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电催化硝酸盐还原合成氨电势相关性的计算见解 被引量:1
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作者 井会娟 龙军 +2 位作者 李欢 傅笑言 肖建平 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2023年第5期205-213,共9页
人类活动和工业生产导致全球氮循环严重失衡,对生命系统的健康造成了一定威胁.因此,开发高效、环保的NO_(x)脱除技术具有重要意义.其中,电化学硝酸盐还原反应(eNO_(3)RR)是反向人工氮循环的重要组成部分,同时也被认为是一种非集成式合成... 人类活动和工业生产导致全球氮循环严重失衡,对生命系统的健康造成了一定威胁.因此,开发高效、环保的NO_(x)脱除技术具有重要意义.其中,电化学硝酸盐还原反应(eNO_(3)RR)是反向人工氮循环的重要组成部分,同时也被认为是一种非集成式合成氨(NH_(3))的可行途径.NH_(3)是生产肥料的重要原料之一,传统哈伯法(H-B)合成氨能耗高,且会排放大量温室气体CO_(2),由可再生电力驱动的电催化氮气还原(eNRR)合成氨被认为是一条更环保和可持续的路线.目前,一些研究表明电催化硝酸盐还原具有比eNRR更高的产氨活性和选择性.然而,一个主要的挑战是在低过电位下产物的选择性,即亚硝酸盐(HNO_(2))和NH_(3)之间的竞争.本文选择了六个具有MN_(4)单元的石墨烯负载的过渡金属单原子催化剂(SACs)作为模型,通过密度泛函理论(DFT)计算研究eNO_(3)RR机理.采用本课题组开发的反应相图分析(RPD)方法从全局热力学最优的角度构建了六个MN_(4)催化剂的二维准活性和选择性相图,其中FeN_(4)催化剂展示出较高的准活性和适当的选择性.DFT计算结果表明,产生HNO_(2)和NH_(3)的最优路径共享一个关键中间体(NO_(2)*),其吸附结构和在后续转化中的偏好决定了产物选择性.结合电势相关性动力学势垒计算和微观动力学模拟结果,动力学研究表明,理论上两种产物不同电压下的法拉第效率(FE)趋势会发生反转,与FeN_(4)催化剂上实验测得的HNO_(2)和NH_(3)的FE趋势和反转电压吻合,这归因于两个重要的基元步骤(R4:NO_(2)*-→cisHNO_(2)*和R7:NO_(2)*→HNO_(2)+*)具有不同的电荷转移系数(β),前者(R4)具有更大的电荷转移系数,使得生成NH_(3)的动力学能垒随电压的降低而下降得更快,这就把NH_(3)从低过电势下的低选择性到高过电势下的高选择性归因到动力学问题,较好地理解了两种产物的FE发生发转的原因.最后,从电子结构方面对R4和R7两个关键基元步骤的初态和过渡态进行了电子局域化函数和晶体轨道哈密顿布居分析.综上,理论计算的机理研究很好地解释实验观察的结果,其机理方面的理解对于将来理性设计高效的eNO_(3)RR合成NH_(3)催化剂具有一定的指导意义. 展开更多
关键词 电催化合成氨 密度泛函理论计算 反应相图分析 活性 选择性
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Optimal set integer programming algorithm for multiple maneuvering targets tracking in clutter 被引量:1
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作者 xiaoyan fu Yingmin Jia Xiaohe Liu 《Journal of Systems Engineering and Electronics》 SCIE EI CSCD 2013年第4期555-563,共9页
The aim of this paper is to solve the problems of multitarget tracking in clutter. Firstly, the data association of measurement-to-target is formulated as an integer programming problem. Through using the linear progr... The aim of this paper is to solve the problems of multitarget tracking in clutter. Firstly, the data association of measurement-to-target is formulated as an integer programming problem. Through using the linear programming (LP) based branchand-bound method and adjusting the constraint conditions, an optimal set integer programming (OSIP) algorithm is then proposed for tracking multiple non-maneuvering targets in clutter. For the case of maneuvering targets, this paper introduces the OSIP algorithm into the filtering step of the interacting multiple model (IMM) algorithm resulting in the IMM based on OSIP algorithm. Extensive Monte Carlo simulations show that the presented algorithms can obtain superior estimations even in the case of high density noises. 展开更多
关键词 data association target tracking integer programming clutter.
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Theoretical understanding of electrocatalysis beyond thermodynamic analysis
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作者 Huan Li Chenxi Guo +2 位作者 Jun Long xiaoyan fu Jianping Xiao 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2022年第11期2746-2756,共11页
As the green and sustainable development of human society highly relies on renewable energy,it has been recognized that electrocatalysis is a key technology to this end.High efficient ways of carbon-neutralization(eCO... As the green and sustainable development of human society highly relies on renewable energy,it has been recognized that electrocatalysis is a key technology to this end.High efficient ways of carbon-neutralization(eCO_(2)RR),reverse artificial nitrogen cycle(RANC),and oxygen chemistry(OER and ORR)all can be driven by electrocatalysis.Advanced theoretical study is an important means to fundamentally understanding electrocatalytic reactions.Herein,we review a few significant issues in theoretical electrocatalysis.First,electrochemical barriers and potential effects are essential for a more accurate description of reaction mechanism and activity.Meanwhile,consideration of competitive reaction path is also one of the important aspects,as novel insights and anomalous volcano trend can be obtained.Finally,a microenvironment exerted by confined space can tune the capacitance of electrochemical interface and(electro)chemical potential of proton,resulting in a possibility to improve reaction activity,which opens a new avenue for design of catalyst. 展开更多
关键词 ELECTROCATALYSIS Capacitor model Potential-dependent barrier Anomalous volcano CONFINEMENT
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河套盆地临河坳陷不同构造带原油地球化学特征及来源 被引量:2
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作者 付晓燕 路俊刚 +3 位作者 师玉雷 周然然 袁满 陈世加 《天然气地球科学》 CAS CSCD 北大核心 2024年第1期176-191,共16页
近年来河套盆地临河坳陷不断获得勘探突破,但原油地球化学特征和油源的研究集中在南部的吉兰泰构造带,有关中部纳林湖和北部兴隆构造带仍缺乏研究。开展岩石热解、TOC和饱和烃色谱色质实验分析,结果表明:(1)研究区原油形成于强还原咸水... 近年来河套盆地临河坳陷不断获得勘探突破,但原油地球化学特征和油源的研究集中在南部的吉兰泰构造带,有关中部纳林湖和北部兴隆构造带仍缺乏研究。开展岩石热解、TOC和饱和烃色谱色质实验分析,结果表明:(1)研究区原油形成于强还原咸水环境,母源从南向北呈由水生和藻类为主到以陆生生物为主的变化;(2)吉兰泰构造带的原油均来自本地固阳组烃源岩,兴隆构造带原油具有“自生自储”特征,以本地同层烃源岩为主,纳林湖构造带原油具有“混源”特征;(3)成熟度、母源的变化和强还原环境中富硫生油母质的存在导致原油从低硫中黏度轻质油到高硫高黏度重质油的物性变化。原油和烃源岩的特征及油源关系的确定可以为生烃机理和资源量等进一步深入研究提供指导,也有利于油气勘探部署。 展开更多
关键词 原油地球化学特征 油源对比 烃源岩 临河坳陷 河套盆地
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A novel long persistent luminescent material CaGeO_(3):Tb^(3+)with photo-stimulation properties
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作者 Wei Meng xiaoyan fu +7 位作者 Tongyan Lin Zewen Liu Naihui Chen Jiaxu Zhang Runyao Liu Rujun Yang Long Chen Hongwu Zhang 《Journal of Rare Earths》 SCIE EI CAS CSCD 2024年第7期1233-1239,I0002,共8页
A novel green long afterglow material CaGeO_(3):Tb^(3+)was synthesized by high temperature solid phase method.According to the experimental results,CaGeO_(3):Tb^(3+)is a green long persistent luminescent(LPL)material ... A novel green long afterglow material CaGeO_(3):Tb^(3+)was synthesized by high temperature solid phase method.According to the experimental results,CaGeO_(3):Tb^(3+)is a green long persistent luminescent(LPL)material with excellent performance.CaGeO_(3):Tb^(3+)shows LPL emission peak at 442,490.9,548.7,588.5 and 623.8 nm,corresponding to ^(5)D_(3) to^(7)F_(4)and^(5)D_(4)to^(7)F_(J)(J=6,5,4,3)transitions of Tb^(3+).Its CIE coordinates are(0.27,0.50),indicating that the afterglow emission is close to the light of green region.In addition,after the excitation source is turned off,the afterglow time is longer than 90 min.After an interval of 7 h,the photo-stimulation luminescence(PSL)can be observed by using 980 nm laser cyclic excitation.The thermoluminescence(ThL)results show that there are three types of traps in the material and their depths are 0.666,0.774 and 0.892 eV respectively,which are caused by the doping of Tb^(3+).All the results show that CaGeO_(3):Tb^(3+)is an excellent long afterglow luminescent material. 展开更多
关键词 Long persistent luminescence Photo-stimulation TRAP CaGeO_(3):Tb^(3+) Rare earths
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Long afterglow yellow luminescence from Pr^(3+) doped SrSc_(2)O_(4) 被引量:2
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作者 xiaoyan fu Shenghui Zheng +2 位作者 Yanfeng Meng Wenzhi Sun Hongwu Zhang 《Journal of Rare Earths》 SCIE EI CAS CSCD 2022年第4期567-571,I0003,共6页
A yellow emitting long afterglow luminescence material SrSc_(2)O_(4):Pr^(3+)was successfully prepared by solid state reaction method.SrSc_(2)O_(4):Pr^(3+)phosphor shows a long afterglow luminescence peak at about 495,... A yellow emitting long afterglow luminescence material SrSc_(2)O_(4):Pr^(3+)was successfully prepared by solid state reaction method.SrSc_(2)O_(4):Pr^(3+)phosphor shows a long afterglow luminescence peak at about 495,545,621,630 and 657 nm,respectively,corresponding to the f–f transitions of Pr^(3+).The afterglow chromaticity coordinates of SrSc_(2)O_(4):1 at%Pr^(3+)were calculated to be(0.35,0.41),indicating that the afterglow emission is close to the light of yellow region.And,the afterglow luminescence of the optimal sample doped by 1 at%Pr^(3+)can persist for over 3 h.The thermoluminescence results suggest that there are three types of traps with depth of 0.61,0.69 and 0.78 eV exiting for all the samples,which are produced by the addition of Pr^(3+)ions.The trap density of SrSc_(2)O_(4):1 at%Pr^(3+)is the maximum when the incorporation of Pr^(3+)ions reaches 1 at%,which thus results in the longest afterglow luminescence.All the results indicate that SrSc_(2)O_(4):Pr^(3+)can be a potential candidate of novel long afterglow phosphors. 展开更多
关键词 Long afterglow luminescence SrSc_(2)O_(4):Pr^(3+) TRAPS Long afterglow luminescent mechanism Rare earths
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