La掺杂的TiO2纳米棒在常温常压下可促进电催化的N2转化为NH3

doi:10.1016/S1872-2067(21)63795-6

催化学报 ›› 2021, Vol. 42 ›› Issue (10): 1755-1762.DOI: 10.1016/S1872-2067(21)63795-6

La掺杂的TiO₂纳米棒在常温常压下可促进电催化的N₂转化为NH₃

李莉^a, 陈海军^a^,^b, 李磊^b, 李白海^b, 吴千宝^a, 崔春华^a, 邓彪^a, 罗永岚^a, 刘倩^a(), 李廷帅^a, 张芳^c, Abdullah M. Asiri^d, 冯哲圣^b, 王焱^b(), 孙旭平^a()

^a电子科技大学基础与前沿研究院, 四川成都610054, 中国
^b电子科技大学材料与能源学院, 四川成都611731, 中国
^c国家纳米技术工程研究中心, 上海200241, 中国
^d阿卜杜勒阿齐兹国王大学理学院化学系和先进材料研究卓越中心, 吉达, 沙特阿拉伯

收稿日期:2021-01-22 接受日期:2021-03-01 出版日期:2021-10-18 发布日期:2021-06-20
通讯作者: 刘倩,王焱,孙旭平
作者简介:$ 电子信箱:xpsun@uestc.edu.cn
#电子信箱:wy@uestc.edu.cn;
*电子信箱:liuqian@uestc.edu.cn;
第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(22072015);上海市科技创新项目(18JC1410604)

La-doped TiO₂ nanorods toward boosted electrocatalytic N₂-to-NH₃ conversion at ambient conditions

Li Li^a, Haijun Chen^a^,^b, Lei Li^b, Baihai Li^b, Qianbao Wu^a, Chunhua Cui^a, Biao Deng^a, Yonglan Luo^a, Qian Liu^a(), Tingshuai Li^a, Fang Zhang^c, Abdullah M. Asiri^d, Zhe-Sheng Feng^b, Yan Wang^b(), Xuping Sun^a()

^aInstitute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
^bSchool of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China
^cNational Engineering Research Center for Nanotechnology, Shanghai 200241, China
^dChemistry Department, Faculty of Science & Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia

Received:2021-01-22 Accepted:2021-03-01 Online:2021-10-18 Published:2021-06-20
Contact: Qian Liu,Yan Wang,Xuping Sun
About author:First author contact:
^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22072015);Shanghai Scientific and Technological Innovation Project(18JC1410604)

摘要/Abstract

摘要：

氨在化肥、染料、药品和炸药的制造中起着重要作用. 目前, 传统的Haber-Bosch工艺主要用于NH₃的大规模工业化生产, 在苛刻的反应条件(300~500 ºC, 150~300 atm)下不可避免地伴随着温室气体的过量排放. 因此, 必须寻求一种绿色并且可持续的方法来生产NH₃. 电化学还原N₂ (NRR)已成为在环境条件下将N₂连续固定NH₃的一种有吸引力的替代方法. 由于稳定的N≡N具有较强的偶极矩并与析氢反应存在激烈竞争, 因此需要高效的NRR催化剂. TiO₂是典型的n型半导体, 被认为是一种很有前途的NRR电催化剂. 最近的研究表明, La₂O₃对N₂还原电催化也具有活性, 然而镧金属的稀土性质限制了其大规模应用. 本文研究发现镧可以作为一种有效的掺杂剂提高TiO₂的NRR活性.
通过水热法制备了镧掺杂的TiO₂纳米棒(La-TiO₂). 透射电子显微镜结果表明, 原始TiO₂与La-TiO₂在形貌上都是纳米棒, 镧的引入对其形貌并没有显著影响. 选区电子衍射证实了La-TiO₂纳米棒的高结晶度和四边形单晶结构. 电子自旋共振分析结果表明La-TiO₂纳米棒中存在氧空位. La-TiO₂的线性扫描伏安曲线结果表明, 在N₂饱和电解液中的电流密度明显大于在Ar饱和电解液中, 说明NRR的发生. 为了进一步证实这一假设, 在五个不同电位下分别进行了一系列的计时电流测试, 结果表明, 连续电解2 h后在-0.70 V时, NH₃产率最高, 达23.06 μg h^-1 mg_cat^-1, 并且法拉第效率也最大, 达14.54%. 此外, 电解2 h后, 没有检测到副产物N₂H₄, 表明La-TiO₂催化剂对NH₃合成具有良好的选择性. 本文还比较了La-TiO₂/CP, TiO₂/CP和CP的NRR电催化性能, 结果表明, La-TiO₂/CP的NH₃产率最高, 说明La的引入提高了La-TiO₂的NRR活性. La-TiO₂/CP通过在-0.70 V下连续6次循环测试以及连续48 h电解测试证实La-TiO₂对NRR电催化具有良好的电化学稳定性.
通过对La-O_v构型进行密度泛函理论计算, 重点研究*N₂ + H⁺ + e^- → *NNH的反应步骤, 由于*N₂加氢的自由能垒较低, La-TiO₂更容易激活N₂分子, 计算了La-TiO₂和纯TiO₂上*NNH中间体的电荷密度差异, *NNH与La-TiO₂之间存在更多的电荷转移. 采用N-N键的积分晶体轨道哈密顿布居(ICOHP)分析出La-TiO₂的ICOHP负值较小(-16.67 vs. -19.93), 说明N-N键的活化更多.

关键词: 镧掺杂, 电催化氮还原, 氧空位, TiO₂, 密度泛函理论

Abstract:

Electrochemical N₂ reduction provides a green and sustainable alternative to the Haber-Bosch technology for NH₃ synthesis. However, the extreme inertness of N₂ molecules is a formidable challenge, which requires the development of an active electrocatalyst to drive the N₂ reduction reaction (NRR) for NH₃ production at ambient conditions. Herein, we demonstrate the development of La-doped TiO₂ nanorods as an efficient NRR electrocatalyst for ambient NH₃ synthesis. The optimized La-TiO₂ catalyst offers a large NH₃ yield of 23.06 μg h^-1 mg_cat^-1 and a high Faradaic efficiency of 14.54% at -0.70 V versus reversible hydrogen electrode in 0.1 M LiClO₄, outperforming most La- and Ti-based catalysts reported before. Significantly, it also demonstrates high electrochemical stability and its activity decay is negligible after 48 h test. The mechanism is further revealed by density functional theory calculations.

Key words: La doping, Electrocatalytic N₂ reduction, Oxygen vacancy, TiO₂, Density functional theory

李莉, 陈海军, 李磊, 李白海, 吴千宝, 崔春华, 邓彪, 罗永岚, 刘倩, 李廷帅, 张芳, Abdullah M. Asiri, 冯哲圣, 王焱, 孙旭平. La掺杂的TiO₂纳米棒在常温常压下可促进电催化的N₂转化为NH₃[J]. 催化学报, 2021, 42(10): 1755-1762.

Li Li, Haijun Chen, Lei Li, Baihai Li, Qianbao Wu, Chunhua Cui, Biao Deng, Yonglan Luo, Qian Liu, Tingshuai Li, Fang Zhang, Abdullah M. Asiri, Zhe-Sheng Feng, Yan Wang, Xuping Sun. La-doped TiO₂ nanorods toward boosted electrocatalytic N₂-to-NH₃ conversion at ambient conditions[J]. Chinese Journal of Catalysis, 2021, 42(10): 1755-1762.

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图/表 4

Fig. 1. (a) Schematic illustration of the preparation of La-TiO2 nanorods; XRD patterns (b) and Raman spectra (c) of pristine TiO2 and La-TiO2; TEM image (d), HRTEM image (e), SAED pattern (f), and STEM image and corresponding EDX elemental mapping images (g) of La-TiO2.

Fig. 2. XPS spectra of Ti 2p (a) and O 1s (b) for La-TiO2 and pristine TiO2; EPR spectra (c) and BET adsorption-desorption isotherms (d) of La-TiO2 and pristine TiO2.

Fig. 3. (a) Chronoamperometry curves of La-TiO2/CP under different potentials in N2-saturated 0.1 M LiClO4; (b) Corresponding UV-Vis absorption spectra of the electrolytes stained with the indophenol indicator; (c) NH3 yields and FEs of La-TiO2/CP under various potentials; (d) Comparison of NH3 yields at -0.70 V over different electrodes; (e) Cycling tests of La-TiO2/CP at -0.70 V; (f) Chronoamperometry curve of La-TiO2/CP at -0.70 V for 48 h.

Fig. 4. (a) Free energy diagram for NRR process on pure TiO2 (110) and La-TiO2 (110): Asterisk (*) denotes the status of adsorption. (b) The corresponding intermediate configurations of La-TiO2 (110) through alternating pathway. (c) Charge density difference of the *NNH intermediates for pure TiO2 and La-TiO2, respectively. Isosurface level is 0.004 e/?3. Yellow and blue isosurface are demonstrated as positive and negative changes of density, respectively. (d) The crystal orbital Hamilton population (COHP) between N-N bond of the adsorbed *NNH intermediates for pure TiO2 and La-TiO2, respectively.

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La掺杂的TiO₂纳米棒在常温常压下可促进电催化的N₂转化为NH₃

La-doped TiO₂ nanorods toward boosted electrocatalytic N₂-to-NH₃ conversion at ambient conditions

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