氮掺杂石墨炭包覆的钴纳米催化剂作高效、高稳定性电催化制氢

doi:10.11944/j.issn.1000-0518.2019.05.180266

摘要/Abstract

摘要：

电催化制氢是解决当前能源危机的重要手段之一。研究高效稳定的非贵金属电催化剂是电催化制氢商业应用的重点。本文通过直接高温热解双金属沸石咪唑骨架,制备了一种氮掺杂石墨炭(NC)包覆均匀分布的钴纳米颗粒电催化剂(V-Co@NC,这里V是vacancy缩写),前躯体中的Zn元素有效地防止钴纳米颗粒的聚集,并有助于生成均匀分布的钴纳米颗粒。这种特殊的纳米结构可防止钴与电解液的直接接触,提升了其循环稳定性,同时,氮元素的掺杂提升了导电性,有利于电催化制氢性能的提升。结果表明,所制备的V-Co@NC催化剂在酸性和碱性电解液中均具有良好的催化性能,且经过5000次循环测试后催化活性基本保持不变,具有良好的应用前景。为高活性和高选择性的电催化制氢催化剂的发展提供一种全新的途径。

关键词: 制氢, 电催化, 非贵金属催化剂, 高稳定性

Abstract:

Electrocatalytic hydrogen evolution reaction(HER) provides one of the most important pathways for the crisis of energy consumption. The research of both highly efficient as well as highly stable non-noble metal electrocatalysts is the key point of commercial application of HER. In this paper, through direct pyrolysis of bimetallic ZnCo zeolitic imidazolate frameworks(ZIFs), the electrocatalyst of evenly distributed Co nanoparticle coated by nitrogen-doped graphitic carbon(V-Co@NC, V, vacancy) could be easily prepared. The existence of Zn element in the precursor could prevent efficiently the aggregation of Co nanoparticles, and help for the formation of uniformly distributed Co nanoparticles. Such unique nanostructure prevents direct contact between cobalt and electrolyte, promots their durability. Meanwhile, the existence of nitrogen dopants enhances the conductivity of catalyst, and contributes to the HER activity greatly. As a result, as-prepared V-Co@NC catalyst exhibits high electrocatalytic activity towards HER in both acidic and alkaline electrolyte, meanwhile the activity remains stable even after 5000 cycles. These performances indicate promising commercial application of the V-Co@NC catalyst. This work opens a new way for the development of HER electrocatalysts with both high activity and stability.

Key words: hydrogen evolution reaction, electrocatalysis, non-noble metal electrocatlysts, high durability

李新杰,徐鹤,于美,张超,郭安儒,刘畅. 氮掺杂石墨炭包覆的钴纳米催化剂作高效、高稳定性电催化制氢[J]. 应用化学, 2019, 36(5): 571-577.

LI Xinjie,XU He,YU Mei,ZHANG Chao,GUO Anru,LIU Chang. Nitrogen-Doped Graphitic Carbon Coated Cobalt Nanocatalysts for Highly Efficient and Durable Hydrogen Evolution Reaction[J]. Chinese Journal of Applied Chemistry, 2019, 36(5): 571-577.

参考文献

[1]	Zou X,Zhang Y.Noble Metal-Free Hydrogen Evolution Catalysts for Water Splitting[J]. Chem Soc Rev,2015,44(15):5148-5180.
[2]	CHEN Si,SUN Lizhen,SHU Xinxin,et al. Graphene-Based Catalysts for Efficient Electrocatalytic Applications[J]. Chinese J Appl Chem,2018,35(3):272-285(in Chinese). 陈思,孙立臻,舒欣欣,等. 石墨烯基催化剂的设计合成与电催化应用[J]. 应用化学,2018,35(3):272-285.
[3]	Yan J,Zheng Y,Jaroniec M,et al. Design of Electrocatalysts for Oxygen- and Hydrogen-Involving Energy Coversion Reactions[J]. Chem Soc Rev,2015,44(8):2060-2086.
[4]	Moralesguio C G,Stern L,Hu X.Nanostructured Hydrotreating Catalysts for Electrochemical Hydrogen Evolution[J]. Chem Soc G Rev,2014,43(18):6555-6559.
[5]	Gong M,Li Y,Wang H,et al. An Advanced Ni-Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation[J]. J Am Chem Soc,2013,135(23):8452-8455.
[6]	YAO Huiying,YANG Tao,HUANG Xing,et al. Coordination Complexes Based on MX4 Structure as Catalyst for Hydrogen Evolution Reaction[J]. Chinese J Appl Chem,2018,35(3):328-341(in Chinese). 姚会影,杨涛,黄幸,等. 基于MX4结构的配位化合物析氢反应催化性能[J]. 应用化学,2018,35(3):328-341.
[7]	Vrubel H,Hu X.Molybdenum Boride and Carbide Catalyze Hydrogen Evolution in Both Acidic and Basic Solutions[J]. Angew Chem,2012,124(51):12875-12878.
[8]	Arzac G M,Rojas T C,Fernandez A.Boron Compounds as Stabilizers of a Complex Microstructure in a Co-B-Based Catalyst for NaBH4 Hydrolysis[J]. ChemCatChem,2011,3(8):1305-1313.
[9]	Ganem B,Osby J O.Synthetically Useful Reactions with Metal Boride and Aluminide Catalysts[J]. Chem Rev,1986,86(5):763-780.
[10]	Muir S,Yao X.Progress in Sodium Borohydride as a Hydrogen Storage Material: Development of Hydrolysis Catalysts and Reaction Systems[J]. Hydrogen Energy,2011,36(10):5983-5997.
[11]	Kong S,Wang H,Lu Z,et al. CoSe2 Nanoparticles Grown on Carbon Fiber Paper:An Efficient and Stable Electrocatalyst for Hydrogen Evolution Reaction[J]. J Am Chem Soc,2014,136(13):4897-4900.
[12]	Kibsgaard J,Jaramillo T F.Molybdenum Phosphosulfide:An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction[J]. Angew Chem Int Ed,2014,53(52):14433-14437.
[13]	Xia B,Jiang Q,Zhao C,et al. Selenide-Based Electrocatalysts and Scaffolds for Water Oxidation Applications[J]. Adv Mater,2016,28(1):77-85.
[14]	Staszak-Jirkovsky J,Malliakas C D,Lopes P P,et al. Design of Active and Stable Co-Mo-Sx Chalcogels as pH-Universal Catalysts for the Hydrogen Evolution Reaction[J]. Nat Mater,2016,15(2):197-203.
[15]	Subbaraman R,Tripkovic D,Strmcnik D,et al. Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces[J]. Science,2011,334(10):1256-1260.
[16]	Yin H,Zhao S,Zhao K,et al. Ultrathin Platinum Nanowires Grown on Single-Layered Nickel Hydroxide with High Hydrogen Evolution Activity[J]. Nat Commun,2015,6:6430.
[17]	Kibsgaard J,Tsai C,Chan K,et al. Designing an Improved Transition Metal Phosphide Catalyst for Hydrogen Evolution Using Experimental and Theoretical Trends[J]. Energy Environ Sci,2015,8(10):3022-3029.
[18]	Tang C,Gan L,Zhang R,et al. Ternary FexCo1-xP Nanowire Array as a Robust Hydrogen Evolution Reaction Electrocatalyst with Pt-like Activity:Experimental and Theoretical Insight[J]. Nano Lett,2016,16(10):6617-6621.
[19]	Popczun E J,McKone J R,Read C G,et al. Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction[J]. J Am Chem Soc,2013,135(25):9267-9270.
[20]	Ye R,Angel-Vicente P. del,Liu Y,et al. High-Performance Hydrogen Evolution from MoS2(1-x)P x Solid Solution[J]. Adv Mater,2016,28(7):1427-1432.
[21]	Jin Y,Wang H,Li J,et al. Porous MoO2 Nanosheets as Non-noble Bifunctional Electrocatalysts for Overall Water Splitting[J]. Adv Mater,2016,28(19):3785-3790.