富氧空位Co3O4纳米线的制备及其电解水性能研究

doi:10.11949/0438-1157.20200597

摘要/Abstract

摘要：

在室温下利用NaBH₄溶液还原Co₃O₄纳米线获得富含氧空位（V_O）的三维自支撑纳米线阵列用作全水解电催化剂，其中NaBH₄处理10 min的Co₃O₄/NF在碱性介质中对析氧反应（OER）和析氢反应（HER）表现出很高的活性，在10 mA·cm^-2电流密度下分别仅需240和132 mV的过电位。V_O-Co₃O₄/NF同时作为阴极和阳极电催化剂时，在10 mA·cm^-2下电解水槽电压仅为1.63 V，其耐久性可达60 h以上。该工作为富含氧空位结构的过渡金属氧化物双功能电催化剂的制备提供了新的方法和思路。

关键词: 氧空位, Co₃O₄, 纳米结构, 电化学, 制氢, 析氧反应

Abstract:

A novel kind of vacancy-rich nanowire arrays were prepared by reducing rough Co₃O₄ nanowires with NaBH₄ solution on 3D nickel foam at room temperature for overall water splitting. Co₃O₄/NF treated by NaBH₄ for 10 min was highly active for oxygen evolution reaction (OER) and simultaneously efficient for hydrogen evolution reaction (HER) with the need of the overpotentials of 240 and 132 mV to drive 10 mA·cm^-2 in alkaline media, respectively. Furthermore, the electrocatalysts as both cathode and anode in a two-electrode system presented excellent durability for over 60 h at 10 mA·cm^-2, maintaining the cell voltage of merely 1.63 V. This work provides new methods and ideas for the preparation of transition metal oxide bifunctional electrocatalysts rich in oxygen vacancies.

Key words: oxygen vacancy, Co₃O₄, nanostructure, electrochemistry, hydrogen production, oxygen evolution reaction

中图分类号:

O 646

原荷峰,马自在,王淑敏,李晋平,王孝广. 富氧空位Co₃O₄纳米线的制备及其电解水性能研究[J]. 化工学报, 2020, 71(12): 5831-5841.

YUAN Hefeng,MA Zizai,WANG Shumin,LI Jinping,WANG Xiaoguang. Engineering oxygen vacancy-rich Co₃O₄ nanowire as high-efficiency and durable bifunctional electrocatalyst for overall alkaline water splitting[J]. CIESC Journal, 2020, 71(12): 5831-5841.

图/表 9

图1 Co3O4/NF和VO-Co3O4/NF的XRD谱图

Fig.1 XRD patterns of Co3O4/NF and VO-Co3O4/NF

图2 Co3O4/NF和VO-Co3O4/NF的SEM照片

Fig.2 SEM images of Co3O4/NF and VO-Co3O4/NF

图3 Co3O4/NF和VO-Co3O4/NF的微结构表征((e) 中用实线表示VO-Co3O4的晶格区域，虚线表示非晶区域)

Fig.3 Microstructure characterization of Co3O4/NF and VO-Co3O4/NF(The lattice fringes and amorphous domain of VO-Co3O4/NF are labeled in solid and doted ellipse respectively in (e))

图4 Co3O4/NF和VO-Co3O4/NF的XPS谱图

Fig.4 XPS spectra of Co3O4/NF and VO-Co3O4/NF

图5 VO-Co3O4/NF在1.0 mol·L-1 KOH中的析氢性能测试

Fig.5 HER performance of VO-Co3O4/NF in 1.0 mol·L-1 KOH

图6 VO-Co3O4/NF的析氧性能测试((a)~(d))和双功能VO-Co3O4/NF催化剂的全水解性能测试((e),(f))

Fig.6 OER performance of VO-Co3O4/NF ((a)—(d)) andoverall water splitting performance of bifunctional VO-Co3O4/NF((e),(f))

图7 VO-Co3O4/NF在OER耐久性((a),(b))和HER耐久性((c),(d))实验后的XRD谱图和SEM照片

Fig.7 XRD patterns and SEM images of VO-Co3O4/NF after OER ((a),(b)) and HER ((c),(d)) durability test, respectively

图A1 Co3O4/NF和VO-Co3O4/NF电化学表征

Fig.A1 Electrochemical characterization of Co3O4/NF and VO-Co3O4/NF

图A2 VO-Co3O4/NF在OER((a),(b))和HER((c),(d))计时电位测试后的高分辨XPS光谱图chronopotentiometric test respectively

Fig.A2 High resolution XPS spectra of Co 2p and O 1s for VO-Co3O4/NF after OER((a),(b)) and HER((c),(d))

参考文献 36

1	Abe J O, Popoola A P I, Ajenifuja E, et al. Hydrogen energy, economy and storage: review and recommendation [J]. Int. J. Hydrogen Energy, 2019, 44(29): 15072-15086.
2	Jamesh M I. Recent progress on earth abundant hydrogen evolution reaction and oxygen evolution reaction bifunctional electrocatalyst for overall water splitting in alkaline media [J]. J. Power Sources, 2016, 333: 213-236.
3	Yang M Q, Wang J, Wu H, et al. Noble metal-free nanocatalysts with vacancies for electrochemical water splitting [J]. Small, 2018, 14(15): 1703323.
4	Tang C, Zhang R, Lu W B, et al. Fe-doped CoP nanoarray: a monolithic multifunctional catalyst for highly efficient hydrogen generation [J]. Adv. Mater., 2017, 29(2): 1602441.
5	黄颖彬, 张敏, 柳鹏,等. 氧还原和析氧反应的双功能电催化剂―氮磷共掺碳负载四氧化三钴 [J]. 催化学报, 2016, 37(8): 1249-1256.
	Huang Y B, Zhang M, Liu P, et al. Co3O4 supported on N, P-doped carbon as a bifunctional electrocatalyst for oxygen reduction and evolution reactions [J]. Chinese J. Catal., 2016, 37(8): 1249-1256.
6	Yan D F, Chen R, Xiao Z H, et al. Engineering the electronic structure of Co3O4 by carbon-doping for efficient overall water splitting [J]. Electrochim. Acta, 2019, 303: 316-322.
7	Cai Z, Bi Y M, Hu E Y, et al. Single-crystalline ultrathin Co3O4 nanosheets with massive vacancy defects for enhanced electrocatalysis [J]. Adv. Energy Mater., 2018, 8(3): 1701694.
8	Tong Y, Mao H N, Xu Y L, et al. Oxygen vacancies confined in Co3O4 quantum dots for promoting oxygen evolution electrocatalysis [J]. Inorg. Chem. Front., 2019, 6(8): 2055-2060.
9	Cheng G H, Kou T Y, Zhang J, et al. O22-/O-functionalized oxygen-deficient Co3O4 nanorods as high performance supercapacitor electrodes and electrocatalysts towards water splitting [J]. Nano Energy, 2017, 38: 155-166.
10	Zhang L J, Li H J, Li K Z, et al. Morphology-controlled fabrication of Co3O4 nanostructures and their comparative catalytic activity for oxygen evolution reaction [J]. J. Alloys Comp., 2016, 680: 146-154.
11	Yang L, Zhou H, Qin X, et al. Cathodic electrochemical activation of Co3O4 nanoarrays: a smart strategy to significantly boost the hydrogen evolution activity [J]. Chem. Commun., 2018, 54(17): 2150-2153.
12	Liu Y W, Xiao C, Li Z, et al. Vacancy engineering for tuning electron and phonon structures of two-dimensional materials [J]. Adv. Energy Mater., 2016, 6(23): 1600436.
13	Zhang Z, Zhang T R, Lee J Y. Enhancement effect of borate doping on the oxygen evolution activity of α-nickel hydroxide [J]. ACS Appl. Nano. Mater., 2018, 1(2): 751-758.
14	Zhuang L Z, Jia Y, He T W, et al. Tuning oxygen vacancies in two-dimensional iron-cobalt oxide nanosheets through hydrogenation for enhanced oxygen evolution activity [J]. Nano Res., 2018, 11(6): 3509-3518.
15	Liu P F, Yang S, Zhang B, et al. Defect-rich ultrathin cobalt-iron layered double hydroxide for electrochemical overall water splitting [J]. ACS Appl. Mater. Interfaces., 2016, 8(50): 34474-34481.
16	Song F, Schenk K, Hu X L. A nanoporous oxygen evolution catalyst synthesized by selective electrochemical etching of perovskite hydroxide CoSn(OH)6 nanocubes [J]. Energ. Environ. Sci., 2016, 9(2): 473-477.
17	Yang H Y, Chen Z L, Guo P F, et al. B-doping-induced amorphization of LDH for large-current-density hydrogen evolution reaction [J]. Appl. Catal. B-Environ., 2020, 261: 118240.
18	Peng S J, Gong F, Li L L, et al. Necklace-like multishelled hollow spinel oxides with oxygen vacancies for efficient water electrolysis [J]. J. Am. Chem. Soc., 2018, 140(42): 13644-13653.
19	Wei R J, Fang M, Dong G F, et al. High-index faceted porous Co3O4 nanosheets with oxygen vacancies for highly efficient water oxidation [J]. ACS Appl. Mater. Interfaces, 2018, 10(8): 7079-7086.
20	Liu D L, Wang C H, Yu Y F, et al. Understanding the nature of ammonia treatment to synthesize oxygen vacancy-enriched transition metal oxides [J]. Chem, 2019, 5(2): 376-389.
21	Hu Q, Huang X W, Wang Z Y, et al. Slower removing ligands of metal organic frameworks enables higher electrocatalytic performance of derived nanomaterials [J]. Nano Lett., 2014, 14(6): 3309-3313.
22	Xu L, Jiang Q Q, Xiao Z H, et al. Plasma-engraved Co3O4 nanosheets with oxygen vacancies and high surface area for the oxygen evolution reaction [J]. Angew. Chem. Int. Ed., 2016, 55: 5277-5281.
23	杨永馨, 徐征, 赵谡玲,等. 形貌可控的NaMgF3: Gd3+纳米晶体的合成及其光致发光特性研究[J]. 光谱学与光谱分析, 2020, 40(1): 10-14.
	Yang Y X, Xu Z, Zhao S L, et al. Shape-controlled synthesis of NaMgF3: Gd3+ nanocrystals and its upconversion photoluminescence properties [J]. Spectrosc. Spect. Anal., 2020, 40(1): 10-14.
24	Han X P, He G W, He Y, et al. Engineering catalytic active sites on cobalt oxide surface for enhanced oxygen electrocatalysis [J]. Adv. Energy Mater., 2018, 8(10): 1702222.
25	Zhang J J, Wang H H, Zhao T J, et al. Oxygen vacancy engineering of Co3O4 nanocrystals through coupling with metal support for water oxidation [J]. ChemSusChem, 2017, 10: 2875-2879.
26	Gao R, Li Z Y, Zhang X L, et al. Carbon-dotted defective CoO with oxygen vacancies: a synergetic design of bifunctional cathode catalyst for Li-O2 batteries [J]. ACS Catal., 2016, 6(1): 400-406.
27	Liang Y, Yang Y, Xu K, et al. Crystal plane dependent electrocatalytic performance of NiS2 nanocrystals for hydrogen evolution reaction [J]. J. Catal., 2020, 381: 63-69.
28	Ji D, Peng L S, Shen J J, et al. Inert V2O3 oxide promotes the electrocatalytic activity of Ni metal for alkaline hydrogen evolution [J]. Chem. Commun., 2019, 55(22): 3290-3293.
29	Wu C, Liu D, Li H, et al. Molybdenum carbide-decorated metallic cobalt@nitrogen-doped carbon polyhedrons for enhanced electrocatalytic hydrogen evolution [J]. Small, 2018, 14(16): 1704227.
30	王文峰, 秦山, 张荣荣, 等. 纳米八面体形FeP@PC的制备及催化析氢性能[J]. 高等学校化学学报, 2019, 40(9): 1979-1987.
	Wang W F, Qin S, Zhang R R, et al. Preparation of UIO-66-based porous nano-octahedral FeP@PC for efficient and durable hydrogen evolution [J]. Chem. J. Chinese U., 2019, 40(9): 1979-1987.
31	Wang H Y, Hung S F, Chen H Y, et al. In operando identification of geometrical-site-dependent water oxidation activity of spinel Co3O4 [J]. J. Am. Chem. Soc., 2016, 138(1): 36-39.
32	Bergmann A, Jones T E, Martinez-Moreno E, et al. Unified structural motifs of the catalytically active state of Co(oxyhydr)oxides during the electrochemical oxygen evolution reaction [J]. Nat. Catal., 2018, 1(9): 711-719.
33	Masa J, Weide P, Peeters D, et al. Amorphous cobalt boride (Co2B) as a highly efficient nonprecious catalyst for electrochemical water splitting: oxygen and hydrogen evolution [J]. Adv. Energy Mater., 2016, 6(6): 1502313.
34	Tung C W, Hsu Y Y, Shen Y P, et al. Reversible adapting layer produces robust single-crystal electrocatalyst for oxygen evolution [J]. Nat. Commun., 2015, 6: 8106.
35	Chen Z, Cai L, Yang X F, et al. Reversible structural evolution of NiCoOxHy during the oxygen evolution reaction and identification of the catalytically active phase [J]. ACS Catal., 2017, 8(2): 1238-1247.
36	McCrory C C L, Jung S, Ferrer I M, et al. Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices [J]. J. Am. Chem. Soc., 2015, 137(13): 4347-4357.

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富氧空位Co₃O₄纳米线的制备及其电解水性能研究

Engineering oxygen vacancy-rich Co₃O₄ nanowire as high-efficiency and durable bifunctional electrocatalyst for overall alkaline water splitting

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