046)the Open Project Program of Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices,Huizhou University(No.EFMDN2021004M).
文摘Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structure of the catalysts,external factors such as visible light irradiation can improve the efficiency of hydrogen production as well.In the present study,a Z-scheme heterostructured VO-Cu_(0.5)Ni_(0.5)O catalysts were constructed by introducing a plenteous phase interface and oxygen vacancy(Vo).The catalytic activity of as-prepared VO-Cu_(0.5)Ni_(0.5)O toward AB methanolysis has been improved dramatically with the assistance of visible light irradiation.The turnover frequency(TOF)under visible light irradiation was measured to be 29_(mol)H_(2)·mol_(cat.)^(-1)·min^(-1),which is 1.4 times larger than the TOF in the absence of visible light.Systematic characterization experiments and density functional theory(DFT)calculations were conducted to unveil the causation of enhanced catalytic activity.The results demonstrated that the enhancement of the catalytic activity of VO-Cu_(0.5)Ni_(0.5)O originated from the electronic structure modification induced by the formation of heterojunctions,the introduction of oxygen vacancies,and the assistance of visible light cooperatively.The formation of heterojunction and the introduction of oxygen vacancies provoked the upshift of the d-band center;while the visible light irradiation induced the photogenerated electrons to transfer from Cu to Ni sites at the interface.Such electron structure modulation is beneficial for the construction of abundant active sites,thereby enhancing the adsorption of methanol on the Ni sites,which is considered as the rate-determine step for the methanolysis of AB.The strong interaction between Ni and O weakened the O-H bond of methanol,accelerating the methanolysis of AB.These results demonstrate the utilization of combined heterojunction,oxygen vacancy,and visible light to explore highly active AB methanolysis catalysts,which should shed light on the exploration of more effective catalysts for AB methanolysis.
基金National Key Research and Development Program of China(2020YFA0710302)The Major Research Plan of the National Natural Science Foundation of China(91963206)+2 种基金The National Natural Science Foundation of China(52072169,51972164,51972167,22279053)The Fundamental Research Funds for the Central Universities(14380193)The Program for Guangdong Introducing Innovative and Entrepreneurial Teams(2019ZT08L101).
文摘On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil particles.However,soil particles on the Earth with the similar composition lack such structures and properties.This discrepancy raises a key question whether there is a direct relationship between solar wind irradiation and the alterations in the structure and chemical performance of extraterrestrial materials.To address this question,this work investigates the effects of proton irradiation,simulating solar wind radiation,on the structure and photothermal catalytic properties of the classic catalyst In_(2)O_(3).It reveals that proton irradiation induces structural features in In_(2)O_(3) analogous to those characteristics of solar wind weathering observed in extraterrestrial materials.Furthermore,after proton beam irradiation with an energy of 30 keV and a dose of 3×10^(17) protons·cm^(-2),the methanol production yield of the In_(2)O_(3) catalyst increased to 2.6 times of its preirradiation level,and the methanol selectivity improved to 2.1 times of the original value.This work provides both theoretical and experimental support for the development of high-efficiency,radiation-resistant photothermal catalysts.
文摘The authors regret<During the submission process,Hongxiang Zhang and Honggen Peng served as the first and the second corresponding author,respectively.The original manuscript submitted for this paper also listed two co-corresponding authors(Hongxiang Zhang and Honggen Peng).But the corresponding author of Honggen Peng was omitted in the final published manuscript.So,we apply to designate Honggen Peng(penghonggen@ncu.edu.cn)as the second co-corresponding author and the corresponding unit is“a,b">.
基金supported by the National Natural Science Foundation of China(No.22368014)Guizhou Provincial S&T Project(Nos.GCC[2023]011,ZK[2022]011)Guizhou Provincial Higher Education Institution Program(No.Qianjiaoji[2023]082).
文摘The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein,an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy(Co-O_(V))on the Co/BiOCl-O_(V)photocatalyst was developed for photocatalytic degradation of glyphosate(GLP)wastewater of high performance/selectivity.Under full-spectrum-light irradiation,a high GLP degradation rate of 99.8%with over 90%C-P bond-breaking selectivity was achieved within 2 h,while effectively circumventing toxicant residues such as aminomethylphosphonic acid(AMPA).X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-O_(V)carrier and photothermal/pyroelectric effect.The oriented formation of more•O_(2)^(−)on Co/BiOCl-O_(V)could be achieved with the Co-O_(V)coupled center that had excellent O2 adsorption/activation capacity,as demonstrated by quantum calculations.The formed unique Co-O_(V)active sites could largely decrease the C-P bond-breaking energy barrier,thus greatly improving the selectivity toward the initial C-P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP.The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C-X bonds.
文摘The regulation of peroxymonosulfate(PMS)activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle.This work demonstrates a strategy to constructed ethylene glycol(EG)well-coupled S-scheme heterojunction of NiFe_(2)O_(4-x)/NiS with oxygen vacancy(VO)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation,a 99%PMS decomposition efficiency is achieved.Photoassisted Kelvin probe force microscopy and in-situ electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe_(2)O_(4-x)/NiS with an S-scheme heterojunction,which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation.The S-scheme NiFe_(2)O_(4-x)/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate(0.15 min^(-1))at a low PMS dosage of 0.1 g/L,which is 19 times greater than that of the pristine NiS(0.0077 min^(-1)).Density functional theory calculations confirmed that VO in NiFe_(2)O_(4-x)/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer.Moreover,in-situ experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation,unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe_(2)O_(4-x)/NiS during the reaction.This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation,providing a promising solution the cost-effective and efficient treatment of organic wastewater.
基金supported by the National Natural Science Foundation of China(22078365,22478437)the Natural Science Foundation of Shandong Province(ZR2023MB076)。
文摘The synergy of metal/oxygen vacancy(O_(v))pairs is critical in catalyzing activation of C-H,C=C,and C-O bonds.However,gaining fundamental understanding on spatial distance of metallic and O_(v)sites on catalyst surface would lead to unexpected chemoselectivity toward important and challenging reactions.In this work,we have proposed and validated unique Ni-O-Ce-O_(v)enriched Ni/CeO_(2)catalysts prepared by a deposition-precipitation method,for the transfer hydrogenation of lignin-derived guaiacol toward cyclohexanol rather than benzene derivatives.The counter-intuitively designed high Ni loading Ni_(2)0/CeO_(2)catalyst(20 wt%Ni content)displays a distance of 0.5 nm for Ni/O_(v)pairs with a remarkable activity(TOF:166.5 h^(-1))and 90%+selectivity for C_(Ar)=C_(Ar)bond saturation,outperforming better metal-dispersed Ni_(5)/CeO_(2)catalyst with limited presence of Ni-O-Ce-O_(v)sites.The high hydrogenation activity against hydrogenolysis reactions on Ni_(2)0/CeO_(2)catalyst is attributed to tunable Ni/O_(v)distances,which constrain the cleavage of CAr-OH bond and deep deoxygenation.Such spatial distribution effect has also facilitated tandem dehydrogenation(O-H bond cleavage)and hydrogenation(C_(Ar)=C_(Ar)hydrogenation)reactions,leading to cyclohexanol as the target product in the absence of externally added H_(2).Insights into spatial distribution of O_(v)sites open an alternative perspective in designing efficient catalysts toward producing value-added cyclic oxygenates through upgrading of lignin compounds.
基金financial support of the National Natural Science Foundation of China(NSFC)(22372039 and 22305247)the Natural Science Foundation of Fujian Province of China(2021J06010)the Fuzhou University Testing Fund of Precious Apparatus(2025T022)。
文摘Transition metal-based electrocatalysts are a promising alternative to noble metal catalysts for electrochemical upgrading of biomass-derived 5-hydroxymethylfurfural(HMF)into high-value 2,5-furandicarboxylic acid(FDCA).However,the rational design of efficient electrocatalysts with precisely tailored structure-activity correlations remains a critical challenge.Herein,we report a hierarchically structured self-supporting electrode(Vo-NiCo(OH)_(2)-NF)synthesized through in situ electrochemical reconstruction of NiCo-Prussian blue analogue(NiCo-PBA)precursor,in which oxygen vacancy(Vo)-rich Co-doped Ni(OH)_(2)nanosheet arrays are vertically aligned on nickel foam(NF),creating an interconnected conductive network.When evaluated for the HMF oxidation reaction(HMFOR),Vo-NiCo(OH)_(2)-NF exhibits exceptional electrochemical performance,achieving near-complete HMF conversion(99%),ultrahigh FDCA Faradaic efficiency(97.5%),and remarkable product yield(96.2%)at 1.45 V,outperforming conventional Co-doped Ni(OH)_(2)(NiCo(OH)_(2)-NF)and pristine Ni(OH)_(2)(Ni(OH)_(2)-NF)electrodes.By combining in situ spectroscopic characterization and theoretical calculations,we elucidate that the synergistic effects of Co-doping and oxygen vacancy engineering effectively modulate the electronic structure of Ni active centers,favor the formation of high-valent Ni^(3+)species,and optimize HMF adsorption,thereby improving the HMFOR performance.This work provides valuable mechanistic insights for catalyst design and may inspire the development of advanced transition metal-based electrodes for efficient biomass conversion systems.
文摘Correction to:Rare Met.https://doi.org/10.1007/s12598-021-01864-4 In the original publication,the affiliation of the 5th author(Corresponding author)was published incorrectly.The correct affiliation is given in this Correction.The original publication has been corrected.
基金upported by the National Natural Science Foundation of China(Nos.U22A20253,52272293,and 52401275)the Fellowship of China Postdoctoral Science Foundation(No.2021M701116).
文摘Modulating the adsorption energy of intermediate species via alloying presents a promising approach to enhance the electrocatalytic nitrate reduction to ammonia(NRA).Nonetheless,the synthesis of alloy catalysts that are uniformly distributed and structurally stable poses significant challenges.Herein,the CuNi alloy was successfully anchored on oxygen vacancy-rich N-Ti_(3)C_(2)T_(x) through metal-support interactions(MSI).The three-dimensional(3D)wrinkled morphology of N-Ti_(3)C_(2)T_(x) MXene was achieved by employing melamine-formaldehyde spheres(MFs)as self-sacrificial templates,which effectively prevented the restacking of the Ti_(3)C_(2)T_(x) layers,thereby increasing specific surface area and promoting the formation of surface oxygen vacancies.Ti–O–M structure plays a crucial role in inhibiting both particle migration and metal atom diffusion.X-ray photoelectron spectroscopy(XPS)analysis confirms moderate metal-support interactions between the CuNi alloy and N-Ti_(3)C_(2)T_(x),leading to the establishment of stable Ti–O–M bonds and charge redistribution within the Ti-O-M framework.The Cu_(5)Ni_(5)/N-Ti_(3)C_(2)T_(x) sample achieves an impressive Faradaic efficiency(FE)of 97.50%at−0.27 V vs.RHE,alongside the highest NH3 yield rate of 527.44µmol h−1 cm−2.In-situ electrochemical Raman spectroscopy and theoretical calculations reveal that the high intrinsic catalytic activity of NRA can be attributed to the synergistic effects between the CuNi alloy and the interfacial metal-oxygen interactions.This work provides significant perspectives on the design of interfacial metal interactions and the development of durable electrocatalysts.
基金supported by Jilin Province Science and Technology Development Program(Nos.20200201001JC,20210502002ZP,20230101367JC,20220301011GX)Jilin Province Science and Technology Major Project(No.222648GX0105103875).
文摘The development of efficient and robust non-precious metal electrocatalyst to drive the sluggish hydrogen oxidation reaction(HOR)is the key to the practical application of anion exchange membrane fuel cells(AEMFC),which relies on the rational regulation of intermediates’binding strength.Herein,we reported a simple strategy to manipulate the adsorption energy of OH^(∗)on electrocatalyst surface via engineering Ni/NbO_(x) heterostructures with manageable oxygen vacancy(Ov).Theoretical calculations confirm that the electronic effect between Ni and NbO_(x) could weaken the hydrogen adsorption on Ni,and the interfacial oxygen vacancy tailor hydroxide binding energy(OHBE).The optimized HBE and OHBE contribute to reduce formation energy of water during the alkaline HOR process.Furthermore,in situ Raman spectroscopy monitor the dynamic process that OH^(∗)adsorbed on oxygen vacancy and react with adjacent H^(∗)adsorbed Ni,confirming the vital role of OH^(∗)for alkaline HOR process.As a result,the optimal Ni/NbO_(x) exhibits a remarkable intrinsic activity with a specific activity of 0.036mA/cm^(2),which is 4-fold than that of pristine Ni counterpart and surpasses most non-precious electrocatalysts ever reported.
基金financially supported by the Doctoral Funding projects from Heze University(No.XY22BS07)
文摘This work presents a hierarchical yolk-shell NiZn-Co_(3)O_(4)sphere with abundant oxygen vacancy by utilizing structure optimization and composition regulation for efficient detection of triethylamine(TEA)gas.A comparative exploration of TEA gas sensing characterization for different Co_(3)O_(4)-based sensors is conducted systematically.The result shows that the sensor based on the NiZn–Co_(3)O_(4)HCSS displays the highest sensing response of 42.5 at a working temperature of 180°C.In particular,the Ni Zn–Co_(3)O_(4)HCSS device possesses a fast responserecovery speed,excellent anti-humidity and outstanding long-term stability of up to 40 days to TEA gas.The improved TEA gas sensing property can be attributed to the intriguing hierarchical core–shell architecture and abundant oxygen vacancy induced by NiZn co-doping.Moreover,to study the sensing mechanism in detail,the adsorption behavior and charge transfer phenomenon between OV–NiZn–Co_(3)O_(4)(110)and TEA molecule is carried out by the density functional theory(DFT).This work demonstrates an outstanding performance of Ni and Zn co-doped hierarchical core–shell Co_(3)O_(4)in TEA detection by combining theoretical and experimental investigations into mechanisms for optimized TEA gas molecule sensing.
基金financially supported by the National Natural Science Foundation of China(No.52372063)China Postdoctoral Science Foundation(No.2023M730391)
文摘Transition metal oxides(TMOs),thanks to their elevated theoretical capacitance and pseudocapacitive properties,are of particular interest in exploring the advanced supercapacitor electrode materials.The present work reports the rapid laser-assisted synthesis of SiC@-Fe_(2)O_(3-x)anode materials with engineered oxygen vacancies in seconds,which improve the charge transport,redox activity,and structural stability,thus facilitating a substantial enhancement in electrochemical performance.As a result,the resultant SiC@Fe_(2)O_(3-x)nanowires exhibit excellent performances with an areal capacitance of 1082.16 at 5 mA cm^(-2),and retain 86.7%capacitance over 10,000 cycles.Furthermore,the assembled asymmetric supercapacitors(ASC),employing SiC@Fe_(2)O_(3-x)as the negative electrode and Ni(OH)2as the positive electrode,delivers a 1.5 V operating voltage,an energy density of 197μWh cm^(-2),and 80.6%capacitance retention after 14,000cycles,representing their promise toward the applications in next-generation energy storage materials.
基金the Haihe Laboratory of Sus-tainable Chemical Transformations for financial support(No.24HHWCSS00009).
文摘Ammonia is essential for agriculture and,as a next-generation carbon-free fuel,typically produced through the Haber-Bosch method.This process requires high temperature and pressure,leading to significant energy consumption and greenhouse gas emissions.Therefore,achieving ammonia synthesis under milder conditions has been a long-standing goal.In this study,we design and synthesize a series of CeO_(2)-modified Fe/carbon-based catalysts with varying amounts of CeO_(2)(Ce_(x)Fe_(y)/C).The catalyst Ce_(2)Fe_(5)/C demonstrates an ammonia yield rate of 3.5 mmol/(g·h),which is 44 times greater than that of Fe/C and 8 times greater than that of commercial Fe-based catalysts at 300℃and 1 MPa.Temperature-programmed desorption experiments show that Ce_(2)Fe_(5)/C has enhanced nitrogen adsorption capabilities.Multiple analyses confirm that the CeO_(2)in Ce_(2)Fe_(5)/C is rich in oxygen vacancies,which can provide electrons to Fe,facilitating nitrogen adsorption,dissociation,and activity in low-temperature ammonia synthesis.
