氮掺杂碳球负载原子调控的铁-钴镍黄铁矿用于高效氧催化反应

doi:10.1016/S1872-2067(21)63932-3

催化学报 ›› 2022, Vol. 43 ›› Issue (6): 1502-1510.DOI: 10.1016/S1872-2067(21)63932-3

氮掺杂碳球负载原子调控的铁-钴镍黄铁矿用于高效氧催化反应

李斯杰, 谢涌, 赖碧琳, 梁瑛敏, 肖抗, 欧阳婷, 李楠^*(), 刘兆清^#()

广州大学化学化工学院, 清洁能源材料研究所, 教育部清洁能源材料广州重点实验室, 广东广州510006

收稿日期:2021-08-18 接受日期:2021-08-18 出版日期:2022-06-18 发布日期:2022-04-14
通讯作者: 李楠,刘兆清
基金资助:
国家自然科学基金(21875048);广东省自然科学基金(2020B1515020028);广东省自然科学基金(2020A1515011551);广东省高校重点科技项目(2017KZDXM059);广州市羊城学者项目(201831820);广州市科技计划项目(202002010007);广州市科技计划项目(202102010484);广东省大学生攀登计划项目(pdjh2020b0469)

Atomic modulation of Fe-Co pentlandite coupled with nitrogen-doped carbon sphere for boosting oxygen catalysis

Si-Jie Li, Yong Xie, Bi-Lin Lai, Yingmin Liang, Kang Xiao, Ting Ouyang, Nan Li^*(), Zhao-Qing Liu^#()

Institute of Clean Energy and Materials, Guangzhou Key Laboratory for Clean Energy and Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou Higher Education Mega Center, Guangzhou 510006, Guangdong, China

Received:2021-08-18 Accepted:2021-08-18 Online:2022-06-18 Published:2022-04-14
Contact: Nan Li, Zhao-Qing Liu
Supported by:
National Natural Science Foundation of China(21875048);Guangdong Natural Science Foundation(2020B1515020028);Guangdong Natural Science Foundation(2020A1515011551);Major Scientific Project of Guangdong University(2017KZDXM059);Yangcheng Scholars Research Project of Guangzhou(201831820);Science and Technology Research Project of Guangzhou(202002010007);Science and Technology Research Project of Guangzhou(202102010484);College Student Climbing Program(pdjh2020b0469)

摘要/Abstract

摘要：

化石能源的过度消耗使开发新能源成为当务之急, 燃料电池被认为是一种极具发展前景的高效能源转换装置. 氧还原反应(ORR)和氧析出反应(OER)是燃料电池中至关重要的可逆氧电催化反应. 由于氧反应的动力学迟缓, 通常需要使用贵金属Pt和IrO₂分别催化ORR和OER反应. 但其储量有限、价格高, 因此, 亟待开发廉价高效的氧反应催化剂. Co₉S₈属于镍黄铁矿晶型, 由于其具有特殊的d带结构, 被认为是一种多功能的电催化剂. Co₉S₈具有O_h构型的八面体位点和扭曲的C_3v四面体位点, S的配位场效应诱导Co₉S₈中八面体Co的未成对电子在较低的费米能级上分裂成t_2g和e_g能带. 基于d带理论, d带中心向费米能级的靠近有利于反键轨道的填充和更强的键合, 为进一步优化Co₉S₈的电子结构提供了思路.
本文以间苯二酚、甲醛和正硅酸四乙酯进行液相自发成核反应, 由于SiO₂球和酚醛树脂的聚合速率不同形成了RF@SiO₂封装结构. 经过高温碳化和碱蚀刻后, 酚醛树脂外壳发生碳化并塌陷, 形成了碗状的氮掺杂空心碳球(NHCS). 然后将铁原子引入到Co₉S₈中并锚定在空心碳球上, 制备了不同铁含量的Fe_xCo_9‒_xS₈-NHCS复合催化剂. 铁既可以占据钴镍黄铁矿结构中的八面体位, 也可以占据四面体位. 表征结果表明, 当铁钴的比例不超过1:8时, 低自旋的Fe²⁺首先占据八面体位点; 当铁钴的比例超过1:8时, 四面体位的Co也可以被高自旋的Fe²⁺取代. XPS结果表明, 在引入Fe²⁺后, Fe_xCo_9‒_xS₈-NHCS中的Co²⁺峰和Co⁰峰位置都产生了明显的偏移, 表明Fe²⁺在八面体位的占位会影响到四面体位的Co原子, 进而有可能影响到电化学性能. 结合Fe_xCo_9‒_xS₈-NHCS的ORR和OER性能测试结果和结构表征数据可以看出, 当Fe原子的系数x由0增至1, 此时Fe²⁺发生八面体位取代, 金属‒硫键的键长也相应增加, 从而提高了电催化活性. 当x由1增加到4.5, 此时Fe²⁺发生四面体位取代, 电催化活性降低. 因此, 铁钴的比例为1:8的复合催化剂在0.1 mol/L KOH中表现出了较好的ORR (E_1/2 = 0.80 V vs. RHE)和OER (E_j=10 = 1.53 V vs. RHE)双功能电催化性能. 最后, 将最优比的铁钴(铁钴的比例为1:8)复合催化剂应用于碱性的可充电锌空气电池和中性环境的微生物燃料电池. 具有复合催化剂阴极的锌空气电池和微生物燃料电池都表现出高功率密度和较好的稳定性, 证实本文所开发的催化剂具有较好的应用价值. 综上, 本文不仅提出了一种合成高效催化剂的新策略, 也还为促进钴镍黄铁矿结构氧催化剂的发展提供了重要的启示.

关键词: 氧电催化, 过渡金属硫化物, 氮掺杂碳, 钴镍黄铁矿结构, 锌-空气电池

Abstract:

Reversible oxygen reaction plays a crucial role in rechargeable battery systems, but it is limited by the slow reaction kinetics. Herein, the ionic modulation of cobalt pentlandite coupled with nitrogen-doped bowl-like hollow carbon sphere is well designed on octahedral and tetrahedral sites. The robust Fe_xCo_9-_xS₈-NHCS-V with iron replacing at the octahedron possesses prolonged metal sulfur bond and exhibits excellent bifunctional electrocatalytic performance towards oxygen reduction reaction (ORR, E_1/2 = 0.80 V vs. RHE) and excellent oxygen evolution reaction (OER, E_j_{= 10} = 1.53 V vs. RHE) in 0.1 mol/L KOH. Accordingly, a rechargeable Zn-air battery of Fe_xCo_9-_xS₈-NHCS-V cathode endows high energy efficiency (102 mW cm^-2), and a microbial fuel cell achieves a high-power density (791 ± 42 mW m ^-2), outperforming the benchmark Pt/C catalyst.

Key words: Oxygen electrocatalysis, Transition metal sulfide, Nitrogen-doped carbon, Pentlandite structure, Zinc-air battery

李斯杰, 谢涌, 赖碧琳, 梁瑛敏, 肖抗, 欧阳婷, 李楠, 刘兆清. 氮掺杂碳球负载原子调控的铁-钴镍黄铁矿用于高效氧催化反应[J]. 催化学报, 2022, 43(6): 1502-1510.

Si-Jie Li, Yong Xie, Bi-Lin Lai, Yingmin Liang, Kang Xiao, Ting Ouyang, Nan Li, Zhao-Qing Liu. Atomic modulation of Fe-Co pentlandite coupled with nitrogen-doped carbon sphere for boosting oxygen catalysis[J]. Chinese Journal of Catalysis, 2022, 43(6): 1502-1510.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63932-3

https://www.cjcatal.com/CN/Y2022/V43/I6/1502

图/表 7

Fig. 1. Schematic illustration of the synthetic procedure of FexCo9-xS8-NHCS.

Fig. 2. XRD patterns (a), enlarged XRD patterns (b), high-resolution XPS spectra (c) of Co 2p of FexCo9-xS8-NHCSs. (d) Experimental Mössbauer spectroscopy of FexCo9-xS8-NHCS-V at room temperature. (e) Scheme of atomic modulation in pentlandite structure.

Fig. 3. SEM (a-c), TEM (d), HRTEM (e), SAED (f), STEM (g) and EDX elemental mapping (h-k) images of FexCo9-xS8-NHCS-V.

Fig. 4. ORR (a) and OER (b) polarization curves in 0.1 mol/L KOH solution at 1600 r/min. Tafel slopes (c), frequency (d) of the A1g Raman-active mode as a function of composition (x) in FexCo9-xS8-NHCSs. (e) Chronoamperometry curves of FexCo9-xS8-NHCS-V and Pt/C at E = 0.5 V. (f) Faradic efficiency test of FexCo9-xS8-NHCS-V at 10 mA cm-2.

Fig. 5. Open circuit plots (a) and charging-discharging polarization plots (b) of Zn-air batteries. (c) Discharging polarization curves and the corresponding power curves. (d) Long-term charging and discharging with FexCo9-xS8-NHCS-V and Pt/C & IrO2 as the air cathode.

Fig. 6. The high-resolution XPS spectra of Co 2p (a) and Fe 2p (b) and S 2p (c) of FexCo9-xS8-NHCS-Vs before electrochemical test, after ORR stability test, after OER stability test and after cyclic performance in zinc-air battery.

Fig. 7. (a) Scheme of FexCo9-xS8-NHCS-V applied as a cathode in MFC. Cell voltage versus time curves (b) and Power density with the corresponding cell voltage curves of FexCo9-xS8-NHCS-V (c) and Pt/C (d).

参考文献

[1]	L. Yang, X. Zeng, W. Wang, D. Cao, Adv. Funct. Mater., 2018, 28, 1704537.
[2]	Y. Li, R. Cao, L. Li, X. Tang, T. Chu, B. Huang, K. Yuan, Y. Chen, Small, 2020, 16, 1906735.
[3]	K. Tang, C. Yuan, Y. Xiong, H. Hu, M. Wu, Appl. Catal. B, 2020, 260, 118209.
[4]	S. Li, C. Cheng, A. Thomas, Adv. Mater., 2017, 29, 1602547.
[5]	H. Yuan, Y. Hou, I. M Abu-Reesh, J. Chen, Z. He, Mater. Horiz., 2016, 3, 382-401.
[6]	X. T. Wang, T. Ouyang, L. Wang, J. H. Zhong, Z. Q. Liu, Angew. Chem. Int. Ed., 2020, 59, 6492-6499.
[7]	H. F. Wang, C. Tang, B. Wang, B. Q. Li, Q. Zhang, Adv. Mater., 2017, 29, 1702327.
[8]	H. B. Tao, J. Zhang, J. Chen, L. Zhang, Y. Xu, J. G. Chen, B. Liu, J. Am. Chem. Soc., 2019, 141, 13803-13811.
[9]	J. Wang, Z. Huang, W. Liu, C. Chang, H. Tang, Z. Li, W. Chen, C. Jia, T. Yao, S. Wei, J. Am. Chem. Soc., 2017, 139, 17281-17284.
[10]	P. Geng, S. Zheng, H. Tang, R. Zhu, L. Zhang, S. Cao, H. Xue, H. Pang, Adv. Energy Mater., 2018, 8, 1703259.
[11]	G. Zhang, D. Chen, N. Li, Q. Xu, H. Li, J. He, J. Lu, Angew. Chem. Int. Ed., 2020, 59, 8255-8261.
[12]	S. Chen, J. Luo, N. Li, X. Han, J. Wang, Q. Deng, Z. Zeng, S. Deng, Energy Storage Mater., 2020, 30, 187-195.
[13]	S. Wang, B. Y. Guan, X. Wang, X. W. Lou, J. Am. Chem. Soc., 2018, 140, 15145-15148.
[14]	X. Li, K. Li, S. Zhu, K. Fan, L. Lyu, H. Yao, Y. Li, J. Hu, H. Huang, Y. W. Mai, J. B. Goodenough, Angew. Chem. Int. Ed., 2019, 58, 6239-6243.
[15]	Q. Yang, Q. Wang, Y. Long, F. Wang, L. Wu, J. Pan, J. Han, Y. Lei, W. Shi, S. Song, Adv. Energy Mater., 2020, 10, 1903193.
[16]	H. Lin, S. Zhang, T. Zhang, S. Cao, H. Ye, Q. Yao, G. W. Zheng, J. Y. Lee, ACS Nano, 2019, 13, 7073-7082.
[17]	Y. Yang, H. Yao, Z. Yu, S. M. Islam, H. He, M. Yuan, Y. Yue, K. Xu, W. Hao, G. Sun, H. Li, S. Ma, P. Zapol, M. G. Kanatzidis, J. Am. Chem. Soc., 2019, 141, 10417-10430.
[18]	Y. Huang, X. Hu, J. Li, J. Zhang, D. Cai, B. Sa, H. Zhan, Z. Wen, Energy Storage Mater., 2020, 29, 121-130.
[19]	Y. Liu, S. Ma, L. Liu, J. Koch, M. Rosebrock, T. Li, F. Bettels, T. He, H. Pfnür, N. C. Bigall, A. Feldhoff, F. Ding, L. Zhang, Adv. Funct. Mater., 2020, 30, 2002462.
[20]	H. R. Chauke, D. Nguyen-Manh, P. E. Ngoepe, D. G. Pettifor, S. G. Fries, Phys. Rev. B, 2002, 66, 155105.
[21]	G. G. Hoffman, J. K. Bashkin, M. Karplus, J. Am. Chem. Soc., 1990, 112, 8705-8714.
[22]	J. K. Burdett, G. J. Miller, J. Am. Chem. Soc., 1987, 109, 4081-4091
[23]	Z. Wang, Z. Lin, J. Deng, S. Shen, F. Meng, J. Zhang, Q. Zhang, W. Zhong, L. Gu, Adv. Energy Mater., 2021, 11, 2003023.
[24]	B. Qiu, L. Cai, Y. Wang, X. Guo, S. Ma, Y. Zhu, Y. H. Tsang, Z. Zheng, R. Zheng, Y. Chai, Small, 2019, 15, 1904507.
[25]	W. Li, Y. Li, H. Fu, G. Yang, Q. Zhang, S. Chen, F. Peng, Chem. Eng. J., 2020, 381, 122683.
[26]	X. T. Wang, T. Ouyang, L. Wang, J. H. Zhong, T. Ma, Z. Q. Liu, Angew. Chem. Int. Ed., 2019, 58, 13291-13296.
[27]	H. Wang, R. Liu, Y. Li, X. Lü, Q. Wang, S. Zhao, K. Yuan, Z. Cui, X. Li, S. Xin, R. Zhang, M. Lei, Z. Lin, Joule, 2018, 2, 337-348.
[28]	Z. Y. Wang, S. D. Jiang, C. Q. Duan, D. Wang, S. H. Luo, Y. G. Liu, Rare Metals., 2020, 39, 1383-1394.
[29]	Z. Zhou, J. Zheng, R. Shi, N. Zhang, J. Chen, R. Zhang, H. Suo, E. M. Goldys, C. Guo, ACS Appl. Mater. Interfaces, 2017, 9, 6177-6185.
[30]	C. Chen, H. Su, L. N. Lu, Y. S. Hong, Y. Chen, K. Xiao, T. Ouyang, Y. Qin, Z. Q. Liu, Chem. Eng. J., 2021, 408, 127814.
[31]	T. Liu, F. Yang, G. Cheng, W. Luo, Small, 2018, 14, 1703748.
[32]	L. Wang, X. Duan, X. Liu, J. Gu, R. Si, Y. Qiu, Y. Qiu, D. Shi, F. Chen, X. Sun, J. Lin, J. Sun, Adv. Energy Mater., 2020, 10, 1903137.
[33]	X. Du, H. Su, X. Zhang, J. Catal., 2020, 383, 103-116.
[34]	J. Du, R. Wang, Y. R. Lv, Y. L. Wei, S. Q. Zang, Chem. Commun., 2019, 55, 3203-3206.
[35]	S. Zhang, D. Zhai, T. Sun, A. Han, Y. Zhai, W. C. Cheong, Y. Liu, C. Su, D. Wang, Y. Li, Appl. Catal. B, 2019, 254, 186-193.
[36]	Y. Zhao, Q. Fu, D. Wang, Q. Pang, Y. Gao, A. Missiul, R. Nemausat, A. Sarapulova, H. Ehrenberg, Y. Wei, G. Chen, Energy Storage Mater., 2019, 18, 51-58.
[37]	B. Yin, X. Cao, A. Pan, Z. Luo, S. Dinesh, J. Lin, Y. Tang, S. Liang, G. Cao, Adv. Sci., 2018, 5, 1800829.
[38]	I. Bezverkhyy, P. Afanasiev, M. Danot, J. Phys. Chem. B, 2004, 108, 7709-7715.
[39]	L. Sun, C. H. Hendon, S. S. Park, Y. Tulchinsky, R. Wan, F. Wang, A. Walsh, M. Dinca., Chem. Sci., 2017, 8, 4450-4457.
[40]	Y. Du, J. Maassen, W. Wu, Z. Luo, X. Xu, P. D. Ye, Nano Lett., 2016, 16, 6701-6708.
[41]	Y. Ma, J. Li, X. Liao, W. Luo, W. Huang, J. Meng, Q. Chen, S. Xi, R. Yu, Y. Zhao, L. Zhou, L. Mai, Adv. Funct. Mater., 2020, 30, 2005000.
[42]	C. V. Ramana, M. Massot, C. M. Julien, Surf. Interface Anal., 2005, 37, 412-416.
[43]	W. Liu, Y. Hou, H. Pan, W. Liu, D. Qi, K. Wang, J. Jiang, X. Yao, J. Mater. Chem. A, 2018, 6, 8349-8357.
[44]	Y. Liu, X. Xie, G. Zhu, Y. Mao, Y. Yu, S. Ju, X. Shen, H. Pang, J. Mater. Chem. A, 2019, 7, 15851-15861.
[45]	P. Cai, J. Huang, J. Chen, Z. Wen, Angew. Chem. Int. Ed., 2017, 56, 4858-4861.
[46]	Z. Chen, R. Wu, M. Liu, Y. Liu, S. Xu, Y. Ha, Y. Guo, X. Yu, D. Sun, F. Fang, J. Mater. Chem. A, 2018, 6, 10304-10312.

氮掺杂碳球负载原子调控的铁-钴镍黄铁矿用于高效氧催化反应

Atomic modulation of Fe-Co pentlandite coupled with nitrogen-doped carbon sphere for boosting oxygen catalysis

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 7

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.
[2]	张光颖, 刘旭, 张欣欣, 梁志坚, 邢耕宇, 蔡斌, 沈迪, 王蕾, 付宏刚. P修饰提高Fe-N-C的氧反应活性用于高稳定的锌-空气电池[J]. 催化学报, 2023, 49(6): 141-151.
[3]	唐甜蜜, 王寅, 韩憬怡, 张巧巧, 白雪, 牛效迪, 王振旅, 管景奇. 用于氧还原反应的双原子钴-铁催化剂[J]. 催化学报, 2023, 46(3): 48-55.
[4]	苏慧, 姜静, 宋少佳, 安博涵, 李宁, 高旸钦, 戈磊. 过渡金属硫化物相关电催化剂的设计与应用研究[J]. 催化学报, 2023, 44(1): 7-49.
[5]	刘储浩, 吴悦, 方锦杰, 余坷, 李慧, 贺文君, 张永臻, 柳守杰, 陈郑, 董京, 陈晨. 氮掺杂碳催化剂在高效电化学CO₂还原中的协同效应[J]. 催化学报, 2022, 43(7): 1697-1702.
[6]	陈宏彬, 叶雅倩, 陈鑫智, 张利利, 刘国学, 王素清, 丁良鑫. 中空四氧化三钴纳米球镶嵌的氮掺杂多孔碳纳米纤维: 锂-氧电池氧电极双功能催化剂[J]. 催化学报, 2022, 43(6): 1511-1519.
[7]	舒欣欣, 杨茅茂, 刘苗苗, 王怀生, 张进涛. 三维多孔碳限域的磷化钴电催化剂用于高效的锌-空气电池和水分解[J]. 催化学报, 2022, 43(12): 3107-3115.
[8]	刘会兵, 谢日鑫, 牛自强, 贾巧焕, 杨柳, 王世涛, 曹达鹏. “2合1”策略构建双功能氧电极反应电催化剂用于可充电锌-空气电池[J]. 催化学报, 2022, 43(11): 2906-2912.
[9]	陈永婷, 陈俊翔, 陈胜利. 基于表面占位效应和合理动力学模型的电催化火山关系[J]. 催化学报, 2022, 43(1): 2-10.
[10]	周省, 覃佳艺, 赵雪茹, 杨静. 富含吡啶氮-钴活性位点的三维多级大/介孔石墨烯作为高效可逆氧电催化剂用于可充电锌-空气电池[J]. 催化学报, 2021, 42(4): 571-582.
[11]	周亚楠, 朱宇冉, 闫新彤, 曹羽宁, 李佳, 董斌, 杨敏, 李庆忠, 刘晨光, 柴永明. Nb掺杂调控CoSeS多级纳米结构用于增强析氢反应[J]. 催化学报, 2021, 42(3): 431-438.
[12]	任振兴, 刘心娟, 诸葛志豪, 宫银燕, 孙长庆. MoSe₂/ZnO/ZnSe复合物用于高效可见光催化还原Cr(VI)[J]. 催化学报, 2020, 41(1): 180-187.
[13]	孙旭平. 泡沫镍担载NiCoP纳米片用作高效双功能水分解电催化剂[J]. 催化学报, 2019, 40(10): 1405-1407.
[14]	阎程程, 林龙, 汪国雄, 包信和. 过渡金属-氮活性位点在二氧化碳电化学还原反应中的应用[J]. 催化学报, 2019, 40(1): 23-37.
[15]	杨慧敏, 张佰艳, 张斌, 高哲, 覃勇. 原子层沉积制备掺氮碳膜修饰的Pt/CNTs实现甲醇高效电催化氧化[J]. 催化学报, 2018, 39(6): 1038-1043.