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通过调节反应物气体吸附电子转移行为实现热驱动ZnO光催化CO还原和H_(2)氧化反应 被引量:1
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作者 王中明 王洪 +4 位作者 王笑笑 陈旬 于岩 戴文新 付贤智 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2021年第9期1538-1552,共15页
传统热催化和低温光催化体系在实际应用中都存在技术缺陷.近些年,人们通过将光和热耦合,克服它们各自的局限性,开创了光热协同催化新领域.目前已在CO减排、CO甲烷化和VOCs降解等诸多应用领域得到应用.当然,随着光热催化的发展,研究者也... 传统热催化和低温光催化体系在实际应用中都存在技术缺陷.近些年,人们通过将光和热耦合,克服它们各自的局限性,开创了光热协同催化新领域.目前已在CO减排、CO甲烷化和VOCs降解等诸多应用领域得到应用.当然,随着光热催化的发展,研究者也一直在思考光热协同的内在作用机理.目前大多数的机理分析都是从材料本身出发,通过研究表面反应、光吸收或金属与载体之间的电子转移行为来探讨光热协同效应.然而,表面反应只是多相光催化反应的其中一个步骤,此外还包括反应物的扩散和吸附及产物的脱附和扩散,其中反应物的吸附过程因其多变的吸附行为可能在整个反应过程中起着重要的作用.光热协同可能通过作用于气体吸附过程来调节反应的选择性和活性,但到目前为止,两者之间的内在联系尚不清楚.所以,从反应物气体吸附行为(尤其是吸附电子转移行为)的角度深入研究光热协同效应具有重要意义.本文在光催化CO还原和H_(2)氧化体系中引入一定的热条件,希望通过热驱动效应影响H_(2)/CO吸附时的电子转移行为,进而改变反应行为.为简化实验附加条件,选用常见的具有合适带隙宽度以及良好光吸收的ZnO作为研究材料,通过水热法合成了在(100)晶面具有氧空位(V_(Os))的ZnO样品,引入气敏传感系统检测不同光热条件下的H_(2)/CO气体吸附电子转移行为,并结合多种原位手段从物质结构和气体吸附两个角度出发,分析光热条件下气体吸附行为变化的机理.与我们预测一致,在紫外光照下随着温度的升高,光热协同作用于(002)晶面,原位生长了锌空位(V_(Zn)s),为H_(2)分子提供吸附位点.H_(2)从Vos位点吸附转移到V_(Zn)s上,并导致H_(2)(ads)从得电子转变为失电子行为(形成有利于H_(2)氧化的定向吸附),从而发生H_(2)氧化反应.对于同样吸附在高表面能(002)晶面上的CO分子来说,光热协同效应通过抬升材料费米能级来改变其电子转移行为,CO(ads)由失电子转变为得电子行为(形成有利于CO还原的定向吸附),并进一步被失去电子的H_(2)(ads)还原.此外,还发现CO或H_(2)的光催化氧化反应的发生只依赖于CO或H_(2)单分子的定向活化(不考虑O2的吸附和活化),表明其归属于E-R反应过程.而CO的光催化还原反应需要同时满足CO和H_(2)双分子的定向活化,可能归属于L-H反应过程.综上,本文研究结果表明,光热协同内在作用可能是通过改变ZnO材料结构,调节反应物吸附动力学中的电子转移行为,从而引起反应物的定向活化,进而改变反应选择性. 展开更多
关键词 光热协同 电子转移行为 吸附动力学控制 原位表征 费米能级
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氧空位修饰的暴露TiO_(2){001}的Ru/TiO_(2)增强光热协同CO_(2)甲烷化活性和稳定性 被引量:1
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作者 王可 何仕辉 +3 位作者 林云志 陈旬 戴文新 付贤智 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2022年第2期391-402,共12页
利用太阳能在温和条件下实现CO_(2)还原反应,不仅可以缓解过度消耗化石能源造成的能源危机,还可以改善诸如温室效应和海洋酸化等环境问题.光热协同催化可以有效降低催化反应温度,具有较大的应用前景.本文利用Ru与暴露TiO_(2){001}晶面的... 利用太阳能在温和条件下实现CO_(2)还原反应,不仅可以缓解过度消耗化石能源造成的能源危机,还可以改善诸如温室效应和海洋酸化等环境问题.光热协同催化可以有效降低催化反应温度,具有较大的应用前景.本文利用Ru与暴露TiO_(2){001}晶面的TiO_(2)载体产生的金属-载体相互作用,经过高温氢气煅烧后,获得具有丰富表面氧空位的Ru/TiO_(2)催化剂.活性测试结果表明,具有丰富表面氧空位的Ru/TiO_(2)表现出优异的CO_(2)甲烷化活性,反应过程中甲烷的TOF值在300°C时可以达到22 h-1,但该催化剂却表现出较差的稳定性,在反应10小时后,甲烷的TOF值逐渐降低到19 h-1.将紫外光引入到Ru/TiO_(2)热催化甲烷化体系中,甲烷的TOF值增加到30 h-1,且兼具高稳定性.热催化反应过程中逐渐消失的表面氧空位和部分氧化的Ru是活性降低的主要原因.在光热协同反应中,光生电子的产生稳定了Ru表面的电子密度,同时也再生了催化剂上表面氧空位,这有效地提高了反应的活性和稳定性.程序升温原位红外和X射线光电子能谱实验结果表明,当催化剂表面具有丰富的表面氧空位时,CO_(2)可以有效地在Ru纳米粒子上解离成CO中间体,随后吸附在Ru上的CO中间体解离成表面碳物种,并加氢产生甲烷.在热催化反应过程中,Ru纳米粒子逐渐被氧化成Ru Ox物种,且表面氧空位被CO中间物种覆盖,降低了催化反应的稳定性.当紫外光引入到上述反应中,催化剂的表面氧空位可有效提高光生载流子的分离能力.TiO_(2)载体产生的光电子转移至Ru表面,稳定了金属Ru纳米粒子的价态.另外,载体产生的光生空穴加速了H_(2)质子化,提高了催化剂对氢气的活化迁移能力,促进了CO中间体的加氢甲烷化反应,进而再生表面氧空位.因此在紫外光照下,兼顾提高了热催化CO_(2)甲烷化的活性和稳定性.值得注意的是,当Ru负载于暴露少量TiO_(2){001}晶面的TiO_(2)载体上时,产生了强金属-载体相互作用并抑制了H_(2)在催化剂上的吸附活化,不利于产生表面氧空位.因此暴露少量TiO_(2){001}晶面的Ru/TiO_(2)催化剂也不利于光生载流的产生和分离,这导致热催化或光热协同催化反应活性较低. 展开更多
关键词 光热协同催化CO_(2)还原 氧空位 Ru/TiO_(2) 金属-载体相互作用
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Density functional theory study of CO catalytic oxidation on Co_2B_2/TiO_2(110) surface 被引量:2
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作者 Qingsong Zeng Wenkai Chen +2 位作者 Yongfan Zhang wenxin dai Xin Guo 《Journal of Natural Gas Chemistry》 EI CAS CSCD 2010年第3期300-306,共7页
Titanium dioxide with CoB amorphous alloys nanoparticles deposited on the surface is known to exhibit higher catalytic activity than the CoB amorphous.A study of the structure of such system is necessary to understand... Titanium dioxide with CoB amorphous alloys nanoparticles deposited on the surface is known to exhibit higher catalytic activity than the CoB amorphous.A study of the structure of such system is necessary to understand this effect.A quantum chemical study of Co2B2 on the TiO2(110) surface was studied using periodic slab model within the framework of density functional theory(DFT).The results of geometry optimization indicated that the most stable model of adsorption was Co2B2 cluster adsorbed on the hollow site of TiO2 .The adsorption energy calculated for Co2B2 on the hollow site was 439.3 kJ/mol.The adsorption of CO and O2 was further studied and the results indicated that CO and O2 are preferred to adsorb on the Co2 site.Co-adsorption of CO and O2 shows that Co2B2 /TiO2 is a good catalyst for the oxidation of CO to carbon dioxide in the presence of oxygen. 展开更多
关键词 density functional theory Co-B alloy CO TIO2 O2
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Inhibitory Effects of AURKB Gene on Apoptosis and Cancer Cell Growth in HCT 116 Cells
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作者 Wangyuan ZENG wenxin dai 《Medicinal Plant》 CAS 2019年第6期77-86,共10页
[Objectives]To explore the inhibitory effect of AURKB gene in apoptosis and cancer cell growth in HCT 116 cells.[Methods]The in vitro cytology studies were carried out to confirm the expression of the AURKB gene in HC... [Objectives]To explore the inhibitory effect of AURKB gene in apoptosis and cancer cell growth in HCT 116 cells.[Methods]The in vitro cytology studies were carried out to confirm the expression of the AURKB gene in HCT 116 cells and make clear its role in cell activity,cell cycle control and apoptosis,and investigate the effect of AURKB gene in colorectal cancer(CRC).Quantitative reverse transcription/polymerase chain reaction(PCR)analysis and immunofluorescence(IF)staining for markers of AURKB gene were used to examine the effect of AURKB on HCT 116.The AURKB gene target was examined using western blot analysis.In addition,inhibition of AURKB expression was examined using RNA interference(RNAi)on HCT 116 cells in vitro.[Results]HCT 116 cells infected with AURKB shRNA virus suppressed expression of AURKB in vitro.AURKB gene knockdown HCT 116 cells showed reducing cell apoptosis in vitro.Finally,it demonstrated that AURKB function can induce apoptosis of HCT cells.[Conclusions]AURKB is a key regulator of colorectal cancer.AURKs are potential novel molecular targets for the prevention of cancer cell proliferation. 展开更多
关键词 COLORECTAL cancer AURKB APOPTOSIS Cell growth
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SARS-CoV-2 spike host cell surface exposure promoted by a COPI sorting inhibitor
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作者 Yiqun Li Mingrui Yang +9 位作者 Yanan Nan Jiaming Wang Sanjiao Wang Dongxiao Cui Jiajian Guo Pengfei He wenxin dai Shuqi Zhou Yue Zhang Wenfu Ma 《Acta Pharmaceutica Sinica B》 SCIE CAS CSCD 2023年第7期3043-3053,共11页
Via an insufficient coat protein complex I(COPI)retrieval signal,the majority of SARSCo V-2 spike(S)is resident in host early secretory organelles and a tiny amount is leaked out in cell surface.Only surface-exposed S... Via an insufficient coat protein complex I(COPI)retrieval signal,the majority of SARSCo V-2 spike(S)is resident in host early secretory organelles and a tiny amount is leaked out in cell surface.Only surface-exposed S can be recognized by B cell receptor(BCR)or anti-S therapeutic monoclonal antibodies(m Abs)that is the trigger step for B cell activation after S m RNA vaccination or infected cell clearance by S m Abs.Now,a drug strategy to promote S host surface exposure is absent.Here,we first combined structural and biochemical analysis to characterize S COPI sorting signals.A potent S COPI sorting inhibitor was then invented,evidently capable of promoting S surface exposure and facilitating infected cell clearance by S antibody-dependent cellular cytotoxicity(ADCC).Importantly,with the inhibitor as a probe,we revealed Omicron BA.1 S is less cell surface exposed than prototypes because of a constellation of S folding mutations,possibly corresponding to its ER chaperone association.Our findings not only suggest COPI is a druggable target against COVID-19,but also highlight SARS-Co V-2 evolution mechanism driven by S folding and trafficking mutations. 展开更多
关键词 COPI inhibitor SARS-CoV-2 spike Spike sorting motifs Protein folding Protein trafficking Anti-COVID-19 Omicron variants and drug discovery
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High value-added fluorescence upconversion agents-assisted nanosemiconductors for efficient wide spectral response photocatalysis:Exerting energy transfer effect and applications 被引量:1
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作者 Kailian Zhang Man Zhou +7 位作者 Changlin Yu Xiaoxiao Li Kai Yang Shi Yang wenxin dai Weiya Huang Qizhe Fan Lihua Zhu 《Journal of Rare Earths》 SCIE EI CAS CSCD 2021年第3期243-260,I0001,共19页
The design of the photocatalytic materials has made a great of remarkable progress in the area of the enhancement photocatalytic activity,but there are still lots of problems such as wide band gap,low utilization of s... The design of the photocatalytic materials has made a great of remarkable progress in the area of the enhancement photocatalytic activity,but there are still lots of problems such as wide band gap,low utilization of sunlight,low quantum efficiency and poor stability,which further limit the extensive practical applications.Thus,it is a hot research topic and key scientific problem to be solved that how to design and prepare the catalysts,which can respond to visible and near-infrared light in sunlight.Inspired by efficient nonlinear optical upconversion materials,upconversion-based nanocomposites can indirectly broaden the absorption ranges of semiconductors by co nverting the captured long-band visible and near-infrared incident light into high-energy short-band visible or ultraviolet light,which can be adopted as the promising candidate in wide-spectral-light-activating photocatalytic materials coupling with conventional semiconductors.According to our recent works and literature reports,recent review summarizes the research progress of photocatalytic materials with upconversion effect on photolysis of water for hydrogen production,degradation of organic and inorganic pollutants,reduction of CO_(2) and photodynamic therapy.The prepared nanocomposites can suppress the recombination of electrons and holes,and greatly improve the photocatalytic efficiency by the synergistic effect.It maybe stimulates a great interest in rational design and preparation of efficient full-spectrum photocatalytic systems and their wide application in solar energy conversion. 展开更多
关键词 Fluorescence upconversion Hydrogen production PHOTOCATALYSIS Treatment of pollutants Photodynamic therapy Rare earths
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Coupling a titanium dioxide based heterostructure photoanode with electroless-deposited nickel-phosphorus alloy coating on magnesium alloy for enhanced corrosion protection
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作者 Yue Liu Feng Peng +5 位作者 Guang-Ling Yang Zhi-Hui Xie wenxin dai Yuejun Ouyang Liang Wu Chuan-Jian Zhong 《Journal of Materials Science & Technology》 SCIE EI CAS CSCD 2022年第31期252-265,共14页
The utilization of photoelectrochemical cathodic protection(PECCP)enables an indirect corrosion pro-tection of metals with low self-corrosion potential by introducing a metallic nickel interlayer.However,the ability t... The utilization of photoelectrochemical cathodic protection(PECCP)enables an indirect corrosion pro-tection of metals with low self-corrosion potential by introducing a metallic nickel interlayer.However,the ability to enhance the PECCP efficiency remains challenging because of the inherent property of the semiconductor.Herein,this ability is demonstrated by coupling a covalent organic framework(TpBD)dec-orated TiO 2 photoanode(TiO 2/TpBD)with nickel coating on magnesium alloy for an effective corrosion protection.The composite photoanode showed direct PECCP for the nickel interlayer and indirect corro-sion protection of the magnesium alloy.The composite structure of the nanotube array and the covalent organic framework for the photoanode were confirmed by field emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).The en-hanced photoelectrochemical conversion capability and PECCP performance of the nickel-coated Mg alloy were evidenced by the results from electrochemical and photoelectrochemical measurements including Mott-Schottky curves,photoinduced potential variations,and electrochemical impedance spectroscopy(EIS).Lastly,a corrosion protection mechanism is proposed,where the enhanced PECCP efficiency is at-tributed to the formation of a direct Z-scheme heterojunction,which is substantiated by the results from valence band(VB)XPS and electron spin resonance characterizations. 展开更多
关键词 Magnesium alloy Corrosion Nickel coating ELECTROLESS Photoelectrochemical cathodic protection
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