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Electronically modulated d-band centers of MOF-derived carbon-supported Ru/HfO_(2) for oxygen reduction and aqueous/flexible zinc-air batteries
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作者 Chuan Hu Fengli Wei +4 位作者 Qinrui Liang Qiming Peng Yuting Yang Tayirjan Taylor Isimjan Xiulin Yang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第5期247-255,I0007,共10页
The construction of oxide/metal composite catalysts is a competent means of exploiting the electronic interactions between oxide/metal to enhance catalytic activity.In this work,we construct a novel heterogeneous comp... The construction of oxide/metal composite catalysts is a competent means of exploiting the electronic interactions between oxide/metal to enhance catalytic activity.In this work,we construct a novel heterogeneous composite(Ru/HfO_(2)-NC)with Ru/HfO2nanoparticles nested in nitrogen-doped porous carbon via a zeolitic imidazole frameworks-assisted(ZIF)co-precipitation and calcination approach.In particular,ZIF guides an in-situ construction of nested configuration and confines the scattered nanoparticles.Strikingly,Ru/HfO_(2)-NC exhibits unusual ORR activity,superb durability,and methanol tolerance in0.1 M KOH solution with high half-wave potential(E1/2)of 0.83 V and follows a near-4e-reaction pathway.Additionally,the ZAB assembled with cathodic Ru/HfO_(2)-NC outputs a power density of 157.3 m W cm^(-2),a specific capacity of 775 mA h g-1Zn,and a prolonged lifespan of 258 h at 5 mA cm^(-2).Meanwhile,the catalyst has demonstrated potential applicability in flexible ZAB.As suggested by experimental results and density functional theory(DFT)analysis,the remarkable property possibly originated from the optimization of the adsorption and desorption of reactive intermediates caused by the reconfiguration of the electronic structure between Ru and HfO_(2). 展开更多
关键词 Ru/HfO_(2) Charge interaction Oxygen vacancy Oxygen reduction Zinc-air battery
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Dielectric polarization in MgFe_(2)O_(4) coating and bulk doping to enhance high-voltage cycling stability of Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2) cathode material
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作者 Xiaoqian Xu Yizhen Huang +7 位作者 Dan Li Qichang Pan Sijiang Hu Yahao Li Hongqiang Wang Youguo Huang Fenghua Zheng Qingyu Li 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第6期200-211,I0007,共13页
Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_... Charging P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)to 4.5 V for higher capacity is enticing.However,it leads to severe capacity fading,ascribing to the lattice oxygen evolution and the P2-O2 phase transformation.Here,the Mg Fe_(2)O_(4) coating and Mg,Fe co-doping were constructed simultaneously by Mg,Fe surface treatment to suppress lattice oxygen evolution and P2-O2 phase transformation of P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)at deep charging.Through ex-situ X-ray diffraction(XRD)tests,we found that the Mg,Fe bulk co-doping could reduce the repulsion between transition metals and Na+/vacancies ordering,thus inhibiting the P2-O2 phase transition and significantly reducing the irreversible volume change of the material.Meanwhile,the internal electric field formed by the dielectric polarization of Mg Fe_(2)O_(4) effectively inhibits the outward migration of oxidized O^(a-)(a<2),thereby suppressing the lattice oxygen evolution at deep charging,confirmed by in situ Raman and ex situ XPS techniques.P2-Na NM@MF-3 shows enhanced high-voltage cycling performance with capacity retentions of 84.8% and 81.3%at 0.1 and 1 C after cycles.This work sheds light on regulating the surface chemistry for Na-layered oxide materials to enhance the high-voltage performance of Na-ion batteries. 展开更多
关键词 P2-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2) MgFe_(2)O_(4) Bulk doping Lattice oxygen evolution P2-O2 phase transformation
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Valence electronic engineering of superhydrophilic Dy-evoked Ni-MOF outperforming RuO_(2) for highly efficient electrocatalytic oxygen evolution
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作者 Zhiyang Huang Miao Liao +6 位作者 Shifan Zhang Lixia Wang Mingcheng Gao Zuyang Luo Tayirjan Taylor Isimjan Bao Wang Xiulin Yang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第3期244-252,I0007,共10页
Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy ... Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts. 展开更多
关键词 Dy@Ni-MOF Dy incorporation Electronic interaction SUPERHYDROPHILICITY Oxygen evolution reaction
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Mg,Ti-base surface integrated layer and bulk doping to suppress lattice oxygen evolution of Ni-rich cathode material at a high cut-off voltage 被引量:1
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作者 Fan Peng Youqi Chu +7 位作者 Yu Li Qichang Pan Guangchang Yang Lixuan Zhang Sijiang Hu Fenghua Zheng Hongqiang Wang Qingyu Li 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第8期434-444,I0012,共12页
The Nickel-rich layered cathode materials charged to 4.5 V can obtain a specific capacity of more than 200 m Ah g^(-1).However,the nickel-rich layered cathode materials suffer from the severe capacity fade during high... The Nickel-rich layered cathode materials charged to 4.5 V can obtain a specific capacity of more than 200 m Ah g^(-1).However,the nickel-rich layered cathode materials suffer from the severe capacity fade during high-voltage cycling,which is related to the phase transformation and the surface sides reactions caused by the lattice oxygen evolution.Here,the simultaneous construction of a Mg,Ti-based surface integrated layer and bulk doping through Mg,Ti surface treatment could suppress the lattice oxygen evolution of Nirich material at deep charging.More importantly,Mg and Ti are co-doped into the particles surface to form an Mg_(2)TiO_(4) and Mg_(0.5–x)Ti_(2–y)(PO_(4))_(3) outer layer with Mg and Ti vacancies.In the constructed surface integrated layer,the reverse electric field in the Mg_(2)TiO_(4) effectively suppressed the outward migration of the lattice oxygen anions,while Mg_(0.5–x)Ti_(2–y)(PO_(4))_(3) outer layer with high electronic conductivity and good lithium ion conductor could effectively maintained the stability of the reaction interface during highvoltage cycling.Meanwhile,bulk Mg and Ti co-doping can mitigate the migration of Ni ions in the bulk to keep the stability of transition metal–oxygen(M-O)bond at deep charging.As a result,the NCM@MTP cathode shows excellent long cycle stability at high-voltage charging,which keep high capacity retention of 89.3%and 84.3%at 1 C after 200 and 100 cycles under room and elevated temperature of 25 and 55°C,respectively.This work provides new insights for manipulating the surface chemistry of electrode materials to suppress the lattice oxygen evolution at high charging voltage. 展开更多
关键词 Ni-rich layered oxide Mg Ti-base surface integrated layer Bulk doping Lattice oxygen evolution
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Synthesis and Crystal Structure of a Cu(Ⅱ) Coordination Polymer: [Cu(L)(1,10-phen)]_n 被引量:1
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作者 王翠翠 杨鸽鸽 +1 位作者 李海叶 蒋毅民 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2014年第9期1300-1304,共5页
A new complex [Cu(L)(1,10-phen)]n(1, L = N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space ... A new complex [Cu(L)(1,10-phen)]n(1, L = N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P21/c with a = 11.481(2), b = 18.094(4), c = 8.5198(17) , β = 102.26(3)°,V = 1729.5(6) 3, Z = 4, Dc = 1.759 g/cm3, F(000) = 932, μ = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu(Ⅱ) ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu(Ⅱ) units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure. 展开更多
关键词 铜(Ⅱ)离子 晶体结构 配位聚合物 CU 合成 X射线衍射分析 超分子结构 元素分析
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Interface engineering of porous Fe^(2)P-WO_(2.92) catalyst with oxygen vacancies for highly active and stable large-current oxygen evolution and overall water splitting
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作者 Qimin Peng Qiuting He +3 位作者 Yan Hu Tayirjan Taylor Isimjan Ruobing Hou Xiulin Yang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第2期574-582,共9页
Constructing a low cost,and high-efficiency oxygen evolution reaction(OER)electrocatalyst is of great significance for improving the performance of alkaline electrolyzer,which is still suffering from highenergy consum... Constructing a low cost,and high-efficiency oxygen evolution reaction(OER)electrocatalyst is of great significance for improving the performance of alkaline electrolyzer,which is still suffering from highenergy consumption.Herein,we created a porous iron phosphide and tungsten oxide self-supporting electrocatalyst with oxygen-containing vacancies on foam nickel(Fe_(2)P-WO_(2.92)/NF)through a facile insitu growth,etching and phosphating strategies.The sequence-controllable strategy will not only generate oxygen vacancies and improve the charge transfer between Fe_(2)P and WO_(2.92) components,but also improve the catalyst porosity and expose more active sites.Electrochemical studies illustrate that the Fe_(2)P-WO_(2.92)/NF catalyst presents good OER activity with a low overpotential of 267 mV at 100 mA cm^(-2),a small Tafel slope of 46.3 mV dec^(-1),high electrical conductivity,and reliable stability at high current density(100 mA cm^(-2) for over 60 h in 1.0 M KOH solution).Most significantly,the operating cell voltage of Fe_(2)P-WO_(2.92)/NF‖Pt/C is as low as 1.90 V at 400 mA cm^(-2) in alkaline condition,which is one of the lowest reported in the literature.The electrocatalytic mechanism shows that the oxygen vacancies and the synergy between Fe_(2)P and WO_(2.92) can adjust the electronic structure and provide more reaction sites,thereby synergistically increasing OER activity.This work provides a feasible strategy to fabricate high-efficiency and stable non-noble metal OER electrocatalysts on the engineering interface. 展开更多
关键词 Fe^(2)P-WO_(2.92) Interface engineering Oxygen vacancy Oxygen evolution Overall water splitting
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Delicate surface vacancies engineering of Ru doped MOF-derived Ni-NiO@C hollow microsphere superstructure to achieve outstanding hydrogen oxidation performance
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作者 Yuting Yang Yi Huang +4 位作者 Shuqing Zhou Yi Liu Luyan Shi Tayirjan Taylor Isimjan Xiulin Yang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第9期395-404,I0011,共11页
Surface vacancy defects,as the bridge between theoretical structural study and the design of heterogenous catalysts,have captured much attention.This work develops a metal-organic framework-engaged replacement-pyrolys... Surface vacancy defects,as the bridge between theoretical structural study and the design of heterogenous catalysts,have captured much attention.This work develops a metal-organic framework-engaged replacement-pyrolysis approach to obtain highly dispersed Ru nanoparticles immobilized on the vacancy-rich Ni-NiO@C hollow microsphere(Ru/Ni-NiO@C).Fine annealing at 400°C introduces nickel and oxygen vacancies on Ru/Ni-NiO@C surface,resulting in an improved electrical conductivity and rapid mass-charge transfer efficiency.Ru/Ni-NiO@C with a hollow micro/nanostructure and interconnected meso-porosity favors the maximal exposure of abundant active sites and elevation of hydrogen oxidation reaction(HOR)activity.Experimental results and density functional theory(DFT)calculations reveal that an electronic effect between Ru and Ni-NiO@C,in conjunction with nickel/oxygen vacancies in the NiO species could synergistically optimize hydrogen binding energy(HBE)and hydroxide binding energy(OHBE).The HBE and OHBE optimizations thus created confer Ru/Ni-NiO@C with a mass activity over 7.75 times higher than commercial Pt/C.Our work may provide a constructive route to make a breakthrough in elevating the hydrogen electrocatalytic performance. 展开更多
关键词 Ru/Ni-NiO@C Vacancy defects Electrocatalysis Metal-organic framework Hydrogen oxidation
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Detection of Target Genes in Viable Bacteria and Extracellular DNA Using Loop-Mediated Isothermal Amplification Assay
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作者 YANG Qianqian ZHANG Xuzhi +5 位作者 JIANG Xiaoyu LI Yang ZHAO Jun HAO Zhihui WANG Pingping QU Keming 《渔业科学进展》 CSCD 北大核心 2020年第2期41-50,共10页
When the loop-mediated isothermal amplification(LAMP)assay is used for detecting target genes,DNA extraction is unnecessary in many cases.Simple pretreatment(e.g.heating)is enough to obtain rather sensitive responses.... When the loop-mediated isothermal amplification(LAMP)assay is used for detecting target genes,DNA extraction is unnecessary in many cases.Simple pretreatment(e.g.heating)is enough to obtain rather sensitive responses.Even test samples without any pretreatment can be used as template.This feature suggests that LAMP is superior to PCR in developing point-of-care test strategies.In this study,using Stx1 gene from E.coli as model,we verified that viable cells,dead cells and extracellular DNA could function as template in the LAMP assay.In the incubation at 63℃,viable bacteria in the LAMP reaction mixture lysed completely within 2 min,providing DNA template for nucleic acid amplification.The Stx1 gene in diluted culture medium,spiked tap water,spiked seawater and real seawater all could be detected,with or without the step of DNA extraction.We found that the complex substances in real sample(e.g.natural seawater)exhibited considerable inhibitory effect on the sensitivity of the LAMP assay.These outcomes are meaningful for building a point-of-care strategy by employing the LAMP assay for environmental monitoring,bio-resource surveys,food safety,etc.in particular those based on environmental DNA. 展开更多
关键词 Loop-mediated isothermal amplification DNA extraction-free Direct gene detection Viable cell Extracellular DNA
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Surface ligand engineering on metal nanocatalysts for electrocatalytic CO_(2) reduction
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作者 Qian Guo Tangqi Lan +2 位作者 Ziyun Su Fuqin Zheng Wei Chen 《Materials Reports(Energy)》 2023年第1期78-85,I0003,共9页
Electrocatalytic reduction of CO_(2) into fuels and commodity chemicals has emerged as a potential way to balance the carbon cycle and produce reusable carbon fuels.However,the challenges of the competing reaction of ... Electrocatalytic reduction of CO_(2) into fuels and commodity chemicals has emerged as a potential way to balance the carbon cycle and produce reusable carbon fuels.However,the challenges of the competing reaction of hydrogen evolution reaction,low CO_(2) concentration on the catalyst surface and the diversity of products significantly limit the catalytic activity and selectivity.Hereby,metal nanomaterials,protected by surface sta-bilizing ligands,have been widely studied in the field of CO_(2) reduction due to their structural diversity and outstanding physical and chemical properties.Nevertheless,the surface organic ligands may lower the activity of electrocatalysts,while ligand detachment would cause original structure collapse and selectivity reduction.Therefore,the implementation of strategies based on designing nano-metal catalysts to promote CO_(2) reduction from the perspective of metals and ligands has attracted increasing attention.Herein,we highlight the recent studies on the regulation of surface ligands of metal clusters and metal nanoparticles to promote CO_(2) electro-reduction.Meanwhile,we further summarize the relationship between the surface structure of metal nano-catalysts and the catalytic performance for CO_(2) reduction reaction(CO_(2) RR).This mini review offers an inspiration in remaining challenges and future directions on nano-metal catalysts for electrocatalytic CO_(2) RR. 展开更多
关键词 CO_(2)reduction reaction Cluster NANOPARTICLE ELECTROCATALYSIS Catalyst Carbon neutrality
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Construction of internal electric field to suppress oxygen evolution of Ni-rich cathode materials at a high cutoff voltage
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作者 Youqi Chu Anjie Lai +4 位作者 Qichang Pan Fenghua Zheng Youguo Huang Hongqiang Wang Qingyu Li 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第10期114-125,I0004,共13页
The Nickel-rich layered cathode materials have been considered as promising cathode for lithium-ion batteries(LIBs),which due to it can achieve a high capacity of than 200 mAh g^(-1)under a high cutoff voltage of4.5 V... The Nickel-rich layered cathode materials have been considered as promising cathode for lithium-ion batteries(LIBs),which due to it can achieve a high capacity of than 200 mAh g^(-1)under a high cutoff voltage of4.5 V.However,the nickel-rich layered cathode materials show severely capacity fading at high voltage cycling,induced by the hybrid O anion and cation redox promote O^(α-)(α<2)migration in the crystal lattice under high charge voltage,lead to the instability of the oxygen skeleton and oxygen evolution,promote the phase transition and electrolyte decomposition.Here,Li_(1-x)TMO_(2-y)/Li_(2)SO_(4) hybrid layer is designed by a simple pyrolysis method to enhance the high voltage cycle stability of NCM.In such constructed hybrid layer,the inner spinel structure of Li_(1-x)TMO_(2-y)layer is the electron-rich state,which could form an electron cloud coupling with the NCM with surface oxygen vacancies,while Li_(2)SO_(4) is p-type semiconductors,thus constructing a heterojunction interface of Li_(1-x)TMO_(2-y)//Li_(2)SO_(4) and Li_(1-x)TMO_(2-y)//NCM,thereby generating internal self-built electric fields to inhibit the outward migration of bulk oxygen anions.Moreover,the internal self-built electric fields could not only strengthen the bonding force between the Li_(1-x)TMO_(2-y)/Li_(2)SO_(4) hybrid layer and host NCM material,but also boost the charge transfer.As consequence,the modified NCM materials show excellent electrochemical performance with capacity retention of 97.7%and 90.1%after 200 cycles at 4.3 V and 4.5 V,respectively.This work provides a new idea for the development of high energy density applications of Nickel-rich layered cathode materials. 展开更多
关键词 Ni-rich layered oxide Li_(1-x)TMO_(2-y)/Li_(2)SO_(4) Dual-modified Electrochemical performance
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A New α-Cyclopiazonic Acid Alkaloid Identified from the Weizhou Island Coral-Derived Fungus Aspergillus flavus GXIMD 02503
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作者 WANG Jiamin LI Zhichao +6 位作者 ZHANG Yanting CHEN Chunmei CHEN Weihao GAO Chenghai LIU Yonghong TAN Yanhui LUO Xiaowei 《Journal of Ocean University of China》 SCIE CAS CSCD 2022年第5期1307-1312,共6页
A new oxygenated tricyclic cyclopiazonic acid(CPA)alkaloid,asperorydine Q(1),along with seven known compounds,namely,asperorydines O(2)and J(3),speradine H(4),cyclopiamides A(5)and H(6),saadamysin(7),and pyrazinemetha... A new oxygenated tricyclic cyclopiazonic acid(CPA)alkaloid,asperorydine Q(1),along with seven known compounds,namely,asperorydines O(2)and J(3),speradine H(4),cyclopiamides A(5)and H(6),saadamysin(7),and pyrazinemethanol(8),were isolated from the coral-associated Aspergillus flavus GXIMD 02503.The structures were elucidated by physicochemical properties and comprehensive spectroscopic data analysis.Compounds 1−5 and 7−8 exhibited potent inhibition of lipopolysaccharide(LPS)-induced nuclear factor-κB(NF-κB)with the IC50 values ranging from 6.5 to 21.8μmol L^(−1).In addition,the most potent one,pyrazinemethanol(8),dose-dependently suppressed receptor activator of NF-κB ligand(RANKL)-induced osteoclast differentiation without obvious cytotoxicity in bone marrow macrophages cells(BMMCs),suggesting it is a promising lead compound for the treatment of osteolytic diseases. 展开更多
关键词 coral-derived fungi Aspergillus flavus cyclopiazonic acid NF-κB OSTEOCLASTOGENESIS
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Advances in Toxicity of Ramulus et Uncus Uncariae
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作者 Jingchen JIANG 《Medicinal Plant》 CAS 2022年第1期98-102,共5页
Ramulus et Uncus Uncariae is one of the 31 regional characteristic Chinese medicinal materials identified by Guangxi Zhuang Autonomous Region in 2021,with antihypertensive,antiarrhythmic,anti-cerebral ischemia,sedativ... Ramulus et Uncus Uncariae is one of the 31 regional characteristic Chinese medicinal materials identified by Guangxi Zhuang Autonomous Region in 2021,with antihypertensive,antiarrhythmic,anti-cerebral ischemia,sedative,antithrombotic,anti-tumor and other pharmacological effects,and is neurotoxic and hepatotoxic.In this article,the chemical constituents,pharmacological effects,toxic effects,toxic manifestations in whole animals and mechanism of toxicity of Ramulus et Uncus Uncariae are reviewed. 展开更多
关键词 Ramulus et Uncus Uncariae TOXICITY NEUROTOXICITY HEPATOTOXICITY
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Highly dispersed 1 nm Pt Pd bimetallic clusters for formic acid electrooxidation through a CO-free mechanism
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作者 Zhongying Fang Ziwei Zhang +8 位作者 Shemsu Ligani Fereja Jinhan Guo Xinjie Tong Yue Zheng Rupeng Liu Xiaolong Liang Leting Zhang Zongjun Li Wei Chen 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第3期554-564,I0015,共12页
Direct formic acid fuel cell(DFAFC) is an important research project in clean energy field.However,commercialization of DFAFC is still largely limited by the available catalysts with unsatisfied activity,durability an... Direct formic acid fuel cell(DFAFC) is an important research project in clean energy field.However,commercialization of DFAFC is still largely limited by the available catalysts with unsatisfied activity,durability and cost for formic acid electrooxidation(FAEO).Using Pt-and Pd-based nanoclusters as electrocatalysts is a particularly promising strategy to solve the above problem,but two attendant problems need to be solved firstly.(Ⅰ) The controllable synthesis of practicable and stable sub-2 nm clusters remains challenging.(Ⅱ) The catalyzing mechanism of sub-2 nm metal clusters for FAEO has not yet completely understood.Herein,different from traditional solution synthesis,by designing a novel supporting material containing electron-rich and electron-deficient functional groups,size-and dispersioncontrollable synthesis of ~1 nm PtPd nanoclusters is realized by an electrochemical process.The electrocatalytic properties and reaction mechanism of the PtPd nanoclusters for the FAEO were studied by different electrochemical techniques,in-situ fourier transform infrared(FTIR) spectra and density functional theory(DFT) calculations.The tiny PtPd nanoclusters have much higher catalytic activity and durability than commercial Pt/C,Pd/C and 3.5 nm PtPd nanoparticles.The present study shows that the metalreactant interaction plays a decisive role in determining the catalytic activity and cluster-support interaction plays a decisive role in enhancing the durability of electrocatalyst.The ratio and arrangement of Pt and Pd atoms on the surface of 1 nm PtPd cluster as well as the overall valence state,d-band center and specific surface area make them exhibit different catalytic performance and reaction mechanism from nanoparticle catalysts.In addition,in situ FTIR and DFT calculations showed that on the surface of PtPd clusters,the generation of CO_(2)through trans-COOH intermediate is the most optimal reaction pathway for the FAEO. 展开更多
关键词 CLUSTER Formic acid oxidation ELECTROCATALYSIS In situ FTIR Reaction mechanism
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Targeted isolation of antitubercular cycloheptapeptides and an unusual pyrroloindoline-containing new analog,asperpyrroindotide A,using LC–MS/MS-based molecular networking
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作者 Yi-Qian Han Qun Zhang +8 位作者 Wei-Feng Xu Yang Hai Rong Chao Cui-Fang Wang Xue-Mei Hou Mei-Yan Wei Yu-Cheng Gu Chang-Yun Wang Chang-Lun Shao 《Marine Life Science & Technology》 SCIE CAS CSCD 2023年第1期85-93,共9页
Further insights on the secondary metabolites of a soft coral-derived fungus Aspergillus versicolor under the guidance of MS/MS-based molecular networking led to the isolation of seven known cycloheptapeptides,namely,... Further insights on the secondary metabolites of a soft coral-derived fungus Aspergillus versicolor under the guidance of MS/MS-based molecular networking led to the isolation of seven known cycloheptapeptides,namely,asperversiamides A–C(1–3)and asperheptatides A–D(4–7)and an unusual pyrroloindoline-containing new cycloheptapeptide,asperpyrroindotide A(8).The structure of 8 was elucidated by comprehensive spectroscopic data analysis,and its absolute configuration was determined by advanced Marfey’s method.The semisynthetic transformation of 1 into 8 was successfully achieved and the reaction conditions were optimized.Additionally,a series of new derivatives(10−19)of asperversiamide A(1)was semi-synthesized and their anti-tubercular activities were evaluated against Mycobacterium tuberculosis H37Ra.The preliminary structure−activity relationships revealed that the serine hydroxy groups and the tryptophan residue are important to the activity. 展开更多
关键词 Marine natural product MS/MS-based molecular networking Cycloheptapeptides SEMI-SYNTHESIS Anti-tubercular activity
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Pt_(1)/Ni_(6)Co_(1)layered double hydroxides/N-doped graphene for electrochemical non-enzymatic glucose sensing by synergistic enhancement of single atoms and doping
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作者 Baojun Long Peiyu Cao +9 位作者 Yuanmeng Zhao Qianqian Fu Yan Mo Yueming Zhai Juejing Liu Xingyi Lyu Tao Li Xiaofeng Guo Changsheng Shan Minghua Zeng 《Nano Research》 SCIE EI CSCD 2023年第1期318-324,共7页
The development of novel single-atom catalysts is important for highly efficient electrochemical catalysis and sensing.In this work,a novel Pt single atoms(SAs)supported on Ni_(6)Co_(1)layered double hydroxides/nitrog... The development of novel single-atom catalysts is important for highly efficient electrochemical catalysis and sensing.In this work,a novel Pt single atoms(SAs)supported on Ni_(6)Co_(1)layered double hydroxides/nitrogen-doped graphene(Pt_(1)/Ni_(6)Co_(1)LDHs/NG)was constructed for electrochemical enzyme-free catalysis and sensing towards glucose.The loading of Pt single atoms increases with doping of Co atoms that generate more anchoring sites for Pt SAs.The resulting Pt_(1)/Ni_(6)Co_(1)LDHs/NG exhibits low oxidative potential of 0.440 V with high sensitivity of 273.78μA·mM^(−1)·cm^(−2)toward glucose,which are 85 mV lower and 15 times higher than those of Ni(OH)_(2),respectively.Pt_(1)/Ni_(6)Co_(1)LDHs/NG also shows excellent selectivity and great stability during 5-week testing.Theoretical and experimental results show that the boosted performance of Pt_(1)/Ni_(6)Co_(1)LDHs/NG originates from its stronger binding energy with glucose and the synergistic effect of Pt SAs,Co doping,and NG.This work provides a general strategy of designing highly active SACs for extending their application in electrochemical sensing. 展开更多
关键词 single-atom catalysts electrochemical sensor layered double hydroxides nitrogen-doped graphene synergistic effect
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Simultaneous Bulk-and Surface-initiated Living Polymerization Studied with a Heterogeneous Stochastic Reaction Model
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作者 Jia-Shu Ma Zhi-Ning Huang +4 位作者 Jia-Hao Li Bang-Ping Jiang Yan-Da Liao Shi-Chen Ji Xing-Can Shen 《Chinese Journal of Polymer Science》 SCIE EI CAS CSCD 2024年第3期364-372,I0008,共10页
To better characterize the properties of surface-initiated polymers, simultaneous bulk-and surface-initiated polymerizations are usually carried out by assuming that the properties of the surface-initiated polymers re... To better characterize the properties of surface-initiated polymers, simultaneous bulk-and surface-initiated polymerizations are usually carried out by assuming that the properties of the surface-initiated polymers resemble those of the bulk-initiated polymers. Through a Monte Carlo simulation using a heterogeneous stochastic reaction model, it was discovered that the bulk-initiated polymers exhibit a higher molecular weight and a lower dispersity than the corresponding surface-initiated polymers, which indicates that the equivalent assumption is invalid. Furthermore, the molecular weight distributions of the two types of polymers are also different, suggesting different polymerization mechanisms. The results can be simply explained by the heterogeneous distributions of reactants in the system. This study is helpful to better understand surface-initiated polymerization. 展开更多
关键词 Surface-initiated polymerization Polymer brush Stochastic reaction model Heterogeneous polymerization Simultaneous polymerization
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Photocatalytic vinyl radical-mediated multicomponent 1,4-/1,8-carboimination across alkynes and olefins/(hetero)arenes
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作者 Shan-Shan Li Yu-Shi Jiang +5 位作者 Xue-Ling Luo Xuming Ran Yuqiang Li Dong Wu Cheng-Xue Pan Peng-Ju Xia 《Science China Chemistry》 SCIE EI CAS CSCD 2024年第2期558-567,共10页
We developed a highly selective and efficient multicomponent transformation by utilizing alkynes and olefins/(hetero)arenes through photoinduced energy-transfer catalysis.The reaction involves the formation of three d... We developed a highly selective and efficient multicomponent transformation by utilizing alkynes and olefins/(hetero)arenes through photoinduced energy-transfer catalysis.The reaction involves the formation of three distinct chemical bonds,namely C(sp~3)–C(sp~2),C(sp~2)–C(sp~3),and C(sp~3)–N,in a single coordinated manner.The strategy used a vinyl radical-mediated radical relay approach under mild conditions,exhibiting a broad substrate scope(>70 examples),excellent functional-group tolerance,and remarkable regio-and anti-stereoselectivity.Through the utilization of a combination of experimental techniques and density functional theory(DFT),we delved deeper into the mechanistic intricacies of this distinctive system.Results revealed that the selective radical addition to electron-deficient alkynes,rather than olefins,was governed by the inherent reactivity of alkyl radicals.This discovery presented a highly effective approach for the synthesis of stereodefined multisubstituted alkenes. 展开更多
关键词 alkyne-olefin coupling DFT studies regio-and anti-stereoselectivity multisubstituted alkenes
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通过铝电解的电解渗硼制备可湿性的TiB2-TiB/Ti阴极(英文) 被引量:3
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作者 黄有国 王益 +2 位作者 张晓辉 王红强 李庆余 《Journal of Central South University》 SCIE EI CAS CSCD 2019年第10期2681-2687,共7页
针对铝电解工业现有技术中TiB2涂层阴极寿命短、强度低的问题,采用密度和热膨胀率相近的三种材料的电解渗硼方法,合成了TiB2涂层和TiB晶须在金属Ti基体中的TiB2-TiB/Ti梯度复合材料。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和X射线能... 针对铝电解工业现有技术中TiB2涂层阴极寿命短、强度低的问题,采用密度和热膨胀率相近的三种材料的电解渗硼方法,合成了TiB2涂层和TiB晶须在金属Ti基体中的TiB2-TiB/Ti梯度复合材料。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和X射线能谱(EDS)等分析手段测定了材料的相组成和截面形貌。结果表明,表面连续涂覆厚度为8~10μm的均匀TiB2层,而与TiB2层连接的TiB晶须分散嵌入基体中。TiB晶须的最大长度约为220μm,通过B4C的强烈还原,TiB2和TiB的生长速率得到提高,这种复合材料的新型梯度设计有助于延长TiB2阴极在铝电解中的寿命和提高其强度。 展开更多
关键词 铝电解 电解渗硼 二硼化钛 梯度材料
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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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Tracking the multiple-step formation of an iron(Ⅲ) complex and its application in photodynamic therapy for breast cancer 被引量:2
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作者 Zhong-Hong Zhu Qian Hu +5 位作者 Hui-Ling Pan Yuexing Zhang Haibing Xu Mohamedally Kurmoo Jin Huang Ming-Hua Zeng 《Science China Chemistry》 SCIE EI CAS CSCD 2019年第6期719-726,共8页
A tandem reaction of pyridin-2-ylmethanamine(L1′) with 8-hydroxyquinoline-2-carbaldehyde(HL1) assisted by FeCl_3 was observed to give the new nitrogen heterocycle HL3(HL3=2-(imidazo[1,5-a]pyridin-3-yl)quinolin-8-ol) ... A tandem reaction of pyridin-2-ylmethanamine(L1′) with 8-hydroxyquinoline-2-carbaldehyde(HL1) assisted by FeCl_3 was observed to give the new nitrogen heterocycle HL3(HL3=2-(imidazo[1,5-a]pyridin-3-yl)quinolin-8-ol) as its Fe(Ⅲ) complex,[Fe(L3)Cl_2](Fe1). Electrospray ionization mass spectrometry(ESI-MS) reveals its formation involves three steps:(1) coordination of both HL1 and L1′ to Fe,(2) aldehyde-amine coupling, and(3) ring closure. The results of electronic absorption spectroscopy, cyclic voltammetry, and density functional theory(DFT) calculations show the proximity of the optical transition energy to that of the excitation of ~3O_2 to ~1O_2, which prompted us to explore its application as a photosensitizer for photodynamic therapy(PDT). Photo-toxicity studies show that Fe1 exhibits the highest anti-proliferation efficiency in human breast cancer MDA-MB-231 cells under light irradiation. Moreover, studies with orthotopic models of breast cancer further expounded the anti-tumor activity of Fe1 with no significant toxicity to other organs and low retention in the body. 展开更多
关键词 TANDEM formation iron(Ⅲ) COMPLEX DFT calculation photodynamic therapy BREAST cancer
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