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Heterointerface Engineering-Induced Oxygen Defects for the Manganese Dissolution Inhibition in Aqueous Zinc Ion Batteries
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作者 Wentao Qu Yong Cai +1 位作者 Baohui Chen Ming Zhang 《Energy & Environmental Materials》 SCIE EI CAS CSCD 2024年第3期112-122,共11页
Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during t... Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy. 展开更多
关键词 electrochemical activation HETEROINTERFACE manganese dissolution inhibition oxygen defects zinc ion batteries
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Oxygen-defects evolution to stimulate continuous capacity increase in Co-free Li-rich layered oxides 被引量:2
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作者 Yibin Zhang Xiaohui Wen +3 位作者 Zhepu Shi Bao Qiu Guoxin Chen Zhaoping Liu 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第7期259-267,I0006,共10页
Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the i... Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides. 展开更多
关键词 Li-rich layered oxide Irreversible oxygen loss Nano-scale oxygen defect Li_(2)MnO_(3)-domain activation
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In-situ oriented oxygen-defect-rich Mn-N-O via nitridation and electrochemical oxidation based on industrial-scale Mn_(2)O_(3) to achieve high-performance aqueous zinc ion battery
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作者 Yao Liu Shuailong Guo +7 位作者 Wei Ling Mangwei Cui Hao Lei Jiaqi Wang Wenzheng Li Qingjiang Liu Lukuan Cheng Yan Huang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第1期11-18,I0001,共9页
As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batter... As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batteries(ARZBs)have been emerging as promising large-scale energy storage systems owing to their high energy densities,low manufacturing cost and intrinsic high safety.However,the direct application of industrial-scale Mn2O3(MO)cathode exhibits poor electrochemical performance especially at high current rates.Herein,a highly reversible Mn-based cathode is developed from the industrial-scale MO by nitridation and following electrochemical oxidation,which triples the ion diffusion rate and greatly promotes the charge transfer.Notably,the cathode delivers a capacity of 161 m Ah g^(-1) at a high current density of 10 A g^(-1),nearly-three times the capacity of pristine MO(60 m Ah g^(-1)).Impressive specific capacity(243.4 m Ah g^(-1))is obtained without Mn^(2+) additive added in the electrolyte,much superior to the pristine MO(124.5 m Ah g^(-1)),suggesting its enhanced reaction kinetics and structural stability.In addition,it possesses an outstanding energy output of 368.4 Wh kg^(-1) at 387.8 W kg^(-1),which exceeds many of reported cathodes in ARZBs,providing new opportunities for the large-scale application of highperformance and low-cost ARZBs. 展开更多
关键词 Aqueous rechargeable zinc-ion battery Mn-based cathode Oxygen defect NITRIDATION Electrochemical oxidation
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Thermal stable Pt clusters anchored by K/TiO_(2)—Al_(2)O_(3)for efficient cycloalkane dehydrogenation
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作者 Zhendong Wang Bofeng Zhang +1 位作者 Guozhu Liu Xiangwen Zhang 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第8期187-198,共12页
Catalytic dehydrogenation of cycloalkanes is considered a valuable endothermic process for alleviating the thermal barrier issue of hypersonic vehicles.However,conventional Pt-based catalysts often face the severe pro... Catalytic dehydrogenation of cycloalkanes is considered a valuable endothermic process for alleviating the thermal barrier issue of hypersonic vehicles.However,conventional Pt-based catalysts often face the severe problem of metal sintering under high-temperature conditions.Herein,we develop an efficient K_(2)CO_(3)-modified Pt/TiO_(2)—Al_(2)O_(3)(K—Pt/TA)for cycloalkane dehydrogenation.The optimized K—Pt/TA showed a high specific activity above 27.9 mol·mol^(-1)·s^(-1)(H_(2)/Pt),with toluene selectivity above 90.0%at 600℃with a high weight hourly space velocity of 266.4 h^(-1).The introduction of alkali metal ions could generate titanate layers after high-temperature hydrogen reduction treatment,which promotes the generation of oxygen vacancy defects to anchored Pt clusters.In addition,the titanate layers could weaken the surface acidity of catalysts and inhibit side reactions,including pyrolysis,polymerization,and isomerization reactions.Thus,this work provides a modification method to develop efficient and stable dehydrogenation catalysts under high-temperature conditions. 展开更多
关键词 Cycloalkane dehydrogenation Pt clusters Oxygen vacancy defects COKING Stability DEACTIVATION
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Building stabilized Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode enables an outstanding room‐/low‐temperature aqueous Zn‐ion batteries
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作者 Ao Wang Dai‐Huo Liu +9 位作者 Lin Yang Fang Xu Dan Luo Haozhen Dou Mengqin Song Chunyan Xu Beinuo Zhang Jialin Zheng Zhongwei Chen Zhengyu Bai 《Carbon Energy》 SCIE EI CAS CSCD 2024年第8期25-35,共11页
Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+)storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this w... Vanadium oxide cathode materials with stable crystal structure and fast Zn^(2+)storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries.In this work,a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide.The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide(V‐O)layers,establishing stabilized two‐dimensional channels for fast Zn^(2+)diffusion.The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects(Od),which boosts the Zn^(2+)diffusion kinetics.As a result,as‐prepared Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O cathode shows outstanding Zn‐storage capabilities under room‐and lowtemperature environments(e.g.,440.3 mAh g^(−1)at room temperature and 294.3 mAh g^(−1)at−60°C).Importantly,it shows a long cycling life and high capacity retention of 93.4%over 2500 cycles at 2 A g^(−1)at−60°C.Furthermore,the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations.The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/lowtemperature vanadium‐based cathode materials. 展开更多
关键词 aqueous zinc‐ion batteries Cu_(0.17)Mn_(0.03)V_(2)O_(5−□)·2.16H_(2)O oxygen defects room‐/lowtemperature performance stabilized nanostructure
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Oxygen‑Defect Enhanced Anion Adsorption Energy Toward Super‑Rate and Durable Cathode for Ni–Zn Batteries 被引量:4
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作者 Jia Yao Houzhao Wan +10 位作者 Chi Chen Jie Ji Nengze Wang Zhaohan Zheng Jinxia Duan Xunying Wang Guokun Ma Li Tao Hanbin Wang Jun Zhang Hao Wang 《Nano-Micro Letters》 SCIE EI CAS CSCD 2021年第11期128-141,共14页
The alkaline zinc-based batteries with high energy density are becoming a research hotspot.However,the poor cycle stability and low-rate performance limit their wide application.Herein,ultra-thin CoNiO2 nanosheet with... The alkaline zinc-based batteries with high energy density are becoming a research hotspot.However,the poor cycle stability and low-rate performance limit their wide application.Herein,ultra-thin CoNiO2 nanosheet with rich oxygen defects anchored on the vertically arranged Ni nanotube arrays(Od-CNO@Ni NTs)is used as a positive material for rechargeable alkaline Ni–Zn batteries.As the highly uniform Ni nanotube arrays provide a fast electron/ion transport path and abundant active sites,the Od-CNO@Ni NTs electrode delivers excellent capacity(432.7 mAh g^(−1))and rate capability(218.3 mAh g^(−1) at 60 A g^(−1)).Moreover,our Od-CNO@Ni NTs//Zn battery is capable of an ultra-long lifespan(93.0%of initial capacity after 5000 cycles),extremely high energy density of 547.5 Wh kg^(−1) and power density of 92.9 kW kg^(−1)(based on the mass of cathode active substance).Meanwhile,the theoretical calculations reveal that the oxygen defects can enhance the interaction between electrode surface and electrolyte ions,contributing to higher capacity.This work opens a reasonable idea for the development of ultra-durable,ultra-fast,and high-energy Ni–Zn battery. 展开更多
关键词 Ni-Zn battery Oxygen defect Nanotube array CoNiO2 nanosheet Adsorption energy
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Oxygen defect-rich double-layer hierarchical porous Co3O4 arrays as high-efficient oxygen evolution catalyst for overall water splitting 被引量:2
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作者 Puxuan Yan Meilin Huang +6 位作者 Benzhi Wang Zixia Wan Mancai Qian Hu Yan Tayirjan Taylor Isimjan Jianniao Tian Xiulin Yang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2020年第8期299-306,I0011,共9页
Construction of oxygen evolution electrocatalysts with abundant oxygen defects and large specific surface areas can significantly improve the conversion efficiency of overall water splitting.Herein,we adopt a controll... Construction of oxygen evolution electrocatalysts with abundant oxygen defects and large specific surface areas can significantly improve the conversion efficiency of overall water splitting.Herein,we adopt a controlled method to prepare oxygen defect-rich double-layer hierarchical porous Co3O4 arrays on nickel foam(DL-Co3O4/NF)for water splitting.The unique array-like structure,crystallinity,porosity,and chemical states have been carefully investigated through SEM,TEM,XRD,BET,and XPS techniques.The designated DL-Co3O4/NF has oxygen defects of up to 67.7%and a large BET surface area(57.4 m2g-1).Electrochemical studies show that the catalyst only requires an overpotential of 256 mV to reach 20 mA cm-2,as well as a small Tafel slope of 60.8 mV dec-1,which is far better than all control catalysts.Besides,the catalyst also demonstrates excellent overall water splitting performance in a two-electrode system and good long-term stability,far superior to most previously reported catalysts.Electrocatalytic mechanisms indicate that abundant oxygen vacancies provide more active sites and good conductivity.At the same time,the unique porous arrays facilitate electrolyte transport and gas emissions,thereby synergistically improving OER catalytic performance. 展开更多
关键词 Metal-organic frameworks Array-like structure Oxygen defects Oxygen evolution Water splitting
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First-principles study of the influences of oxygen defects upon the electronic properties of Nb-doped TiO_2 by GGA + U methods 被引量:2
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作者 宋晨路 杨振辉 +4 位作者 苏婷 王慷慨 王菊 刘涌 韩高荣 《Chinese Physics B》 SCIE EI CAS CSCD 2014年第5期453-460,共8页
The influence of oxygen defects upon the electronic properties of Nb-doped TiO2 has been studied by using the general gradient approximation (GGA)+U method. Four independent models (i.e., an undoped anatase cell, ... The influence of oxygen defects upon the electronic properties of Nb-doped TiO2 has been studied by using the general gradient approximation (GGA)+U method. Four independent models (i.e., an undoped anatase cell, an anatase cell with a Nb dopant at Ti site (NbTi), an anatase cell with a Nb-dopant and an oxygen vacancy (NbTi+Vo), and an anatase cell with a Nb-dopant and an interstitial oxygen (NbTi+Oi)) were considered. The density of states, effective mass, Bader charge, charge density, and electron localization function were calcul^ited. The results show that in the NbTi+Vo cell both eg and t2g levels of Ti 3d orbits make contributions to the electronic conductivity, and the oxygen vacancies (Vo) collaborate with Nb-dopants to favor the high electrical conductivity by inducing the Nb-dopants to release more excess charges. In NbTi+Oi, an unoccupied impurity level appears in the band gap, which served as an acceptor level and suppressed the electronic conductivity. The results qualitatively coincide with experimental results and possibly provide insights into the preparation of TCOs with desirable conductivity. 展开更多
关键词 TiO2 oxygen defects excess charges GGA+U method
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Defect-rich Mg-Al MMOs supported TEPA with enhanced charge transfer for highly efficient and stable direct air capture 被引量:1
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作者 Meng Zhao Jiewen Xiao +1 位作者 Wanlin Gao Qiang Wang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第5期401-410,共10页
Due to the advantages of low energy consumption and high CO_(2) selectivity, the development of solid amine-based materials has been regarded as a hot research topic in the field of DAC for the past decades.The adsorp... Due to the advantages of low energy consumption and high CO_(2) selectivity, the development of solid amine-based materials has been regarded as a hot research topic in the field of DAC for the past decades.The adsorption capacity and stability over multiple cycles have been the top priorities for evaluation of practical application value. Herein, we synthesized a novel DAC material by loading TEPA onto defect-rich Mg_(0.55)Al-O MMOs with enhanced charge transfer effect. The optimal Mg_(0.55)Al-O-TEPA67% demonstrates the highest CO_(2)uptake of(3.0 mmol g^(-1)) and excellent regenerability, maintaining ~90% of the initial adsorption amount after 80 adsorption/desorption cycles. The in situ DRIFTS experiments suggested the formation of bicarbonate species under wet conditions. DFT calculations indicated that the stronger bonding between Mg_(0.55)Al-O support and solid amine was caused by the abundance of oxygen defects on MMOs confirmed by XPS and ESR, which favors the charge transfer between the support and amine,resulting in intense interaction and excellent regenerability. This work for the first time conducted comprehensive and systematic investigation on the stabilization mechanism for MMOs supported solid amine adsorbents with highest uptake and superior cyclic stability in depth, which is different from the most popular SiO_(2)-support, thus providing facile strategy and comprehensive theoretical mechanism support for future research about DAC materials. 展开更多
关键词 Direct air capture Solid amine-based materials Mixed metal oxides Oxygen defects Charge transfer effect
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Tunable oxygen defect density and location for enhancement of energy storage
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作者 Jun Chen Jiangao Li +7 位作者 Ling Sun Zhong Lin Zhengguang Hu Hongtao Zhang Xiaoling Wu Dongbo Zhang Guoan Cheng Ruiting Zheng 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2021年第8期736-747,I0015,共13页
Defect engineering is in the limelight for the fabrication of electrochemical energy storage devices.However,determining the influence of the defect density and location on the electrochemical behavior remains challen... Defect engineering is in the limelight for the fabrication of electrochemical energy storage devices.However,determining the influence of the defect density and location on the electrochemical behavior remains challenging.Herein,self-organized TiO_(2)nanotube arrays(TNTAs)are synthesized by anodization,and their oxygen defect location and density are tuned by a controllable post-annealing process.TNTAs annealed at 600℃ in N2 exhibit the highest capacity(289.2 m Ah g^(-1)at 0.8 C)for lithium-ion storage,while those annealed at 900℃ in N2 show a specific capacitance of 35.6 m F cm^(-2)and stability above96%after 10,000 cycles for supercapacitor.Ex situ electron paramagnetic resonance spectra show that the surface-exposed oxygen defects increase,but the bulk embedded oxygen defects decrease with increasing annealing temperature.Density functional theory simulations reveal that a higher density of bulk oxygen defects corresponds to higher localized electrons states,which upshift the Fermi level and facilitate the lithium intercalation kinetic process.Meanwhile,differential charge density calculation indicates that the increase of surface oxygen defects in the anatase(101)plane leads to higher density excess electrons,which act as negative charge centers to enhance the surface potential for ion adsorption.This oxygen-deficient location and density tunable strategy introduce new opportunities for high-energy and high-power-density energy storage systems. 展开更多
关键词 Oxygen defects Excess electrons SUPERCAPACITORS Lithium-ion batteries DFT calculations
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Achieving high-performance multilayer MoSe2 photodetectors by defect engineering
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作者 Jintao Hong Fengyuan Zhang +8 位作者 Zheng Liu Jie Jiang Zhangting Wu Peng Zheng Hui Zheng Liang Zheng Dexuan Huo Zhenhua Ni Yang Zhang 《Chinese Physics B》 SCIE EI CAS CSCD 2021年第8期518-523,共6页
Optoelectronic properties of MoSe2 are modulated by controlled annealing in air.Characterizations by Raman spectroscopy and XPS demonstrate the introduction of oxygen defects.Considerable increase in electron and hole... Optoelectronic properties of MoSe2 are modulated by controlled annealing in air.Characterizations by Raman spectroscopy and XPS demonstrate the introduction of oxygen defects.Considerable increase in electron and hole mobilities reveals the highly improved electron and hole transport.Furthermore,the photocurrent is enhanced by nearly four orders of magnitudes under 7 nW laser exposure after annealing.The remarkable enhancement in the photoresponse is attributed to an increase in hole trapping centers and a reduction in resistance.Furthermore,the annealed photodetector shows a fast time response on the order of 10 ms and responsivity of 3×10^(4) A/W. 展开更多
关键词 MoSe2 oxygen defects electrical properties optoelectronic properties
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Formation Enthalpy Calculation of Oxygen Vacancy Defect in Doped Lithium Niobate Crystals
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作者 QIANGLiang-sheng LIYao +2 位作者 TANGDong-yan XUChong-quan WEIYong-de 《Chemical Research in Chinese Universities》 SCIE CAS CSCD 2004年第1期65-67,共3页
The relationship between temperature and oxygen vacancy concentration is deduced in this paper. Based on the data of thermal weight-loss experiment, the formation enthalpies of congruent and several doped LN crystals ... The relationship between temperature and oxygen vacancy concentration is deduced in this paper. Based on the data of thermal weight-loss experiment, the formation enthalpies of congruent and several doped LN crystals have been calculated. It was found that the formation enthalpy of oxygen vacancies can be decreased evidently by doping valence-changeable ions. The experimental results were discussed and a new reduction process of the photorefractive LN crystal at a relatively low temperature was proposed, and the reduced crystals showed a good effect in practical use. 展开更多
关键词 Formation enthalpy calculation Oxygen vacancy defect Doped lithium niobate crystal
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Synergy in magnetic Ni_(x)Co_(1)O_(y) oxides enables base-free selective oxidation of 5-hydroxymethylfurfural on loaded Au nanoparticles
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作者 Hao Zhang Yinghao Wang +5 位作者 Qizhao Zhang Bang Gu Qinghu Tang Qiue Cao Kun Wei Wenhao Fang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第3期526-536,I0014,共12页
The base-free aerobic oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-furandicarboxylic acid(FDCA)in water is recognized as an important and sustainable upgrading process for cellulosic carbohydrates.However,selectiv... The base-free aerobic oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-furandicarboxylic acid(FDCA)in water is recognized as an important and sustainable upgrading process for cellulosic carbohydrates.However,selectivity control still remains a challenge.Here,we disclose that the unique synergy in magnetic Ni_(x)Co_(1)O_(y)(x=1,3 and 5) bimetallic oxides can induce reactive oxygen defects and simultaneously stabilize small-sized metallic Au nanoparticles in the Au/Ni_(x)Co_(1)O_(y)catalysts.Such catalytic features render effective adsorption and activation of O_(2),OH and C=O groups,realizing selective oxidation of HMF to FDCA.On a series of magnetic Au/Ni_(x)Co_(1)O_(y)catalysts with almost identical Au loadings(ca.0.5 wt%) and particle sizes(ca.2.7 nm),the variable Ni/Co molar ratios give rise to the tunable electron density of Au sites and synergistic effect between NiO and CoO_(y).The initial conversion rates of HMF and its derived intermediates(i.e., DFF,HMFCA and FFCA) show a volcano-like dependence on the number of oxygen defects(i.e.,O_(2)^(-)and O^(-)) and electron-rich Au0sites.The optimum Au/Ni3Co1Oycatalyst exhibits a highest productivity of FDCA(12.5 mmol_(FDCA)mol_(Au)^(-1)h^(-1)) among all the Au catalysts in the literature and achieves> 99% yield of FDCA at 120℃ and 10 bar of O_(2).In addition,this catalyst can be easily recovered by a magnet and show superior stability and reusability during six consecutive cycling tests.This work may shed a light on Au catalysis for the base-free oxidation of biomass compounds by smartly using the synergy in bimetallic oxide carriers. 展开更多
关键词 Aerobic oxidation 2 5-Furandicarboxylic acid C=O group conversion Magnetic catalyst Oxygen defects Synergistic effect
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Regulating Oxygen Vacancy Defects in Heterogeneous NiO-CeO_(2)−δ Hollow Multi-shelled Structure for Boosting Oxygen Evolution Reaction
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作者 WANG Huan GONG Guannan +3 位作者 SUN Guohua QI Jian YU Ranbo WANG Dan 《Chemical Research in Chinese Universities》 SCIE CAS CSCD 2024年第3期475-483,共9页
CeO_(2) with excellent oxygen storage-exchange capacity and NiO with excellent surface activity were used to construct a heterogeneous NiO-CeO_(2)−δhollow multi-shelled structure(HoMS)by spray drying.It turned out th... CeO_(2) with excellent oxygen storage-exchange capacity and NiO with excellent surface activity were used to construct a heterogeneous NiO-CeO_(2)−δhollow multi-shelled structure(HoMS)by spray drying.It turned out that as the proportion of CeO_(2) increases,the overpotential and Tafel slope of NiO-CeO_(2)−δHoMSs first decreased and then increased.This is mainly because the construction of the NiO-CeO_(2)−δHoMSs not only increases the specific surface area,but also introduces oxygen vacancy defects,thus improving the interface charge transfer capability of the materials and further improving the oxygen evolution reaction(OER)performance.However,the increase of the calcination temperature will induce the decay of the OER performance of NiO-CeO_(2)−δHoMSs,which is mainly due to the decrease of the specific surface area,the reduction of oxygen vacancy defects,and the weakening of interface charge transfer capability.Furthermore,a series of heterogeneous composite HoMSs,such as Ni/Co,Mo/Ni,Al/Ni and Fe/Ni oxides was successfully constructed by spray drying,which enriched the diversity of HoMSs. 展开更多
关键词 Heterogeneous composite structure Hollow multishelled structure Oxygen vacancy defect Oxygen evolution reaction
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Highly efficient Z-scheme WO_(3-x) quantum dots/TiO_2 for photocatalytic hydrogen generation 被引量:6
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作者 潘伦 张靖雯 +4 位作者 贾旭 马煜航 张香文 王莅 邹吉军 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2017年第2期253-259,共7页
Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation.In this work,Z-scheme semiconductors composed of WO3-x quantum dots supported on TiO2(WO3-xQDS/TiO2) were fabricated by solvoth... Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation.In this work,Z-scheme semiconductors composed of WO3-x quantum dots supported on TiO2(WO3-xQDS/TiO2) were fabricated by solvothermal and hydrogen-reduction methods.Characterization by transmission electron microscopy and X-ray diffraction indicated that the amount and size of the WO3-x QDs could be tuned by modulating the addition of the W precursor.Evidence from X-ray photoelectron spectroscopy and photoluminescence spectroscopy suggested that the hydrogen reduction of the composite induced the formation of oxygen vacancy(W^5+/Vo) defects in WO3.These defects led to ohmic contact between WO3-x and TiO2,which altered the charge-transfer pathway from type Ⅱ heterojunction to Z-scheme,and maintained the highly reductive and oxidative ability of TiO2 and WO3-x,respectively.Therefore,the Z-scheme sample showed 1.3-fold higher photoactivity than pure TiO2 in hydrogen generation.These results suggest that the formation of W^5+/Vo defects at the interface is highly beneficial for the fabrication of Z-scheme photocatalysts. 展开更多
关键词 WO3–x Titanium oxide Hydrogen generation Quantum dots W^5+/oxygen vacancy defect
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Oxygen‑Deficient β‑MnO_(2)@Graphene Oxide Cathode for High‑Rate and Long‑Life Aqueous Zinc Ion Batteries 被引量:5
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作者 Shouxiang Ding Mingzheng Zhang +10 位作者 Runzhi Qin Jianjun Fang Hengyu Ren Haocong Yi Lele Liu Wenguang Zhao Yang Li Lu Yao Shunning Li Qinghe Zhao Feng Pan 《Nano-Micro Letters》 SCIE EI CAS CSCD 2021年第11期203-214,共12页
Recent years have witnessed a booming interest in grid-scale electrochemical energy storage,where much attention has been paid to the aqueous zinc ion batteries(AZIBs).Among various cathode materials for AZIBs,mangane... Recent years have witnessed a booming interest in grid-scale electrochemical energy storage,where much attention has been paid to the aqueous zinc ion batteries(AZIBs).Among various cathode materials for AZIBs,manganese oxides have risen to prominence due to their high energy density and low cost.However,sluggish reaction kinetics and poor cycling stability dictate against their practical application.Herein,we demonstrate the combined use of defect engineering and interfacial optimization that can simultaneously promote rate capability and cycling stability of MnO_(2) cathodes.β-MnO_(2) with abundant oxygen vacancies(VO)and graphene oxide(GO)wrapping is synthesized,in which VO in the bulk accelerate the charge/discharge kinetics while GO on the surfaces inhibits the Mn dissolution.This electrode shows a sustained reversible capacity of~129.6 mAh g^(−1) even after 2000 cycles at a current rate of 4C,outperforming the state-of-the-art MnO_(2)-based cathodes.The superior performance can be rationalized by the direct interaction between surface VO and the GO coating layer,as well as the regulation of structural evolution ofβ-MnO_(2) during cycling.The combinatorial design scheme in this work offers a practical pathway for obtaining high-rate and long-life cathodes for AZIBs. 展开更多
关键词 Manganese oxides Oxygen defects Surface optimization Aqueous zinc battery
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Oxygen vacancies enriched nickel cobalt based nanoflower cathodes: Mechanism and application of the enhanced energy storage 被引量:2
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作者 Jiahui Ye Xingwu Zhai +10 位作者 Long Chen Wen Guo Tiantian Gu Yulin Shi Juan Hou Fei Han Yi Liu Changchun Fan Gang Wang Shanglong Peng Xuhong Guo 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2021年第11期252-261,I0006,共11页
The rational design of oxygen vacancies and electronic microstructures of electrode materials for energy storage devices still remains a challenge. Herein, we synthesize nickel cobalt-based oxides nanoflower arrays as... The rational design of oxygen vacancies and electronic microstructures of electrode materials for energy storage devices still remains a challenge. Herein, we synthesize nickel cobalt-based oxides nanoflower arrays assembled with nanowires grown on Ni foam via the hydrothermal process followed annealing process in air and argon atmospheres respectively. It is found that the annealing atmosphere has a vital influence on the oxygen vacancies and electronic microstructures of resulting NiCo_(2)O_(4) (NCO-Air) and CoNiO_(2) (NCO-Ar) products, which NCO-Ar has more oxygen vacancies and larger specific surface area of 163.48 m^(2)/g. The density functional theory calculation reveals that more oxygen vacancies can provide more electrons to adsorb –OH free anions resulting in superior electrochemical energy storage performance. Therefore, the assembled asymmetric supercapacitor of NCO-Ar//active carbon delivers an excellent energy density of 112.52 Wh/kg at a power density of 558.73 W/kg and the fabricated NCO-Ar//Zn battery presents the specific capacity of 180.20 mAh/g and energy density of 308.14 Wh/kg. The experimental measurement and theoretical calculation not only provide a facile strategy to construct flower-like mesoporous architectures with massive oxygen vacancies, but also demonstrate that NCO-Ar is an ideal electrode material for the next generation of energy storage devices. 展开更多
关键词 NiCo_(2)O_(4) CoNiO_(2) SUPERCAPACITOR Oxygen vacancy defects Flower-like microstructure
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Electrical analysis of inter-growth structured Bi_4Ti_3O_(12)-Na_(0.5)Bi_(4.5)Ti_4O_(15) ceramics 被引量:1
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作者 江向平 江亚林 +3 位作者 江兴安 陈超 涂娜 陈云婧 《Chinese Physics B》 SCIE EI CAS CSCD 2017年第7期386-392,共7页
Inter-growth bismuth layer-structured ferroelectrics(BLSFs), Bi_4Ti_3O_(12)-Na_(0.5)Bi_(4.5)Ti_4O_(15)(BIT-NBT), were successfully synthesized using the traditional solid-state reaction method. X-ray diffr... Inter-growth bismuth layer-structured ferroelectrics(BLSFs), Bi_4Ti_3O_(12)-Na_(0.5)Bi_(4.5)Ti_4O_(15)(BIT-NBT), were successfully synthesized using the traditional solid-state reaction method. X-ray diffraction(XRD) Rietveld refinements were conducted using GSAS software. Good agreement and low residual are obtained. The XRD diffraction peaks can be well indexed into I2 cm space group. The inter-growth structure was further observed in the high-resolution TEM image. Dielectric and impedance properties were measured and systematically analyzed. At the temperature range 763-923 K(below T_c), doubly ionized oxygen vacancies(OVs) are localized and the short-range hopping leads to the relaxation processes with an activation energy of 0.79-1.01 eV. Above T_c, the doubly charged OVs are delocalized and become free ones, which contribute to the long-range dc conduction. The reduction in relaxation species gives rise to a higher relaxation activation energy ~ 1.6 eV. 展开更多
关键词 Bi4Ti3O12-Na0.5Bi4.5Ti4O15 impedance spectroscopy oxygen vacancies-related defect dipoles electrical analysis
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Synergic effects of Cu_xO electron transfer co-catalyst and valence band edge control over TiO_2 for efficient visible-light photocatalysis 被引量:1
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作者 Lina Kong Xintong Zhang +2 位作者 Changhua Wang Fangxu Wan Lan Li 《Chinese Journal of Catalysis》 CSCD 北大核心 2017年第12期2120-2131,共12页
Bandgap engineering by doping and co‐catalyst loading are two primary approaches to designing efficient photocatalysts by promoting visible‐light absorption and charge separation,respectively.Shifting of the TiO2con... Bandgap engineering by doping and co‐catalyst loading are two primary approaches to designing efficient photocatalysts by promoting visible‐light absorption and charge separation,respectively.Shifting of the TiO2conduction band edge is frequently applied to increase visible‐light absorption but also lowers the reductive properties of photo‐excited electrons.Herein,we report a visible‐light‐driven photocatalyst based on valance band edge control induced by oxygen excess defects and modification with a CuxO electron transfer co‐catalyst.The CuxO grafted oxygen‐rich TiO2microspheres were prepared by ultrasonic spray pyrolysis of the peroxotitanate precursor followed by a wet chemical impregnated treatment.We found that oxygen excess defects in TiO2shifted the valence band maximum upward and improved the visible‐light absorption.The CuxO grafted onto the surface acted as a co‐catalyst that efficiently reduced oxygen molecules to active intermediates(i.e.,O2??radial and H2O2),thus consuming the photo‐generated electrons.Consequently,the CuxO grafted oxygen‐rich TiO2microspheres achieved a photocatalytic activity respectively8.6,13.0and11.0as times high as those of oxygen‐rich TiO2,normal TiO2and CuxO grafted TiO2,for degradation of gaseous acetaldehyde under visible‐light irradiation.Our results suggest that high visible‐light photocatalytic efficiency can be achieved by combining oxygen excess defects to improve visible‐light absorption together with a CuxO electron transfer co‐catalyst.These findings provide a new approach to developing efficient heterojunction photocatalysts. 展开更多
关键词 Visible light photocatalysis TiO2 CuxO cocatalyst Oxygen‐excess defect Porous microsphere
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Ultrafine MoO_(x)clusters anchored on g-C_(3)N_(4)with nitrogen/oxygen dual defects for synergistic efficient O_(2)activation and tetracycline photodegradation 被引量:4
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作者 Huidong Shen Xinyu Zhan +6 位作者 Song Hong Liang Xu Chunming Yang Alex W.Robertson Leiduan Hao Feng Fu Zhenyu Sun 《Nano Research》 SCIE EI CSCD 2023年第8期10713-10723,共11页
Photocatalytic O_(2)activation to generate reactive oxygen species is crucially important for purifying organic pollutants,yet remains a challenge due to poor adsorption of O_(2)and low efficiency of electron transfer... Photocatalytic O_(2)activation to generate reactive oxygen species is crucially important for purifying organic pollutants,yet remains a challenge due to poor adsorption of O_(2)and low efficiency of electron transfer.Herein,we demonstrate that ultrafine MoO_(x)clusters anchored on graphitic carbon nitride(g-C_(3)N_(4))with dual nitrogen/oxygen defects promote the photocatalytic activation of O_(2)to generate·O_(2)−for the degradation of tetracycline hydrochloride(TCH).A range of characterization techniques and density functional theory(DFT)calculations reveal that the introduction of the nitrogen/oxygen dual defects and MoO_(x)clusters enhances the O_(2)adsorption energy from−2.77 to−2.94 eV.We find that MoO_(x)clusters with oxygen vacancies(Ov)and surface Ov-mediated Moδ+(3≥δ≥2)possess unpaired localized electrons,which act as electron capture centers to transfer electrons to the MoO_(x)clusters.These electrons can then transfer to the surface adsorbed O_(2),thus promoting the photocatalytic conversion of O_(2)to·O_(2)−and,simultaneously,realizing the efficient separation of photogenerated electron–hole pairs.Our fully-optimized MoO_(x)/g-C_(3)N_(4)catalyst with dual nitrogen/oxygen defects manifests outstanding photoactivities,achieving 79%degradation efficiency toward TCH within 120 min under visible light irradiation,representing nearly 7 times higher activity than pristine g-C_(3)N_(4).Finally,based on the results of liquid chromatograph mass spectrometry and DFT calculations,the possible photocatalytic degradation pathways of TCH were proposed. 展开更多
关键词 MoO_(x)clusters nitrogen/oxygen dual defects electron-hole separation O_(2)activation tetracycline photodegradation
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