分步负载金属法制备铁钴双金属位点高效氧还原电催化剂

doi:10.11949/0438-1157.20240073

摘要/Abstract

摘要：

过渡金属和氮掺杂的碳（M-N-C）由于优异的电催化活性以及较低的生产成本，成为热门的铂基催化剂的替代者。然而，目前的M-N-C催化剂通常涉及金属盐、含氮物质和碳载体的结合，在经过热处理和酸洗过程后得到的催化剂在活性位点密度和传质能力上缺乏足够的性能。采用一种分步负载金属法制备了Fe、Co双金属掺杂的M-N-C催化剂。利用Zn²⁺和Co²⁺的竞争效应，成功合成了一个小尺寸且均匀的Zn-Co-ZIFs双金属沸石咪唑骨架。随后，在不形成金属团簇的前提下将最大量的Fe原子嵌入C-Zn-Co-ZIFs-H⁺前体结构中，使其在热解后能产生大量的FeCo-N _x 活性位点。这种改进显著增加了FeCo-N-C-2催化剂中Fe活性位点的含量（1.9%（质量分数）），并深度优化了其微孔和介孔结构（860 m²·g^-1）。该催化剂在0.1 mol·L^-1 HClO₄和0.1 mol·L^-1 KOH溶液中，氧还原反应（ORR）活性展现出了0.806 V和0.921 V的半波电位，并分别在50000、45000 s恒定电位测试后保持了91.21%和95.32%的活性。将其组装于质子交换膜燃料电池（PEMFCs）和碱性锌-空气液流电池（ZAFBs）中，其性能分别达到了746 mW·cm^-2和164 mW·cm^-2的峰值功率密度，显示出优越的性能。

关键词: 催化剂, 分步负载金属法, 铁钴双金属位点, 电化学, 氧还原反应, 燃料电池, 锌-空气液流电池

Abstract:

Transition metals and nitrogen-doped carbon (M-N-C) have risen to prominence as alternatives to platinum-based catalysts, acclaimed for their superior electrocatalytic activity and comparatively lower production costs. However, the current M-N-C catalysts typically involve the amalgamation of metal salts, nitrogenous substances, and a carbon substrate, which, following a singular thermal treatment and acid leaching process, yield catalysts that are deficient in sufficient performance with respect to the density of active sites and mass transfer capabilities. In this paper, Fe, Co bimetallic doped M-N-C catalysts were prepared by step-by-step metal loading method. Taking advantage of the competitive effect of Zn²⁺ and Co²⁺, a small-sized and uniform Zn-Co-ZIFs bimetallic zeolite imidazole framework was successfully synthesized. Subsequently, the maximum number of Fe atoms is embedded into the C-Zn-Co-ZIFs-H⁺ precursor structure without forming metal clusters, so that it can generate a large number of FeCo-N_x active sites after pyrolysis. This refinement engenders a substantial augmentation in the Fe active site content of the FeCo-N-C-2 catalyst (1.9 wt%), and a profound optimization of its microporous and mesoporous architecture (860 m²·g^-1), culminating in enhanced electrochemical activity and stability. The catalyst exhibited half-wave potentials (E_1/2) for oxygen reduction reaction (ORR) of 0.806 V in 0.1 mol·L^-1 HClO₄ and 0.921 V in 0.1 mol·L^-1 KOH, maintaining 91.21% and 95.32% of its activity respectively after 50,000/45000 seconds of a constant voltage test. Moreover, this catalyst has achieved peak power densities of 746 mW·cm^-2 in proton exchange membrane fuel cells (PEMFCs) and 164 mW·cm^-2 in alkaline zinc-air flow batteries (ZAFBs), demonstrating its superior performance.

Key words: catalyst, step-by-step metal loading method, iron and cobalt-based dual-metal site, electrochemistry, oxygen reduction reaction, fuel cells, zinc-air flow battery

中图分类号:

TQ152

贾旭东, 杨博龙, 程前, 李雪丽, 向中华. 分步负载金属法制备铁钴双金属位点高效氧还原电催化剂[J]. 化工学报, DOI: 10.11949/0438-1157.20240073.

Xudong JIA, Bolong YANG, Qian CHENG, Xueli LI, Zhonghua XIANG. Preparation of high-efficiency iron-cobalt bimetallic site oxygen reduction electrocatalysts by step-by-step metal loading method[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240073.

图/表 8

图1 FeCo-N-C-2催化剂的合成和形貌表征

Fig.1 Synthesis and morphological characterisation of FeCo-N-C-2 catalyst

图2 催化剂的结构表征

Fig.2 Structural characterisation of catalysts

图3 催化剂在酸性环境下的ORR电催化活性

Fig.3 ORR electrocatalytic activity of catalysts in acidic environment

图4 催化剂在碱性环境下的ORR、OER电催化活性

Fig.4 ORR, OER electrocatalytic activity of catalysts in alkaline environment

图5 催化剂的电池器件性能

Fig.5 Battery device performance of catalysts

表S1 FeCo-N-C-2催化剂与其他催化剂的酸性ORR性能比较

Table S1 Acid ORR properties of FeCo-N-C-2 catalyst compared with other catalysts

催化剂	电解液	E_onset	E_1/2	参考文献
FeCo-N-C-2	0.1 mol·L^-1 HClO₄	0.999 V	0.806 V	本文
f-FeCoNC900	0.1 mol·L^-1 HClO₄	0.870 V	0.810 V	[43]
FeCo₂-NPC-900	0.1 mol·L^-1 HClO₄	0.850 V	0.740 V	[44]
FeNi-N₆	0.1 mol·L^-1 HClO₄	0.900 V	0.790 V	[45]
Fe-Zn-SA/NC	0.1 mol·L^-1 HClO₄	0.870 V	0.780 V	[46]

表S2 FeCo-N-C-2催化剂与其他催化剂的碱性ORR性能比较

Table S2 Alkaline ORR properties of FeCo-N-C-2 catalyst compared with other catalysts

催化剂	电解液	E_1/2	参考文献
FeCo-N-C-2	0.1 mol·L^-1 KOH	0.921 V	本文
f-FeCoNC900	0.1 mol·L^-1 KOH	0.890 V	[43]
FeCo₂-NPC-900	0.1 mol·L^-1 KOH	0.870 V	[44]
Fe-Zn-SA/NC	0.1 mol·L^-1 KOH	0.850 V	[46]
FeCo-ISAs/CN	0.1 mol·L^-1 KOH	0.920 V	[47]

表S3 FeCo-N-C-2催化剂与其他催化剂的碱性OER性能比较

Table S3 Alkaline OER properties of FeCo-N-C-2 catalyst compared with other catalysts

催化剂	电解液	过电位	Tafel斜率	参考文献
FeCo-N-C-2	1 mol·L^-1 KOH	0.339 V	65.59 mV·dec^-1	本文
Co-Fe-N-C	1 mol·L^-1 KOH	0.309 V	37.00 mV·dec^-1	[48]
Fe₂/Co₁-GNCL	1 mol·L^-1 KOH	0.350 V	70.00 mV·dec^-1	[49]
CoDNi-N/C	1 mol·L^-1 KOH	0.360 V	72.00 mV·dec^-1	[50]
Fe-NiNC-50	1 mol·L^-1 KOH	0.340 V	54.00 mV·dec^-1	[51]

参考文献 51

1	Liu M Y, Xiao X D, Li Q, et al. Recent progress of electrocatalysts for oxygen reduction in fuel cells[J]. Journal of Colloid and Interface Science, 2022, 607(Pt 1): 791-815.
2	Wang X X, Cullen D A, Pan Y T, et al. Nitrogen-coordinated single cobalt atom catalysts for oxygen reduction in proton exchange membrane fuel cells[J]. Advanced Materials, 2018, 30(11)1706758
3	Wang M M, Lin M T, Li J T, et al. Metal–organic framework derived carbon-confined Ni₂P nanocrystals supported on graphene for an efficient oxygen evolution reaction[J]. Chemical Communications, 2017, 53(59): 8372-8375.
4	Wang Q, Meng Z, Li J T, et al. High retention volume covalent organic polymer for xenon capture: dynamic separation of Xe and Kr[J]. Green Energy and Environment, 2022, 7: 948-956.
5	Zhao Y, Zhang M, Wen X, et al. Microfluidic interface boosted synthesis of covalent organic polymer capsule[J]. Green Chemical Engineering, 2020, 1(1): 63-69.
6	Ding R, Zhang S Q, Chen Y W, et al. Application of machine learning in optimizing proton exchange membrane fuel cells: a review[J]. Energy and AI, 2022, 9: 100170.
7	Kodama K, Nagai T, Kuwaki A, et al. Challenges in applying highly active Pt-based nanostructured catalysts for oxygen reduction reactions to fuel cell vehicles[J]. Nature Nanotechnology, 2021, 16: 140-147.
8	Zhang J W, Yuan Y L, Gao L, et al. Stabilizing Pt-based electrocatalysts for oxygen reduction reaction: fundamental understanding and design strategies[J]. Advanced Materials, 2021, 33(20): e2006494.
9	Zhang B H, An G B, Chen J, et al. Surface state engineering of carbon dot/carbon nanotube heterojunctions for boosting oxygen reduction performance[J]. Journal of Colloid and Interface Science, 2023, 637: 173-181.
10	Hong Y S, Li L B, Huang B Y, et al. Molecular control of carbon-based oxygen reduction electrocatalysts through metal macrocyclic complexes functionalization[J]. Advanced Energy Materials, 2021, 11(33): 2100866.
11	Huang L, Zaman S, Tian X L, et al. Advanced platinum-based oxygen reduction electrocatalysts for fuel cells[J]. Accounts of Chemical Research, 2021, 54(2): 311-322.
12	Wang Y L, Shi R, Shang L, et al. Vertical graphene array for efficient electrocatalytic reduction of oxygen to hydrogen peroxide[J]. Nano Energy, 2022, 96: 107046.
13	Wang Y L, Waterhouse G I N, Shang L, et al. Electrocatalytic oxygen reduction to hydrogen peroxide: from homogeneous to heterogeneous electrocatalysis[J]. Advanced Energy Materials, 2021, 11(15): 2003323.
14	Li Y, Wang H H, Priest C, et al. Advanced electrocatalysis for energy and environmental sustainability via water and nitrogen reactions[J]. Advanced Materials, 2021, 33(6): e2000381.
15	Zhang B, Zheng Y J, Ma T, et al. Designing MOF nanoarchitectures for electrochemical water splitting[J]. Advanced Materials, 2021, 33(17): e2006042.
16	Xie X H, He C, Li B Y, et al. Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells[J]. Nature Catalysis, 2020, 3: 1044-1054.
17	Li J Z, Zhang H G, Samarakoon W, et al. Thermally driven structure and performance evolution of atomically dispersed FeN₄ sites for oxygen reduction[J]. Angewandte Chemie (International Ed. in English), 2019, 58(52): 18971-18980.
18	Pavlenko V, Khosravi H S, Żółtowska S, et al. A comprehensive review of template-assisted porous carbons: modern preparation methods and advanced applications[J]. Materials Science and Engineering: R: Reports, 2022, 149: 100682.
19	Sequeira C A C. Carbon anode in carbon history[J]. Molecules, 2020, 25(21): 4996.
20	Zhang H G, Osgood H, Xie X H, et al. Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks[J]. Nano Energy, 2017, 31: 331-350.
21	Ajmal S, Kumar A, Tabish M, et al. Modulating the microenvironment of single atom catalysts with tailored activity to benchmark the CO₂ reduction[J]. Materials Today, 2023, 67: 203-228.
22	Dong F, Wu M J, Zhang G X, et al. Defect engineering of carbon-based electrocatalysts for rechargeable zinc-air batteries[J]. Chemistry, an Asian Journal, 2020, 15(22): 3737-3751.
23	Sui X L, Zhang L, Li J J, et al. Advanced support materials and interactions for atomically dispersed noble-metal catalysts: from support effects to design strategies[J]. Advanced Energy Materials, 2022, 12(1): 2102556.
24	Maiti K, Maiti S, Curnan M T, et al. Engineering single atom catalysts to tune properties for electrochemical reduction and evolution reactions[J]. Advanced Energy Materials, 2021, 11(38): 2101670.
25	Menga D, Low J L, Li Y S, et al. Resolving the dilemma of Fe-N-C catalysts by the selective synthesis of tetrapyrrolic active sites via an imprinting strategy[J]. Journal of the American Chemical Society, 2021, 143(43): 18010-18019.
26	Aslam S, Khanna M, Kuanr B K. Fabrication of CoFe₂O₄/reduced graphene oxide nanocomposite as a microwave absorber[J]. Advanced Science Letters, 2018, 24(2): 903-906.
27	Yuldashova I I, Tashmetov M Y. The influence of electron beams to structure parameters of multi walled carbon nanotube[J]. Physica B: Condensed Matter, 2019, 571: 280-284.
28	Qiu T, Yang J G, Bai X J. Insight into the change in carbon structure and thermodynamics during anthracite transformation into graphite[J]. International Journal of Minerals, Metallurgy and Materials, 2020, 27(2): 162-172.
29	Ghosh A, do Amaral Razzino C, Dasgupta A, et al. Structural and electrochemical properties of babassu coconut mesocarp-generated activated carbon and few-layer graphene[J]. Carbon, 2019, 145: 175-186.
30	Zhao J, Mao J Y, Li Y R, et al. Friction-induced nano-structural evolution of graphene as a lubrication additive[J]. Applied Surface Science, 2018, 434: 21-27.
31	Maiti K, Balamurugan J, Peera S G, et al. Highly active and durable core-shell fct-PdFe@Pd nanoparticles encapsulated NG as an efficient catalyst for oxygen reduction reaction[J]. ACS Applied Materials & Interfaces, 2018, 10(22): 18734-18745.
32	Dong X B, Zhao C Y, Guan Q X, et al. Metal–organic framework-derived cobalt and nitrogen Co-doped porous carbon with four-coordinated Co–N _x for efficient acetylene hydrochlorination[J]. Applied Organometallic Chemistry, 2018, 32(12): e4570.
33	Singh S K, Takeyasu K, Nakamura J. Active sites and mechanism of oxygen reduction reaction electrocatalysis on nitrogen-doped carbon materials[J]. Advanced Materials, 2019, 31(13): e1804297.
34	Huang J W, Cheng Q Q, Huang Y C, et al. Highly efficient Fe–N–C electrocatalyst for oxygen reduction derived from core–shell-structured Fe(OH)₃@Zeolitic imidazolate framework[J]. ACS Applied Energy Materials, 2019, 2(5): 3194-3203.
35	Cui X Y, Yang S B, Yan X X, et al. Pyridinic-nitrogen-dominated graphene aerogels with Fe–N–C coordination for highly efficient oxygen reduction reaction[J]. Advanced Functional Materials, 2016, 26(31): 5708-5717.
36	Cui X, Gao L K, Lei S, et al. Simultaneously crafting single-atomic Fe sites and graphitic layer-wrapped Fe₃C nanoparticles encapsulated within mesoporous carbon tubes for oxygen reduction[J]. Advanced Functional Materials, 2021, 31(10): 2009197.
37	Tang F, Lei H T, Wang S J, et al. A novel Fe-N-C catalyst for efficient oxygen reduction reaction based on polydopamine nanotubes[J]. Nanoscale, 2017, 9(44): 17364-17370.
38	Jiang H L, Yao Y F, Zhu Y H, et al. Iron carbide nanoparticles encapsulated in mesoporous Fe-N-doped graphene-like carbon hybrids as efficient bifunctional oxygen electrocatalysts[J]. ACS Applied Materials & Interfaces, 2015, 7(38): 21511-21520.
39	Li X L, Liu Q B, Yang B L, et al. An initial covalent organic polymer with closed-F edges directly for proton-exchange-membrane fuel cells[J]. Advanced Materials, 2022, 34(36): e2204570.
40	Jiang J, Zhang A L, Li L L, et al. Nickel–cobalt layered double hydroxide nanosheets as high-performance electrocatalyst for oxygen evolution reaction[J]. Journal of Power Sources, 2015, 278: 445-451.
41	Manivasakan P, Ramasamy P, Kim J. Use of urchin-like Ni(x)Co(3-x)O₄ hierarchical nanostructures based on non-precious metals as bifunctional electrocatalysts for anion-exchange membrane alkaline alcohol fuel cells[J]. Nanoscale, 2014, 6(16): 9665-9672.
42	Wang J, Li L Q, Chen X, et al. A Co-N/C hollow-sphere electrocatalyst derived from a metanilic CoAl layered double hydroxide for the oxygen reduction reaction, and its active sites in various pH media[J]. Nano Research, 2017, 10(7): 2508-2518.
43	Zhang G X, Jia Y, Zhang C, et al. A general route via formamide condensation to prepare atomically dispersed metal–nitrogen–carbon electrocatalysts for energy technologies[J]. Energy & Environmental Science, 2019, 12(4): 1317-1325.
44	Fang X Z, Jiao L, Yu S H, et al. Metal-organic framework-derived FeCo-N-doped hollow porous carbon nanocubes for electrocatalysis in acidic and alkaline media[J]. ChemSusChem, 2017, 10(15): 3019-3024.
45	Zhou Y D, Yang W, Utetiwabo W, et al. Revealing of active sites and catalytic mechanism in N-coordinated Fe, Ni dual-doped carbon with superior acidic oxygen reduction than single-atom catalyst[J]. The Journal of Physical Chemistry Letters, 2020, 11(4): 1404-1410.
46	Xu J, Lai S H, Qi D F, et al. Atomic Fe-Zn dual-metal sites for high-efficiency pH-universal oxygen reduction catalysis[J]. Nano Research, 2021, 14(5): 1374-1381.
47	Zhang D Y, Chen W X, Li Z, et al. Isolated Fe and Co dual active sites on nitrogen-doped carbon for a highly efficient oxygen reduction reaction[J]. Chemical Communications, 2018, 54(34): 4274-4277.
48	Bai L C, Hsu C S, Alexander D T L, et al. A cobalt-iron double-atom catalyst for the oxygen evolution reaction[J]. Journal of the American Chemical Society, 2019, 141(36): 14190-14199.
49	Wei Y S, Sun L M, Wang M, et al. Fabricating dual-atom iron catalysts for efficient oxygen evolution reaction: a heteroatom modulator approach[J]. Angewandte Chemie (International Ed. in English), 2020, 59(37): 16013-16022.
50	Li Z H, He H Y, Cao H B, et al. Atomic Co/Ni dual sites and Co/Ni alloy nanoparticles in N-doped porous Janus-like carbon frameworks for bifunctional oxygen electrocatalysis[J]. Applied Catalysis B: Environmental, 2019, 240: 112-121.
51	Zhu X F, Zhang D T, Chen C J, et al. Harnessing the interplay of Fe–Ni atom pairs embedded in nitrogen-doped carbon for bifunctional oxygen electrocatalysis[J]. Nano Energy, 2020, 71: 104597.

[1]	齐元帅, 彭文朝, 李阳, 张凤宝, 范晓彬. 电化学脱盐机理及相关研究进展[J]. 化工学报, 2024, 75(1): 171-189.
[2]	张家琳, 徐大为, 高越, 李新刚. 泡沫镍负载CeO₂改性CuO催化剂的碳烟燃烧性能研究[J]. 化工学报, 2024, 75(1): 312-321.
[3]	王雪杰, 崔国庆, 王文涵, 杨扬, 王淙恺, 姜桂元, 徐春明. 电内加热Pt/NPC催化剂高效催化甲基环己烷脱氢反应研究[J]. 化工学报, 2024, 75(1): 292-301.
[4]	张强, 王宪飞, 王凯, 骆广生, 路忠凯. 非金属催化剂在环氧化物和环状酸酐共聚中的研究进展[J]. 化工学报, 2024, 75(1): 60-73.
[5]	王欣雨, 王永涛, 姚加, 李浩然. 电子顺磁共振技术在化工基础研究中的应用进展[J]. 化工学报, 2024, 75(1): 74-82.
[6]	闻文, 王慧艳, 周静红, 曹约强, 周兴贵. 石墨负极颗粒对锂离子电池容量衰减及SEI膜生长影响的模拟研究[J]. 化工学报, 2024, 75(1): 366-376.
[7]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[8]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[9]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[10]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[11]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[12]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[13]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[14]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[15]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.