Preparation of CoSOH/Co(OH)2 composite nanosheets and its catalytic performance for oxygen evolution
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摘要: 以硝酸钴与硝酸锌为原料,加入尿素和氟化钠在反应釜120 ℃下均匀生长在碳纸上得到Zn-Co(OH)2复合前驱体,通过在室温下用5 mol/L NaOH和1 mol/L Na2S溶液将前驱体刻蚀并部分硫化合成了CoSOH/Co(OH)2复合材料,考察其在电解水析氧反应(OER)中的催化性能。利用XRD、SEM、TEM、XPS对催化剂的微观结构及物理化学性质进行了表征。结果表明,该方法可以刻蚀Zn原子,留下氧空位并引入掺杂S元素,氧空位和S掺杂对OER反应起到积极促进作用。同时,非晶的CoSOH也有较好的OER活性。CoSOH与Co(OH)2的协同作用使得材料表现出最优催化效果(过电位η = 310 mV,塔菲尔斜率b = 90 mV/dec)及长时间的电化学稳定性,具有较高的电催化产氧性能。Abstract: Zn-Co(OH)2 precursor was hydrothermally deposited on carbon paper at 120 ℃, using cobalt nitrate and zinc nitrate as raw materials. Then Zn-Co(OH)2 was etched and partially sulfided into CoSOH/Co(OH)2 with 5 mol/L NaOH and 1 mol/L Na2S aqueous solution at room temperature. The catalytic performance in oxygen evolution reaction (OER) was investigated. XRD, SEM, TEM, XPS were used to characterize the microstructure, physical and chemical properties of the catalyst. The results show that the used method can etch Zn atoms, create oxygen vacancies and dope sulfur. The oxygen vacancies and doped sulfur play a positive role in enhancing the OER performance. In addition, amorphous CoSOH also exhibited better OER activity. The synergy between CoSOH and Co(OH)2 finally induces the best catalytic properties (overpotential η=310 mV, Tafel slope b=90 mV/dec) and long-term electrochemical stability, that is CoSOH/Co(OH)2 possess superior electrocatalytic oxygen evolution performance.
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Key words:
- hydroxyl sulfide /
- amorphous /
- water electrolysis /
- oxygen evolution reaction /
- nanosheet
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图 5 Zn-Co(OH)2、Co(OH)2和CoSOH/Co(OH)2的电化学测试
Figure 5 Electrochemical test of Zn-Co(OH)2, Co(OH)2 and CoSOH/Co(OH)2
(a): CV activation curve of CoSOH/Co(OH)2; (b): LSV curves; (c): Tafel slope; (d): EIS spectra; (e): Stability test of Co(OH)2 and CoSOH/Co(OH)2; CV curves of CoSOH/Co(OH)2 (f), Co(OH)2(g) and CoSOH/Co(OH)2 (h) at different scan rates; (i): Cdl value
表 1 碱性介质中不同基底的钴基OER电催化剂的性能比较
Table 1 Performance comparison of cobalt-based OER electrocatalysts with different substrates in alkaline solution
Catalyst Tafel slope/(mV·dec−1) Overpotential/mV Electrolyte Substrate Reference CoSOH/Co(OH)2 90 310 1.0 mol/L KOH CFP this work Co9S8/ZnS/C 144 390 1.0 mol/L KOH RDE [7] PA-CoSx(OH)y 48 320 1.0 mol/L KOH GCE [13] CoP3 CPs 76 340 1.0 mol/L KOH CFP [27] Co-Ni-Ox/BG 54.8 310 1.0 mol/L KOH GCE [28] Co-50W-B/CC 96.8 394 1.0 mol/L NaOH CC [29] The current density of all materials corresponding to the overpotential is 10 mA/cm2; RDE: Rotating disk electrode; GCE: Glassy carbon electrode; CC: Carbon Cloth -
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