Preparation of Ni-NiO/N-C electrocatalyst and its performance for water splitting into hydrogen
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摘要: 电催化分解水制氢(HER)被认为是最具应用前景的能量转换方式之一，可同时获得高纯度氢气并实现能量储存与转化，其关键在于低廉、高效且高稳定HER电催化剂的设计与开发。采用一步水热法得到羟基氧化镍/聚苯胺(NiOOH/PANI)催化剂前驱体，经800℃热解后制备出Ni-NiO/N-C负载型电催化剂，并考察其HER性能。采用XRD、SEM、TEM、BET、XPS和Raman等手段对催化剂的物理化学属性进行表征，结果表明催化剂主要呈现出均匀的碳纳米片状堆积结构，Ni和NiO同时存在且均匀分布在载体N-C表面。电化学性能测试结果表明该催化剂的催化性能与催化剂中金属Ni的相对含量密切相关，当前驱体中苯胺添加量为0.6 mL时，所得催化剂Ni-NiO/N-C-0.6上金属Ni相对含量最高，电催化性能最好，在电流密度为10 mA·cm−2时过电位仅为168 mV，且连续工作16 h或经历1000次循环伏安测试后，催化活性基本不变，展现出优异的催化稳定性，具有广阔的应用前景。Abstract: The hydrogen production from hydrogen evolution reaction (HER) in electrochemical water splitting is considered to be one of the most promising energy conversion methods, which can simultaneously obtain high purity hydrogen and realize energy storage and conversion. The key depends on the development of HER electrocatalysts with high efficiency, high stability and low price. A series of NiOOH/polyaniline (NiOOH/PANI) catalyst precursors were prepared via one-pot hydrothermal method. After pyrolysis at 800°C, the Ni-NiO/N-C electrocatalysts were obtained and applied to HER. The XRD, SEM, TEM, BET, XPS and Raman spectroscopy were conducted to analyze the physical and chemical properties of the catalysts. Results show that the catalysts are present in the nanosheet morphology, the nickel and nickel oxide are coexisted and highly dispersed in the carbon support. The results of HER tests demonstrate that the catalytic performance is closely related with the content of nickel in the catalyst, and the Ni-NiO/N-C-0.6 catalyst with the aniline addition of 0.6 mL exhibits the best performance for HER, which has an overpotential of only 168 mV at a current density of 10 mA·cm−2. Besides, the catalyst also has good catalytic stability with almost no detectable activity decay after 16 h HER test or 1000 times of cyclic voltammetry measurements, demonstrating broad application prospects.
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Key words:
- hydrogen energy /
- electrochemical water splitting /
- catalyst /
- nickel /
- nickel oxide /
- nitrogen doped carbon
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图 1 Ni-NiO/N-C催化剂前驱体(a)和催化剂样品的XRD图谱 (b)
Figure 1. XRD patterns of prepared Ni-NiO/N-C catalyst precursors (a) and catalysts (b)
图 2 NiOOH/PANI-0.6 (a)、Ni-NiO/N-C-0.6 (b) 的FESEM图像，Ni-NiO/N-C-0.6催化剂的元素分布图 ((c)~(g))，Ni-NiO/N-C-0.6的HRTEM (h) 和选取电子衍射(SAED) (i) 图像
Figure 2. FESEM images of NiOOH/PANI-0.6 (a), Ni-NiO/N-C-0.6 (b), elemental mapping images ((c)-(g)), HRTEM (h) and selected area electron diffraction (SAED) (i) images of Ni-NiO/N-C-0.6
图 3 Ni-NiO/N-C催化剂的拉曼光谱图
Figure 3. Raman spectra of the prepared Ni-NiO/N-C catalysts
ID/IG—Intensity ratio of peak D to peak G
图 4 Ni-NiO/N-C催化剂的N2吸/脱附曲线图(a)和对应的孔径分布图(b)
Figure 4. N2 adsorption/desorption curves (a) and the corresponding pore size distributions (b) of the prepared Ni-NiO/N-C catalysts
图 5 Ni-NiO/N-C催化剂样品的全谱 (a)、Ni2p3/2 (b)、N1s (c) 和C1s (d) 的XPS光谱图
Figure 5. XPS spectra of survey spectra (a), Ni2p3/2 (b)，N1s (c) and C1s (d) for Ni-NiO/N-C catalyst samples
图 6 Ni-NiO/N-C催化剂在1.0 mol/L KOH溶液中的线性扫描伏安(LSV)图 (a)、塔菲尔(Tafel)斜率图 (b)、电流密度分别为1 mA·cm−2和10 mA·cm−2时的过电位和Tafel斜率柱状图 (c) 及交流阻抗图 (d)
Figure 6. Linear sweep voltammetry (LSV) curves (a), Tafel plots (b), bar graph of overpotentials at 1 mA·cm−2 and 10 mA·cm−2, and the Tafel slope (c) and electrochemical impedance spectroscopy (d) of Ni-NiO/N-C catalysts
图 7 N-C (a)、Ni-NiO/N-C-0.4 (b)、Ni-NiO/N-C-0.6 (c) 和Ni-NiO/N-C-0.8 (d) 在不同扫速下的伏安分析(CV)曲线和双层电容曲线 (e)
Figure 7. Voltammetry analysis (CV) curves at different scan rates of N-C (a), Ni-NiO/N-C-0.4 (b), Ni-NiO/N-C-0.6 (c), Ni-NiO/N-C-0.8 (d), and the capacitive current densities plotted against scan rate (e)
图 8 Ni-NiO/N-C-0.6和Pt/C催化剂的计时电流(i-t)曲线(a)、Ni-NiO/N-C-0.6催化剂在计时电流曲线前后(b)及在连续循环1000个CV前后(c)的LSV极化曲线
Figure 8. Aamperometric timing current (i-t) curves of Ni-NiO/N-C-0.6 and Pt/C catalysts (a), linear sweep voltammetry (LSV) curves of Ni-NiO/N-C-0.6 catalysts before and after the chronocurrent curves (b) and 1000 CV cycles (c)
表 1 Ni-NiO/N-C催化剂样品的比表面积和孔体积数据
Table 1. Specific surface area and pore volume of Ni-NiO/N-C catalyst samples
Sample SBET/(m2·g−1) Pv/(cm3·g−1) N-C 299.33 1.88 Ni-NiO/N-C-0.4 361.40 3.41 Ni-NiO/N-C-0.6 381.75 4.61 Ni-NiO/N-C-0.8 388.25 7.47 Notes: SBET—Specific surface area; Pv—Pore volume. 
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表 2 Ni-NiO/N-C催化剂中各种元素的含量
Table 2. Contents of different elements in the Ni-NiO/N-C catalysts
Sample C/at% N/at% Ni/at% O/at% N-C 81.35 7.32 — 6.41 Ni-NiO/N-C-0.4 84.90 7.06 1.62 9.64 Ni-NiO/N-C-0.6 83.39 7.74 2.20 5.61 Ni-NiO/N-C-0.8 84.84 6.72 2.84 11.32
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[1] LEWIS N S, NOCERA D G. Powering the planet: Chemical challenges in solar energy utilization[J]. Proceedings of the National Academy of Sciences,2006,103(43):15729-15735. doi: 10.1073/pnas.0603395103 [2] 蔡昊源. 电解水制氢方式的原理及研究进展[J]. 环境与发展, 2020, 32(5):129-131.CAI H Y. Principle and research progress of hydrogen production by electrolyzing water[J]. Environment& Development,2020,32(5):129-131(in Chinese). [3] CHENG N, STAMBULA S, WANG D, et al. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction[J]. Nature Communications,2016,7:13638. doi: 10.1038/ncomms13638 [4] WANG C H, HU F, YANG H C, et al. 1.82 wt% Pt/N, P co-doped carbon overwhelms 20 wt% Pt/C as a high-efficiency electrocatalyst for hydrogen evolution reaction[J]. Nano Research,2017,10(1):1-9. doi: 10.1007/s12274-016-1283-7 [5] GONG M, ZHOU W, TSAI M C, et al. Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis[J]. Nature Communications,2014,5:4695. doi: 10.1038/ncomms5695 [6] CHEN Z L, WU R B, LIU Y, et al. Ultrafine Co nanoparticles encapsulated in carbon-nanotubes-grafted graphene sheets as advanced electrocatalysts for the hydrogen evolution reaction[J]. Advanced Materials,2018,30(30):1802011. doi: 10.1002/adma.201802011 [7] JIN X X, WANG R Y, ZHANG L X, et al. Electron configuration modulation of Ni single atoms for remarkably elevated photocatalytic hydrogen evolution[J]. Angewandte Chemie International Edition,2020,59(17):6827-6831. doi: 10.1002/anie.201914565 [8] ZHENG X L, XU J B, YAN K Y, et al. Space-confined growth of MoS2 nanosheets within graphite: The layered hybrid of MoS2 and graphene as an active catalyst for hydrogen evolution reaction[J]. Chemistry of Materials,2014,26(7):2344-2353. doi: 10.1021/cm500347r [9] LV X, YIN S. CoP-embedded nitrogen and phosphorus co-doped mesoporous carbon nanotube for efficient hydrogen evolution[J]. Applied Surface Science,2021,537:147834. doi: 10.1016/j.apsusc.2020.147834 [10] PU Z H, WANG M, KOU Z K, et al. Mo2C quantum dot embedded chitosan-derived nitrogen-doped carbon for efficient hydrogen evolution in a broad pH range[J]. Chemical Communications,2016,52(86):12753-12756. doi: 10.1039/C6CC06267A [11] ANANTHARAJ S, KUNDU S, NODA S. Progress in nickel chalcogenide electrocatalyzed hydrogen evolution reaction[J]. Journal of Materials Chemistry A,2020,8(8):4174-4192. doi: 10.1039/C9TA14037A [12] POPCZUN E J, MCKONE J R, READ C G, et al. Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction[J]. Journal of the American Che-mical Society,2013,135(25):9267-9270. doi: 10.1021/ja403440e [13] CHEN W F, SASAKI K, MA C, et al. Hydrogen-evolution catalysts based on non-noble metal nickel-molybdenum nitride nanosheets[J]. Angewandte Chemie International Edition,2012,51(25):6131-6135. doi: 10.1002/anie.201200699 [14] LOVELL E C, LU X Y, ZHANG Q R, et al. From passivation to activation-tunable nickel/nickel oxide for hydrogen evolution electrocatalysis[J]. Chemical Communications,2020,56(11):1709-1712. doi: 10.1039/C9CC07486D [15] LASZCYSKA A, SZCZYGIE I. Electrocatalytic activity for the hydrogen evolution of the electrodeposited Co–Ni–Mo, Co–Ni and Co–Mo alloy coatings[J]. International Journal of Hydrogen Energy,2020,45(1):508-520. doi: 10.1016/j.ijhydene.2019.10.181 [16] MILES M H, THOMASON M A. Periodic variations of overvoltages for water electrolysis in acid solutions from cyclic voltametric studies. [31 metals as electrocatalysts][J]. Journal of the Electrochemical Society,1976,123(10):1459-1461. doi: 10.1149/1.2132619 [17] DUTTA S, HAN H, JE M, et al. Chemical and structural engineering of transition metal boride towards excellent and sustainable hydrogen evolution reaction[J]. Nano Energy,2019,67:104245. [18] YANG J, WU H L, ZHU M, et al. Optimized mesopores enabling enhanced rate performance in novel ultrahigh surface area meso-/microporous carbon for supercapacitors[J]. Nano Energy,2017,33:453-461. doi: 10.1016/j.nanoen.2017.02.007 [19] BIN D, YANG B B, LI C, et al. In situ growth of NiFe alloy nanoparticles embedded into N-doped bamboo-like carbon nanotubes as a bifunctional electrocatalyst for Zn-Air batteries[J]. ACS Applied Materials & Interfaces,2018,10(31):26178-26187. [20] 张玉晖, 易清风. 铁/钴质量比对MWCNT-聚苯胺复合物氧还原电活性的影响[J]. 化工学报, 2014, 65(6):2113-2119. doi: 10.3969/j.issn.0438-1157.2014.06.023ZHANG Y H, YI Q F. Effect of Fe/Co mass ratio on activity of non-noble metal catalyst for oxygen reduction reaction[J]. Journal of Chemical Industry and Engineering (China),2014,65(6):2113-2119(in Chinese). doi: 10.3969/j.issn.0438-1157.2014.06.023 [21] WU S D, LV X N, PIN D, et al. Highly exposed atomic Fe-N active sites within carbon nanorods towards electrocatalytic reduction of CO2 to CO[J]. Electrochimica Acta,2020,340:135930. doi: 10.1016/j.electacta.2020.135930 [22] AHN S H, HWANG S J, YOO S J, et al. Electrodeposited Ni dendrites with high activity and durability for hydrogen evolution reaction in alkaline water electrolysis[J]. Jour-nal of Materials Chemistry,2012,22(30):15153-15159. doi: 10.1039/c2jm31439h [23] 魏强, 孙慧, 钱君超, 等. CeO2/石墨烯的合成及其在光催化制氢中的应用[J]. 复合材料学报, 2018, 35(3):684-689.WEI Q, SUN H, QIAN J C, et al. Synthesis of CeO2/graphene and its application in photocatalytic hydrogen production[J]. Acta Materiae Compositae Sinica,2018,35(3):684-689(in Chinese). [24] CHEN Y F, LI Z J, ZHU Y B, et al. Atomic Fe dispersed on N-doped carbon hollow nanospheres for high-efficiency electrocatalytic oxygen reduction[J]. Advanced Materials,2019,31(8):1806312. doi: 10.1002/adma.201806312 [25] KHANI H, GRUNDISH N S, WIPF D O, et al. Graphitic-shell encapsulation of metal electrocatalysts for oxygen evolution, oxygen reduction, and hydrogen evolution in alkaline solution[J]. Advanced Energy Materials,2020,10(1):1903215. doi: 10.1002/aenm.201903215 [26] LAI F L, MIAO Y E, HUANG Y P, et al. Nitrogen-doped carbon nanofiber/molybdenum disulfide nanocomposites derived from bacterial cellulose for high-efficiency electrocatalytic hydrogen evolution reaction[J]. ACS Applied Materials & Interfaces,2016,8(6):3558-3566. [27] GOEL C, BHUNIA H, BAJPAI P K. Synthesis of nitrogen doped mesoporous carbons for carbon dioxide capture[J]. RSC Advances,2015,5(58):46568-46582. doi: 10.1039/C5RA05684E [28] YAN X X, GU M Y, WANG Y, et al. In-situ growth of Ni nanoparticle-encapsulated N-doped carbon nanotubes on carbon nanorods for efficient hydrogen evolution electrocatalysis[J]. Nano Research,2020,13(4):975-982. doi: 10.1007/s12274-020-2727-7 [29] ZENG M, LI Y G. Recent advances in heterogeneous electrocatalysts for the hydrogen evolution reaction[J]. Jour-nal of Materials Chemistry A,2015,3(29):14942-14962. doi: 10.1039/C5TA02974K [30] CASTELO-QUIBÉN J, ABDELWAHAB A, PÉREZ-CADENAS M, et al. Carbon-iron electro-catalysts for CO2 reduction. The role of the iron particle size[J]. Journal of CO2 Utilization,2018,24:240-249. doi: 10.1016/j.jcou.2018.01.007 [31] 曾庆乐, 刘小超, 刘超, 等. Co2Ni1O4/不锈钢复合材料的制备及其电催化析氧性能[J]. 复合材料学报, 2021, 38(11):3764-3774.ZENG Q L, LIU X C, LIU C, et al. Synthesis and electrocatalytic oxygen evolution performances of Co2Ni1O4/stainless steel composites[J]. Acta Materiae Compositae Sinica,2021,38(11):3764-3774(in Chinese). -
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