DES合成高活性CoCO3纳米片及析氧反应性能研究

doi:10.11949/0438-1157.20240125

摘要/Abstract

摘要：

氢能因其热值高、清洁无污染等优势，被认为是实现碳中和最有效的能源载体之一。电解水制氢是实现可持续制氢的有效途径。其中，析氧反应（OER）缓慢动力学过程导致水分解效率低下，迫切需要开发高效、稳定的电催化剂。利用多元醇、尿素与CoCl₂·6H₂O之间的配位作用形成超分子三元低共熔溶剂（DES）体系，通过一锅溶剂热法构建表面粗糙的二维CoCO₃纳米片，用于提升电催化OER效率，并针对醇羟基数量对CoCO₃形貌及性能影响进行了探究。研究表明，丙三醇、尿素和CoCl₂·6H₂O三元DES体系制备的CoCO₃-Gly催化剂，呈现更蓬松、更薄、更粗糙的片状结构，具有更加优异的OER性能，电流密度在10 mA·cm^-2时过电位311 mV，经24 h稳定性测试电流保留率达99%。

关键词: 低共熔溶剂, 碳酸钴, 催化剂, 电催化, 析氧反应, 多元醇

Abstract:

Hydrogen energy is considered as one of the most effective energy vectors to achieve carbon neutrality due to its high calorific value and clean, pollution-free characteristics. Electrolysis of water is an effective way to achieve sustainable hydrogen production. Among them, the slow kinetics of the oxygen evolution reaction (OER) leads to low water decomposition efficiency, and it is urgent to develop efficient and stable electrocatalysts. Herein, we utilize the coordination interaction between polyhydric alcohols, urea, and CoCl₂·6H₂O to form supramolecular ternary deep eutectic solvent (DES) systems. By employing a one-pot solvothermal method, surface-roughened two-dimensional CoCO₃ nanosheets were constructed to enhance electrocatalytic OER efficiency. The impact of the number of alcohol hydroxyl groups on the morphology and performance of CoCO₃was studied. The research shows that the CoCO₃-Gly catalyst prepared by using a ternary DES system of glycerol, urea, and CoCl₂·6H₂O exhibits a more fluffy, thinner, and rougher sheet-like structure. The catalyst exhibits superior OER performance, with an overpotential of 311 mV at a current density of 10 mA·cm^-2 and a current retention rate of 99% after 24 h of stability testing.

Key words: deep eutectic solvents, cobalt carbonate, catalyst, electrocatalysis, oxygen evolution reaction, polyhydric alcohols

中图分类号:

TQ 028.8

刘亚超, 谭晓杰, 李旭东, 王瑞, 王慧, 韩璇, 赵青山. DES合成高活性CoCO₃纳米片及析氧反应性能研究[J]. 化工学报, 2024, 75(9): 3320-3328.

Yachao LIU, Xiaojie TAN, Xudong LI, Rui WANG, Hui WANG, Xuan HAN, Qingshan ZHAO. Synthesis of efficient cobalt carbonate nanosheets based on DES for oxygen evolution reaction[J]. CIESC Journal, 2024, 75(9): 3320-3328.

图/表 7

图1 CoCO3、CoCO3-PEG、CoCO3-EG和CoCO3-Gly的SEM图

Fig.1 SEM images of CoCO3, CoCO3-PEG, CoCO3-EG and CoCO3-Gly

图2 CoCO3(a)，CoCO3-PEG(b)，CoCO3-EG(c)和CoCO3-Gly(d)的TEM图；CoCO3(e)，CoCO3-PEG(f)，CoCO3-EG(g)和CoCO3-Gly(h)的HRTEM图；CoCO3-Gly的EDX元素映射图(i)

Fig.2 TEM images of CoCO3 (a), CoCO3-PEG (b), CoCO3-EG (c) and CoCO3-Gly (d); HRTEM images of CoCO3 (e), CoCO3-PEG (f), CoCO3-EG (g) and CoCO3-Gly (h); EDX overlap and element mapping profiles of CoCO3-Gly (i)

图3 CoCO3、CoCO3-PEG、CoCO3-EG和CoCO3-Gly的XRD表征图(a)；EPR光谱图(b)和氮气吸脱附曲线(c)（1G=10-4T）

Fig.3 XRD patterns (a); EPR (b) and N2 adsorption-desorption isothermal (c) curves of CoCO3, CoCO3-PEG, CoCO3-EG and CoCO3-Gly

图4 CoCO3、CoCO3-PEG、CoCO3-EG和CoCO3-Gly的XPS全谱(a)及C 1s(b)、O 1s(c)、Co 2p(d)高分辨率XPS谱图

Fig.4 XPS survey spectra (a); high-resolution XPS C 1s spectra (b)， O 1s spectra (c) and Co 2p spectra (d) of CoCO3, CoCO3-PEG, CoCO3-EG and CoCO3-Gly

图5 CoCO3、CoCO3-PEG、CoCO3-EG、CoCO3-Gly和RuO2的OER极化曲线图(a)； CoCO3、CoCO3-PEG、CoCO3-EG、CoCO3-Gly和RuO2的Tafel图(b)

Fig.5 OER polarization curves of CoCO3, CoCO3-PEG, CoCO3-EG, CoCO3-Gly and RuO2 (a); Tafel plots of CoCO3, CoCO3-PEG, CoCO3-EG, CoCO3-Gly and RuO2 (b)

图6 CoCO3(a），CoCO3-PEG(b)，CoCO3-EG(c)和CoCO3-Gly(d)的CV扫描图（电位区间1.02~1.22 V，扫描速率分别为20、40、60、80、100、120 mV·s-1）； CoCO3，CoCO3-PEG，CoCO3-EG，CoCO3-Gly在1.12 V电位处扫描速率与电流密度关系图及相应的双电层电容Cdl值(e)； CoCO3，CoCO3-PEG，CoCO3-EG和CoCO3-Gly的电化学阻抗图(f)

Fig.6 Cyclic voltammograms of CoCO3 (a), CoCO3-PEG (b), CoCO3-EG (c) and CoCO3-Gly (d) in the region of 1.02—1.22 V （vs RHE） with different scan rates (20, 40, 60, 80, 100 and 120 mV·s-1); capacitive currents against scan rate and corresponding Cdl value of CoCO3, CoCO3-PEG, CoCO3-EG and CoCO3-Gly catalysts at 1.12 V (e); EIS Nyquist plots of CoCO3, CoCO3-PEG, CoCO3-EG and CoCO3-Gly (f)

图7 CoCO3(a)、CoCO3-PEG(b)、CoCO3-EG(c)和CoCO3-Gly(d)恒定电压测试24 h的计时电流曲线图；CoCO3(e)、CoCO3-PEG(f)、CoCO3-EG(g)和CoCO3-Gly(h)经过3000次CV扫描前后LSV曲线

Fig.7 Long-time stability test of CoCO3 (a), CoCO3-PEG (b), CoCO3-EG (c) and CoCO3-Gly (d) at a constant voltage for 24 h LSV curves of CoCO3 (e), CoCO3-PEG (f), CoCO3-EG (g) and CoCO3-Gly (h) before and after 3000 CV scans

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DES合成高活性CoCO₃纳米片及析氧反应性能研究

Synthesis of efficient cobalt carbonate nanosheets based on DES for oxygen evolution reaction

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