孙世刚院士团队 EER 最新综述 ︱ 低温燃料电池 电 催化剂的合理设计 与 合成 最新综述： 本文以阴极和阳极反应的合理设计为重点，综述了燃料电池质子交换膜（ PEMFC ）电催化剂的最 新研究成果 。这些设计基于模型表面刻度获得活性中心 , 包括用于阳极电氧化反应的高指数晶面铂和铂合金纳米晶 ， 以及用于阴极氧还原反应（ ORR ）的铂基合金 / 核 − 壳结构和碳基非贵金属催化剂。重点评述了用于阳极催化剂的高指数纳米晶、合金纳米颗粒及其载体效应，着重介绍了阴极催化剂方面具有新颖结构和不同组份的 ORR 电催化剂的最新进展，还综述了碳基非贵金属催化剂的活性中心结构、催化性能及其在燃料电池中的稳定性 。此外，展望了先进燃料电池电催化剂的发展前景和现状。 Rational Design and Synthesis of Low‑Temperature Fuel Cell Electrocatalysts Abstract: Recent progresses in proton exchange membrane fuel cell electrocatalysts are reviewed in this article in terms of cathodic and anodic reactions with a focus on rational design. These designs are based around gaining active sites using model surface studies and include high-index faceted Pt and Pt-alloy nanocrystals for anodic electrooxidation reactions as well as Pt-based alloy/core–shell structures and carbon-based non-precious metal catalysts for cathodic oxygen reduction reactions (ORR).High-index nanocrystals, alloy nanoparticles, and support effects are highlighted for anodic catalysts, and current developments in ORR electrocatalysts with novel structures and different compositions are emphasized for cathodic catalysts. Active site structures, catalytic performances, and stability in fuel cells are also reviewed for carbon-based non-precious metal catalysts.In addition, further developmental perspectives and the current status of advanced fuel cell electrocatalysts are provided. 文章信息 文章将发表于 EER 期刊 2018 年第 1 卷第 1 期，详情请阅读全文，可免费下载。 文章题目 ： Rational Design and Synthesis of Low‑Temperature Fuel CellElectrocatalysts 引用信息 ： Tian, N., Lu, BA., Yang, XD. et al. Electrochem. Energ. Rev. (2018). https://doi.org/10.1007/s41918-018-0004-1 关键词 ： 燃 料电池，铂，非贵金属催化剂，纳米晶，活性中心，电催化 全文链接 ： https://link.springer.com/article/10.1007/s41918-018-0004-1/fulltext.html 原文（扫描或长按二维码，识别后直达原文页面）： Biographies of Authors Na Tian (first author) received her Ph.D. degree from Xiamen University in 2007 and is now a professor at this University. Her research interests focus on metal nanocrystals with high-energy surfaces, electrocatalysts for oxygen reduction reaction, oxidation of small organic molecules,and CO 2 reduction. Bang - An Lu obtained his M.S. from Harbin Engineering University in 2012. He is currently pursuing a Ph.D. program in Physical Chemistry at Xiamen University. His research interests focus on exploring novel oxygen reduction reaction catalysts. Xiao-Dong Yang received his Ph.D. degree in material science and engineering from Xi’an Jiaotong University in 2014, and then spent 3 years as a post-doctoral fellow at Xiamen University. He became a Lecturer at Huaqiao University in 2017. His current research focuses on the development of polymer electrolyte fuel cells and electrocatalysts. Rui Huang obtained her Ph.D. degree from Xiamen University in 2013, and then did 3 years of postdoctoral research at the Collaborative Innovation Center of Chemistry for Energy Materials. She is actually an engineer at the Department of Chemistry. Her research interests include electrocatalysis, controlled synthesis of nanomaterials, and electrochemical in situ FTIR spectroscopy. Yan-Xia Jiang received her Ph.D. degree from Jilin University in 1999, and then joined the department of Chemistry at Xiamen University and was promoted to full professor in 2007. Her current research interests include electrochemical surface science, electrocatalysis and spectroelectrochemistry. Zhi-You Zhou received his Ph.D. degree in 2004 from Xiamen University and is a professor at the College of Chemistry and Chemical Engineering. His research interests include electrocatalysis, non-precious metal catalysts, fuel cells, and electrochemical in situ FTIR spectroscopy. Shi‑Gang Sun (corresponding author) obtained Doctorat d’Etat in 1986 from Université Pierre et Marie Curie (Paris VI), France, and is a professor of chemistry at Xiamen University. His research interests include electrocatalysis, electrochemical surface science, spectroelectrochemistry, and electrochemical energy conversion and storage. He has been elected Academician of Chinese Academy of Sciences, Fellow of Royal Society of Chemistry and Fellow of International Society of Electrochemistry. 杂志介绍 Electrochemical Energy Reviews (《电化学能源评论》，简称EER)，该期刊旨在及时反映国际电化学能源转换与存储领域的最新科研成果和动态，促进国内、国际的学术交流，设有专题综述和一般综述栏目。EER是国际上第一本专注电化学能源的综述性期刊。EER覆盖化学能源转换与存储所有学科，包括燃料电池，锂电池，金属-空气电池，超级电容器，制氢-储氢，CO 2 转换等。 EER为季刊，每年3月、6月、9月以及12月出版。 创刊号将在 2018 年3月正式出版。 欢迎关注和投稿 期刊执行严格的同行评议，提供英文润色、图片精修、封面图片设计等服务。出版周期 3个月左右，高水平论文可加快出版。欢迎关注和投稿 。 联系我们 E-mail eer@oa.shu.edu.cn Web http://www.springer.com/chemistry/electrochemistry/journal/41918 http://www.eer.shu.edu.cn Tel 86-21-66136010 长按 /扫描关注EER微信公众号
染料敏化太阳能电池（DSSC），也称为Gratzel cell 。目前最成功的是Gratzel等人提出的染料敏化纳米二氧化钛薄膜为光阳极的太阳能光电池(简称为Gratzel电池)，其光电转换效率在模拟日光照射下(AM1.5，1000Wm -2 )已达10%。电极材料TiO 2 具备价格便宜、制备简单、无毒、稳定、应用范围广，且抗腐蚀性能好。但其禁带宽度为3.2eV；吸收范围都在紫外区，因此需要染料敏化。为了吸附更多的染料分子，必须制备多孔、大比表面积的纳米TiO 2 薄膜电极。 多孔纳米 T iO 2 薄膜的制备方法主要有两种：溶胶-凝胶法和由二氧化钛超细粉制得。如由二氧化钛纳米管，碳纳米管阵列的制备已产生了各种方法，包括沉积到一个纳米多孔氧化铝模板；溶液凝胶法以有机凝胶因子作为模板，在水浴中进行种子生长。 同时Gopal等人还发现，添加额外的乙酸到阳极电解液可以改变二氧化钛纳米管的脆性，改善使用时易损坏的倾向，提高其机械强度。此外， 在硼酸环境中制备的钛纳米管表现出紫外光电转化效率为7.8%，在580℃ 退火制得的 6 微米的纳米管阵列表现出最高的转化效率 为12.25%。 此外， Mane 等人研究的 TiO 2 /ZnO 薄膜电极的染料敏化太阳能电池，通过采用化学浴沉积技术制得TiO 2 /ZnO系统禁带宽度为3.2 eV ，敏化的 TiO 2 /ZnO 电池有一个25min的短路电流稳定期 ，设备的光电转换效率为0.67 ％。 染料敏化纳米薄膜太阳能电池多采用液态电解质作为电荷传输材料。液态电解质的选材范围广，电极电势易于调节，因此取得了一定成果。但液态电解质有以下缺点：(1)液态电解质的存在易导致敏化染料的脱附；(2)溶剂挥发，可与敏化染料作用导致染料降解；(3)密封工艺复杂，密封剂也可能与电解质反应。 对于全固态太阳能电池，目前最常用的是空穴传输材料一般为p型。p型半导体材料应满足:(1)在可见光区(染料的吸收范围)内必须是透明的；(2)沉积p型半导体材料的方法不能使吸附在 TiO 2 纳米晶体上的染料溶解或降解；(3)染料的激发态能级在 TiO 2 导带之上，而基态能级在p型半导体价带之下。 参考： 1. 陈振兴. 高分子电池材料. 北京：化学工业出版社，2006 2. Gopal K. Mor, Oomman K. Varghese et al. Solar Energy Materials Solar Cells 90(2006)，2011-2075 3. Rajaram S. Mane, Won Joo Lee, et al. J.Phys.Chem. B 2005,109,24254-24259
一个偶然的机会，其实是跟着李老师做一个小项目：电镀金刚石锯片。发现通过调整镀液中添加剂的成分，可以得到纳米晶结构的镀层。当时，关于纳米晶变形机制的研究也算是如火如荼，主要也在于纳米晶结构材料的制备得到了突破。我最崇拜的就是金属所的卢柯院士课题组，他们采用电沉积的方法首次制备了室温超塑性的纳米晶铜和高强高塑高导电性能的纳米孪晶铜。其实我对材料的力学性能知之甚少，但我的导师连建设教授眼光敏锐，当年他在法国的时候就已经与现在的SPD鼻祖Valiev合作过，当得知我们也可以电沉积镍和镍钴合金之后，就给我讲了很多关于纳米晶变形有意思的研究，而且也提出很多值得做的课题设想。我被连老师的渊博知识，还有纳米晶变形的奇异特性深深吸引。所以决定放弃镁合金的耐腐蚀研究，转入到纳米晶结构材料制备与力学表征的研究课题之中。 这是一个非常痛苦的学习过程，包扩相关的力学知识和样品的测试表征。纳米晶样品倒是很容易制备，但要做小样品的拉伸试验，必须将其表面进行抛光，这是一个很累人的工作。这方面我从江中浩老师身上学到了很多，江老师做事非常仔细认真，我个性比较着急。但抛试样是需要耐心加耐心的工作，在江老师的鼓励和指点之下，我终于做出了合格的试样。其实最艰苦的还是材料的结构表征。因为当时学校里的TEM、SEM资源有限，所以连老师就开车载着我到工学院去做表证。现在想起来，那也真是一段难忘的经历。没有连老师的鼓励与帮助，我估计很难有相关的成果出来。 数据分析费了好长一段时间，因为当时国际上关于纳米晶镍的研究报道简直是铺天盖地，想找到突破口非常的难。还好我们自己制备样品，这个条件具有唯一性。另外，我们抓着应变速率敏感性这一点进行大量的实验，得到丰富的数据，终于我的第一篇关于纳米晶变形的文章被Script Mater接收发表了。有了这个突破口，剩下的工作就是继续细化，继续挖掘数据的过程了。总之，还好，在连老师的指导下，在博士毕业的时候发表了7篇相关的文章，列表如下： Gu C, Lian J, Jiang Z, Jiang Q. Enhanced tensile ductility in an electrodeposited nanocrystalline Ni. Scripta Materialia 2006;54:579. . PAGEREF _Toc234372349 \h 3 Gu C, Lian J, Jiang Z. High strength nanocrystalline Ni-Co alloy with enhanced tensile ductility. Advanced Engineering Materials 2006; 8:252. . PAGEREF _Toc234372350 \h 4 Gu C, Lian J, Jiang Q, Jiang Z. Ductile-Brittle-Ductile transition in an electrodeposited 13 nanometer grain sized Ni-8.6wt.%Co alloy. Materials Science and Engineering A 2007; 459:75. PAGEREF _Toc234372351 \h 4 Lian J, Gu C, Jiang Q, Jiang Z. Strain rate sensitivity of face-centered cubic nanocrystalline materials based on dislocation deformation. Journal of Applied Physics 2006;99: 076103. . PAGEREF _Toc234372352 \h 4 Gu C, Lian J, Jiang Q. Layered nanostructured Ni with modulated hardness fabricated by surfactant-assistant electrodeposition. Scripta Materialia 2007;57:233. C. Gu, J. Lian, Q. Jiang, W. Zheng, Experimental and modeling investigations on strain rate sensitivity of an electrodeposited 20 nm grain sized Ni, J. Phys. D 40(2007) 7440-7446. Lian J, Gu C, Li G, Jiang Q. Strain rate sensitivity and activation volume of electrodeposited nanocrystalline Ni and Ni-Co alloys. Rare Metals; Volume: 26 Special Issue: Sp. Iss. SI Pages: 134-138 Published: AUG 2007 （未完待续）
标签: 纳米晶
