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解析光电化学氮还原合成氨中局域电子结构和合金化的协同效应
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作者 郑建云 吕艳红 +4 位作者 黄爱彬 Bernt Johannessen 曹逊 蒋三平 王双印 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2023年第2期141-151,共11页
氨是氮肥等工业的主要原料,因此氨产量居各种化工产品的首位.目前,90%以上的氨通过传统Haber-Bosch法制得,但该反应需要在高温高压下进行,消耗大量能源,同时排放大量CO_(2).基于此,科研人员致力于寻求一种绿色、高效的合成氨替代方法.其... 氨是氮肥等工业的主要原料,因此氨产量居各种化工产品的首位.目前,90%以上的氨通过传统Haber-Bosch法制得,但该反应需要在高温高压下进行,消耗大量能源,同时排放大量CO_(2).基于此,科研人员致力于寻求一种绿色、高效的合成氨替代方法.其中,利用太阳能,通过光电化学氮还原合成氨是最有潜力和竞争力的方法之一,该方法也为有效利用太阳能提供了新途径.目前,虽然光电化学氮还原研究取得了一定进展,但是氨产率和氮转换效率低限制了其经济可行性.这主要归因于四个方面:(1)牢固的氮氮三键使得氮气难以活化;(2)复杂的多步和多电子反应使得动力学迟缓;(3)析氢竞争反应降低了太阳能-氨的转换效率;(4)氮气在水溶液中的溶解度低导致吸附在光电阴极表面的氮气较少.为解决上述问题,本文通过溅射法在B掺杂的p型(100)晶向硅片上共沉积Au,Co和Pd,然后在600℃下和空气中快速退火,制得由助催化剂/保护层/光吸收层组成的层级硅基光电阴极,并用于氮还原合成氨.成分和结构表征结果表明,层级硅基光电阴极由p型硅光吸收层、二氧化硅保护薄层和AuCoPd合金纳米颗粒助催化剂组成,该电极可表示为AuCoPd-CoOx/SiO_(2)/Si,简称ACP电阴极.角分辨X射线光电子能谱和同步辐射X射线吸收光谱结果表明,形成了局域电子结构AuCoPd合金纳米颗粒,并可分析出Au离子和Pd离子在纳米颗粒上的比例和分布.变压光电化学实验结果表明,ACP光电阴极表现出较好的氮还原合成氨性能,在3 MPa下氨产率达到22.2±0.4μg·h^(-1)·cm^(-2),法拉第效率达到22.9%.同时,ACP光电阴极的光电化学氮还原行为遵循勒夏特列(化学平衡移动)原理:随着反应压强增加,氨产率、法拉第效率和起始光电压均随之增大.原位X射线光电子能谱和原位同步辐射X射线吸收光谱结果表明,Au离子和Pd离子为氮还原反应的活性位点,为氮气活化及加氢提供反应场所;同时,揭示了邻近的Pd元素为Au物种上活化的氮气提供了活性质子,促进了氮还原合成氨反应进程.综上,本文为设计高效且稳定的光电阴极并应用于光电化学氮还原反应提供一定的参考. 展开更多
关键词 光电化学氮固定 电子局域结构 合金化 加压反应 协同机理
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Multi-technique integration separation frameworks after steam reforming for coal-based hydrogen generation 被引量:2
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作者 Xuehua Ruan Wenbo Huo +6 位作者 Jiaming Wang Minggang Guo Wenji Zheng Yun Zou aibin huang Jianxiang Shou Gaohong He 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2021年第7期163-172,共10页
Coal-based H2 generation has abruptly increased in recent years.The PSA-VPSA-SC process is the matured and standard framework for H2 purification and CO_(2) capture in many existing plants,including normal and vacuum ... Coal-based H2 generation has abruptly increased in recent years.The PSA-VPSA-SC process is the matured and standard framework for H2 purification and CO_(2) capture in many existing plants,including normal and vacuum pressure swing adsorption units in series(PSA-VPSA),and shallow condensation unit(SC).However,this standard process is frequently subjected to low H2 recovery ratio and high purification cost.In this work,H2-selective and C02-selective membrane units,i.e.,HM and CO_(2) M,are attempted to support the standard process and ameliorate constraints.In the beginning,HM unit is arranged after VPSA to enhance H2 recovery from the decarbonized stream,i.e.,the PSA-VPSA-SC/HM process.As a result,H2 recovery ratio can be enhanced significantly from 83%to 98%.In the following,VPSA is replaced with CO_(2) M unit to reduce investment and operation cost,i.e.,the PSA-CO_(2) M-SC/HM process.Accordingly,the specific purification cost is diminished from 33.46 to 32.02 USD·(103 m^(3) H_(2))-1,saved by 4.3%,meanwhile the construction cost is falling back and just a little higher than that for the standard process.In the end,another CO_(2) M unit is launched before PSA,i.e.,the CO_(2) M-PSA-CO_(2) M-SC/HM process,which could unbundle CO_(2) enrichment partially from H2 purification,and then save more investment and operation cost.In comparison with the standard process,this ultimate retrofitted process can be superior in all the three crucial indices,i.e.,recovery ratio,investment,and specific purification cost.On the whole,coal-based H2 generation can be ameliorated significantly through high efficient H2-selective and CO_(2)-selective membrane units. 展开更多
关键词 Hydrogen production SEPARATION Membranes Process framework H2-selective membrane CO_(2)-selective membrane
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Preparation of microstructure-controllable superhydrophobic polytetrafluoroethylene porous thin film by vacuum thermal-evaporation 被引量:2
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作者 Na YI Shanhu BAO +5 位作者 Huaijuan ZHOU Yunchuan XIN aibin huang Yining MA Rong LI PingJIN 《Frontiers of Materials Science》 SCIE CSCD 2016年第3期320-327,共8页
The three-dimensional porous network polytetrafluoroethylene (PTFE) thin films were achieved by a vacuum technique through evaporating the pure PTFE powders. The surfaces of PTFE thin films showed various morphologi... The three-dimensional porous network polytetrafluoroethylene (PTFE) thin films were achieved by a vacuum technique through evaporating the pure PTFE powders. The surfaces of PTFE thin films showed various morphologies by adjusting the evaporation temperature and the corresponding contact angle ranging from 133° to 155°. Further analyses of surface chemical composition and morphology by FTIR and FE-SEM revealed that the origin of hydrophobicity for the PTFE thin films could be ascribed to the fluorine-containing groups and the surface morphologies, indicating that abundant -CF2 groups and network structures with appropriate pore sizes played a vital role in superhydrophobicity. By characterization of UV-Vis, the films also showed high transmittance and antireflection effect. The films prepared by this simple method have potential applications such as waterproof membrane and self-cleaning coating. 展开更多
关键词 polytetrafluoroethylene (PTFE) VACUUM SUPERHYDROPHOBICITY
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