铜在自然界中储量丰富，具有优良的导电性、催化性能，并且与Pt、Pd、Au、Ag等贵金属相比非常廉价，在很多领域拥有众多潜在应用价值。随着温室效应的加剧，如何更好地将CO2转化成能源具有非常重要的现实意义，铜是唯一一种可将CO2还原成CH4和C2H4等碳氢化合物且具有较高选择性的金属，利用铜基纳米材料电催化CO2还原是当今研究的热点，电催化CO2还原的反应作为表面催化反应的一种，其催化活性和选择性强烈依赖于催化剂的电子结构和表面结构，即催化剂的组成和形貌，因此制备出具有特定晶面围成的铜纳米粒子并研究其电催化CO2还原的性能，为应对目前研究中的挑战提供了新的思路。 本论文成功制备了高指数晶面铜纳...Copper is abundant in nature, with excellent electrical conductivity, catalytic properties. It’s cheaper compared to Pt, Pd, Ag, Au and other noble metals, so it is a good replacement in many potential areas. With the aggravation of the “greenhouse effect”, how to make better use of CO2 and transfer it into useful energy has very important practical significance. Copper is the only metal that can ...学位：理学硕士院系专业：化学化工学院_物理化学学号：2052013115164

谢爱云

English

Xiamen University Institutional Repository

   学校编码：10384                                 分类号       密级            学号： 20520131151643                                  UDC              硕  士  学  位  论  文  高指数晶面结构 Cu纳米晶的电化学 制备及其电催化 CO2还原性能研究 Electrochemical Synthesis of Copper Nanocrystals with High-Index Facets and Investigation of Their Performance over Electrochemical Reduction of CO2 谢 爱 云 指导教师姓名：田  娜 副教授 孙世刚 教授 专业名称：物  理  化  学 论文提交日期：2 0 1 6 年 5 月 论文答辩时间：2 0 1 6 年 5 月 学位授予日期：2 0 1 6 年   月                  答辩委员会主席：          评    阅    人：          2016 年 5 月 厦门大学博硕士论文摘要库                   厦门大学博硕士论文摘要库   Electrochemical Synthesis of Copper Nanocrystals with High-Index Facets and Investigation of Their Performance over Electrochemical Reduction of CO2    A Dissertation Submitted to the Graduate School of Xiamen University for the Degree of Master of Science By Xie Aiyun  This work was carried out under the supervision of Assoc. Prof. Na Tian Prof. Shi-Gang Sun At Department of Chemistry, Xiamen University May, 2016  厦门大学博硕士论文摘要库                       厦门大学博硕士论文摘要库   厦门大学学位论文原创性声明  本人呈交的学位论文是本人在导师指导下,独立完成的研究成果。本人在论文写作中参考其他个人或集体已经发表的研究成果，均在文中以适当方式明确标明，并符合法律规范和《厦门大学研究生学术活动规范（试行）》。 另外，该学位论文为（孙世刚教授）课题（组）的研究成果，获得（孙世刚教授）课题（组）经费或实验室的资助，在（SSG405）实验室完成。（请在以上括号内填写课题或课题组负责人或实验室名称，未有此项声明内容的，可以不作特别声明。）  声明人（签名）：         年   月   日          厦门大学博硕士论文摘要库                       厦门大学博硕士论文摘要库   厦门大学学位论文著作权使用声明  本人同意厦门大学根据《中华人民共和国学位条例暂行实施办法》等规定保留和使用此学位论文，并向主管部门或其指定机构送交学位论文（包括纸质版和电子版），允许学位论文进入厦门大学图书馆及其数据库被查阅、借阅。本人同意厦门大学将学位论文加入全国博士、硕士学位论文共建单位数据库进行检索，将学位论文的标题和摘要汇编出版，采用影印、缩印或者其它方式合理复制学位论文。 本学位论文属于： （     ）1.经厦门大学保密委员会审查核定的保密学位论文，于   年  月  日解密，解密后适用上述授权。 （  √  ）2.不保密，适用上述授权。 （请在以上相应括号内打“√”或填上相应内容。保密学位论文应是已经厦门大学保密委员会审定过的学位论文，未经厦门大学保密委员会审定的学位论文均为公开学位论文。此声明栏不填写的，默认为公开学位论文，均适用上述授权。） 声明人（签名）： 年   月   日    厦门大学博硕士论文摘要库          厦门大学博硕士论文摘要库摘要 I  摘要 铜在自然界中储量丰富，具有优良的导电性、催化性能，并且与 Pt、Pd、 Au、Ag 等贵金属相比非常廉价，在很多领域拥有众多潜在应用价值。随着温室效应的加剧，如何更好地将 CO2转化成能源具有非常重要的现实意义，铜是唯一一种可将CO2还原成CH4和C2H4等碳氢化合物且具有较高选择性的金属，利用铜基纳米材料电催化 CO2还原是当今研究的热点，电催化 CO2还原的反应作为表面催化反应的一种，其催化活性和选择性强烈依赖于催化剂的电子结构和表面结构，即催化剂的组成和形貌，因此制备出具有特定晶面围成的铜纳米粒子并研究其电催化 CO2还原的性能，为应对目前研究中的挑战提供了新的思路。 本论文成功制备了高指数晶面铜纳米催化剂，合成了铜二十四面体纳米晶，同时研究了其电催化 CO2还原的性能。取得的主要结果如下： 1）首次制备出高指数晶面结构的铜二十四面体纳米晶。在酸性条件下，通过电化学方波电位技术先合成 Cu 纳米粒子，然后再进行 Pb UPD 处理，首次成功在 GC 电极表面制备出由具有开放结构的{530}晶面围成的 Cu 二十四面体纳米晶；研究了铜二十四面体的生长过程与机理，结果表明 Pb UPD 是生成铜二十四面体的重要因素，Pb UPD 使得到的铜二十四面体形貌更完美，同时，Pb UPD也可以作为表征Cu纳米粒子电化学活性面积的一个有力手段，以计算CO2还原实验中得到催化还原的电流密度； 2）铜二十四面体电催化 CO2 还原的研究。采用线扫伏安法、恒电位电解还原法等方法来探究 Cu THH 电催化 CO2的催化活性和选择性，结果表明 Cu THH 对电催化 CO2还原具有一定的活性，但整体对碳氢化合物和液相产物的选择性不高，同时，在反应过程中，纳米粒子的表面结构较难保持，将其用于电催化 CO2还原体系当中有待今后进一步发展和完善。 本论文运用电化学方波电位法和 Pb UPD 技术，首次制备了高指数晶面围厦门大学博硕士论文摘要库摘要 II  成的铜纳米晶，并研究了其电催化 CO2还原的活性和选择性，为探索运用电化学方波电位技术制备除贵金属以外的其他金属催化剂提供了新思路，同时为进一步研究铜基纳米材料电催化 CO2还原提供了有效参考。 关键词：铜纳米晶，高指数晶面，电催化 CO2还原，铅欠电位沉积                     厦门大学博硕士论文摘要库Abstract III  Abstract Copper is abundant in nature, with excellent electrical conductivity, catalytic properties. It’s cheaper compared to Pt, Pd, Ag, Au and other noble metals, so it is a good replacement in many potential areas. With the aggravation of the “greenhouse effect”, how to make better use of CO2 and transfer it into useful energy has very important practical significance. Copper is the only metal that can convert CO2 into hydrocarbons such as CH4 and C2H4 with higher selectivity, so use copper based nanomaterials for catalytic CO2 reduction is a hotspot of current research. Electric catalytic reduction of CO2 is one of the surface catalytic reactions, so its catalytic activity and selectivity strongly depends on the electronic structure and surface structure of catalyst, that is the composition and morphology of the catalyst. Therefore in order to meet the challenges of present studies, the shape-controlled synthesis of copper nanocrystals bounded by specific facets and study its performance for electrochemical reduction of CO2 could be a new idea. In this thesis, we successfully synthesized copper nanocrystals bounded by high-index facets, that is Cu tetrahexahedron (THH), and studied its performance of electrochemical reduction of CO2. The main results are as following: 1) Tetrahexahedral Cu nanocrystals (THH Cu NCs) have been firstly prepared. First of all, Cu nanoparticles were synthesized by using electrochemical square-wave potential method, then Pb UPD on Cu nanoparticles were carried out, which result in the first synthesis of THH Cu NCs enclosed with {530} high-index facets on GC electrode surface. Moreover, we studied the growth process and formation mechanism of THH Cu NCs, the results show that Pb UPD on Cu is an important factor for the final THH shape. With the increase of Pb concentration, the Cu THH became more perfect and angular. Meanwhile, Pb UPD also can be used as a method to calculate the electrochemical surface area of Cu nanoparticles, which are used in calculating the current density of CO2 reduction. 厦门大学博硕士论文摘要库Abstract IV  2) Studied the performance of electrochemical reduction of CO2 on Cu THH. Through electrochemical methods, such as linear sweep voltammetry and potentiostatic electrolysis method,we explored the electrochemical catalytic activity and electrochemical selectivity for electrochemical reduction of CO2. The results show that Cu THH has a certain catalytic activity for CO2 reduction, but the selectivity of hydrocarbons and liquid product according to the overall product is not high,meanwhile, the surface morphology of the nanoparticles is a little difficult to maintain during the reaction process.Therefore, because of its structural instability, although theoretically Cu THH is an ideal catalyst for electrochemical reduction of CO2, to use it for the system of electrochemical reduction of CO2 remains to be further research. This thesis use electrochemical square wave technology and Pb UPD process, prepared successfully Cu THH nanocrystals enclosed by high-index facets for the first time, and explored its catalytic activity and selectivity of electrochemical reduction of CO2, providing a new approach for the preparation of metal nanocrystals other than noble metal nanocrystals through electrochemical methods,and at the same time, providing effective reference for further research of electrochemical reduction of CO2 on copper based nanomaterials. Keywords: copper nanocrystals, high-index facets, CO2 electroreduction, Pb UPD       厦门大学博硕士论文摘要库目录 i  目录  摘要 .............................................................................................................................. I Abstract ................................................................................................................... III 第一章 绪论 .............................................................................................................. 1 §1.1 金属纳米催化剂概述 ...................................................................................... 1 §1.2 铜基纳米催化剂的研究进展 .......................................................................... 2 §1.3 电化学法制备高指数晶面纳米催化剂的研究进展 ...................................... 5 §1.4 铜基催化剂电催化 CO2的还原的研究进展 ............................................... 10 §1.4.1 铜的形貌的影响...................................................................................... 11 §1.4.2 其他因素的影响...................................................................................... 15 §1.4.3 铜电催化 CO2还原的机理与失活研究 ................................................. 17 §1.5 本论文的研究目的与研究设想 .................................................................... 19 参考文献 ................................................................................................................. 21 第二章 实验 ............................................................................................................ 26 §2.1 试剂与溶液 .................................................................................................... 26 §2.2 物理性质表征 ................................................................................................ 27 §2.2.1 扫描电子显微镜（SEM） ..................................................................... 27 §2.2.2 透射电子显微镜 (TEM)和高分辨透射电子显微镜 (HRTEM） ....... 27 §2.2.3 气相色谱.................................................................................................. 28 §2.2.4 核磁共振波谱仪...................................................................................... 29 §2.3 电化学体系 .................................................................................................... 29 §2.3.1 电极及表面处理...................................................................................... 29 §2.3.2 电化学实验.............................................................................................. 29 参考文献 ................................................................................................................. 30 厦门大学博硕士论文摘要库目录 ii  第三章 高指数晶面结构铜纳米晶的电化学制备与表征 ....................... 31 §3.1 铜二十四面体的制备与表征 ........................................................................ 31 §3.1.1 铜二十四面体的制备.............................................................................. 31 §3.1.2 Cu THH 的 Pb 欠电位沉积曲线表征 ................................................... 34 §3.1.3 Cu THH 的 SEM 表征 ............................................................................. 35 §3.1.4 Cu THH 的 TEM 表征 ............................................................................. 37 §3.1.5 Cu THH 的 CO 吸脱附表征 .................................................................... 39 §3.2 铜二十四面体生机理研究 ............................................................................ 41 §3.2.1 Pb UPD 的作用 ........................................................................................ 41 §3.2.2 Pb 离子浓度的影响 ................................................................................. 45 §3.2.3 前驱体电解液的影响.............................................................................. 45 §3.3 铜二十四面体电化学制备的进一步探索 .................................................... 46 §3.3.1 在前驱体镀液中加入 Pb 的方法合成 ................................................... 46 §3.3.2 铜纳米花的制备与表征.......................................................................... 48 §3.4 本章小结 ........................................................................................................ 53 参考文献 ................................................................................................................. 55 第四章 高指数晶面结构铜纳米晶电催化 CO2还原的研究 ............... 56 §4.1 Cu THH上电催化 CO2还原的研究 ............................................................ 56 §4.1.1 电催化 CO2还原电解池的初步设计 ..................................................... 57 §4.1.2 电极电化学活性面积的测定.................................................................. 57 §4.1.3 线性扫描伏安曲线(LSV)的测定 ........................................................... 59 §4.1.4 Cu THH 电催化 CO2还原初步测试 ...................................................... 62 §4.1.5 电催化 CO2还原电解池的优化设计 ..................................................... 65 §4.1.6 Cu THH 在不同电位下电催化 CO2还原的影响 ................................... 66 §4.1.7 CO2还原前后 Cu 纳米粒子形貌对比 .................................................... 68 §4.2 铜片上方波电位沉积的 Cu纳米粒子电催化 CO2还原的研究 ................ 69 §4.2.1 铜片上方波电位沉积 Cu 纳米粒子的制备 ........................................... 69 厦门大学博硕士论文摘要库目录 iii  §4.2.2 铜片上方波沉积 Cu 纳米粒子的 Pb UPD 表征 .................................... 70 §4.2.3 铜片上方波沉积的 Cu 纳米粒子在不同电位下电催化 CO2还原的影响.......................................................................................................................... 71 §4.2.4 CO2还原前后 Cu 粒子形貌对比 ............................................................ 74 §4.3 本章小结 ........................................................................................................ 75 参考文献 ................................................................................................................. 77 结论与展望 .............................................................................................................. 78 作者攻读硕士期间发表与交流的论文 ........................................................... 80 致谢 ............................................................................................................................ 81     厦门大学博硕士论文摘要库Table of Contents iv  Table of Contents Abstract in Chinese………………………………………………...…. I Abstract in English………………………………………………........III Chapter 1 Introduction………………………………………………..1 §1.1 Overview of metal nanocatalysts…………………………………………..1 §1.2 Recent progress of copper based nanocatalysts…………………………..2 §1.3 Research on synthesis of nanocatalysts with high-index facets by electrochemical method………………………………………………………….5 §1.4 Research on electrochemical reduction of CO2 over copper based nanocatalysts……………………………………………………………………10 §1.4.1 The influence of the morphology of copper………………...…………11 §1.4.2 The influence of other factors…………………………………...……..15 §1.4.3 The studies of mechanism and deactivation of copper electric catalysts for CO2 reduction reaction……………………………………………….……17 §1.5 Objectives and plans of the dissertation………………………...……….19 References……………………………………………………………………….21 Chapter 2 Experimental……………………………………………..26 §2.1 Reagents and solution……………………………………………………..26 §2.2 Physical characterization…………………………………………………27 §2.2.1 Scanning electron microscopy (SEM)…………………….……..…....27 §2.2.2 Transmission electron microscopy (TEM) and high resolution TEM (HRTEM)…………………………………………………....………………...28 §2.2.3 Gas chromatography…………………………………………………...28 §2.2.4 Nuclear magnetic resonance spectrometry………………………..…...29 §2.3 Electrochemical system…………………………………………………...29 §2.3.1 Electrodes and surface pretreatment………………………………..….29 §2.3.2 Electrochemical experiments…………………………………………..29 厦门大学博硕士论文摘要库Degree papers are in the “Xiamen University Electronic Theses and Dissertations Database”. Fulltexts are available in the following ways: 1. If your library is a CALIS member libraries, please log on http://etd.calis.edu.cn/ and submitrequests online, or consult the interlibrary loan department in your library. 2. For users of non-CALIS member libraries, please mail to etd@xmu.edu.cn for delivery details.厦门大学博硕士论文摘要库

Electrochemical Synthesis of Copper Nanocrystals with High-Index Facets and Investigation of Their Performance over Electrochemical Reduction of CO2

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Electrochemical Synthesis of Copper Nanocrystals with High-Index Facets and Investigation of Their Performance over Electrochemical Reduction of CO2

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