碳点衍生的碳纳米花负载钴单原子和纳米颗粒用于高效的氧还原反应

doi:10.1016/S1872-2067(22)64146-9

催化学报 ›› 2022, Vol. 43 ›› Issue (9): 2443-2452.DOI: 10.1016/S1872-2067(22)64146-9

• 论文 • 上一篇

碳点衍生的碳纳米花负载钴单原子和纳米颗粒用于高效的氧还原反应

程瑶佳^a, 宋昊强^a, 于镜坤^a, 常江伟^a^,^*(), Geoffrey I. N. Waterhouse^c, 唐智勇^d, 杨柏^e, 卢思宇^a^,^b^,^#()

^a郑州大学化学学院, 绿色催化中心, 河南郑州450000, 中国
^b吉首大学化学与化工学院, 湖南吉首416000, 中国
^c奥克兰大学化学科技学院, 奥克兰1142, 新西兰
^d中国科学院国家纳米科学技术中心, 纳米系统与多级制备中科院重点实验室, 北京100190, 中国
^e吉林大学化学学院, 超分子结构与材料化学学院国家重点实验室, 吉林长春130012, 中国

收稿日期:2022-04-30 接受日期:2022-06-25 出版日期:2022-09-18 发布日期:2022-07-20
通讯作者: 常江伟,卢思宇
基金资助:
国家自然科学基金(52122308);国家自然科学基金(21905253);国家自然科学基金(51973200);河南自然科学基金(02300410372)

Carbon dots-derived carbon nanoflowers decorated with cobalt single atoms and nanoparticles as efficient electrocatalysts for oxygen reduction

Yaojia Cheng^a, Haoqiang Song^a, Jingkun Yu^a, Jiangwei Chang^a^,^*(), Geoffrey I. N. Waterhouse^c, Zhiyong Tang^d, Bai Yang^e, Siyu Lu^a^,^b^,^#()

^aGreen Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou 450000, Henan, China
^bCollege of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, Hunan, China
^cSchool of Chemical Sciences, The University of Auckland, Auckland 1142, New Zealand
^dCAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190, China
^eState Key Laboratory of Supramolecular Structure and Materials College of Chemistry, Jilin University, Changchun 130012, Jilin, China

Received:2022-04-30 Accepted:2022-06-25 Online:2022-09-18 Published:2022-07-20
Contact: Jiangwei Chang, Siyu Lu
Supported by:
National Natural Science Foundation of China(52122308);National Natural Science Foundation of China(21905253);National Natural Science Foundation of China(51973200);Natural Science Foundation of Henan(02300410372)

摘要/Abstract

摘要：

锌空气电池(ZABs)具有高能量密度(1086 mWh g_Zn^-1)、价低、易回收等优势, 引起了学者们的广泛关注. 空气电极发生的氧还原反应(ORR)/氧析出反应(OER)是控制整个ZABs效率的关键. 因此, 设计和开发高效的ORR电催化剂对于ZABs商业化至关重要. 目前, Pt基电催化剂仍是最有效的ORR电催化剂, 但Pt资源稀缺, 价格高昂, Pt基电催化剂稳定性差等缺点阻碍了其商业化. 因此, 研究高活性和高稳定性的ORR非贵金属电催化剂十分重要. 碳点(CDs)作为一种新型的零维高分子碳材料, 具有低毒、高导电性等优势, 被广泛用于碳基材料的前驱体. CDs具有sp²杂化晶核、丰富的边缘位点和大量的官能团(如‒NH₂, ‒COOH和‒OH), 这些表面官能团为过渡金属原子提供了很强的锚定位点, 可用于构筑各种碳负载过渡金属催化剂.

本文设计合成了一种新型的碳基ORR电催化剂, 其由CDs衍生的三维碳纳米花(CNF)负载Co单原子(SAs)和纳米颗粒(NPs)构成. 利用CDs在二次水热过程中形成了3.66 nm的超薄纳米膜并构筑成3D的多孔CNF结构. X射线衍射、高角度环形暗场原子分辨率扫描跃迁电子显微镜和X射线吸收光谱结果表明, 材料中的SAs和NPs共存. 测试结果表明, Co SAs/NPs CNF拥有可以和商业Pt/C相当的ORR活性(E_1/2 = 0.83 V (vs. RHE), j_L = 6.13 mA cm^-2), 且具有良好的稳定性. 同时, 利用SCN^-可以毒化SAs和NPs, 而EDTA只能毒化SAs的特性, 证明了Co SAs和Co NPs协同促进了整个催化反应过程. 理论计算表明, 相邻Co NPs的存在优化了Co-N₄位点的电子结构, 显著降低了ORR决速步骤(*OOH吸附)的能垒. 因此, 在整个催化反应过程中, Co SAs和Co NPs协同改善了ORR过程中的电子和质子转移行为. Co SAs/NPs CNF较大的比表面积和丰富的多孔结构有利于O₂和质子传输, 基于其组装的ZABs的能量密度高达1000.58 mWh g_Zn^-1(理论值的93.69%)和循环运行1300次性能依然稳定. 综上, 本工作为高性能ORR电催化剂的设计提供依据.

关键词: 碳点, 钴单原子, 钴纳米颗粒, 氧还原反应, 锌空电池

Abstract:

The sluggish kinetics of oxygen reduction reaction (ORR) hinders the commercialization of Zn-air batteries (ZABs). Manipulating the electronic structure of electrocatalysts to optimize the adsorption energy of oxygen-containing intermediates during the 4e^- ORR offers a practical route toward improving ORR kinetics. Herein, we designed a novel ORR electrocatalyst containing Co single atoms and nanoparticles supported by carbon dots-derived carbon nanoflowers (Co SAs/NPs CNF). Co SAs/NPs CNF possessed a very high ORR activity (E_1/2 of the Co SAs/NPs CNF catalyst is 0.83 V (vs. RHE)), and outstanding catalytic performance and stability when used as the air-electrode catalyst in rechargeable ZABs (152.32 mW cm^-2, 1000.58 mWh g_Zn^-1, and over 1300 cycles at a current density of 5 mA cm^-2). The Co SAs and Co NPs cooperated to improve electron and proton transfer processes during ORR. Theoretical calculations revealed that the presence of adjacent Co NPs optimized the electronic structure of the isolated Co-N₄ sites, significantly lowering the energy barriers for the rate-determining step in ORR (adsorption of *OOH) and thereby delivering outstanding ORR performance. This work reveals that the combination of supported single-atom sites and metal nanoparticles can be highly beneficial for ORR electrocatalysis, outperforming catalysts containing only Co SAs or Co NPs.

Key words: Carbon dots, Co single atom, Co nanoparticle, Oxygen reduction reaction, Zn-air battery

程瑶佳, 宋昊强, 于镜坤, 常江伟, Geoffrey I. N. Waterhouse, 唐智勇, 杨柏, 卢思宇. 碳点衍生的碳纳米花负载钴单原子和纳米颗粒用于高效的氧还原反应[J]. 催化学报, 2022, 43(9): 2443-2452.

Yaojia Cheng, Haoqiang Song, Jingkun Yu, Jiangwei Chang, Geoffrey I. N. Waterhouse, Zhiyong Tang, Bai Yang, Siyu Lu. Carbon dots-derived carbon nanoflowers decorated with cobalt single atoms and nanoparticles as efficient electrocatalysts for oxygen reduction[J]. Chinese Journal of Catalysis, 2022, 43(9): 2443-2452.

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图/表 5

Fig. 1. (a) Schematic diagram showing the synthesis of Co SAs/NPs CNF. (b) SEM images of Co SAs/NPs CNF. (c,d) TEM and HRTEM images of Co SAs/NPs CNF (inset: particle size distribution of Co NPs). (e) HAADF-STEM image of Co SAs/NPs CNF (the bright spots circles in red are atomically dispersed Co atoms and the blue circles are Co NPs). (f) EDS image and elemental (C, N, and Co) mapping analysis of Co SAs/NPs CNF. (g-i) AFM 2D image, AFM height data, and AFM 3D image of Co SAs/NPs CNF. (j) XRD patterns of Co SAs/NPs CNF and Co3O4/C.

Fig. 2. (a) Nitrogen adsorption/desorption isotherms for Co SAs/NPs CNF (inset is the pore-size distribution). High-resolution N 1s XPS spectrum (b) and High-resolution Co 2p XPS spectrum (c) of Co SAs/NPs CNF. Co K-edge XAS spectra (d) and Co K-edge χ(R) EXAFS spectra (e) for Co SAs/NPs CNF, Co Pc, and Co foil. (f) Co K-edge EXAFS fitting curves for Co SAs/NPs CNF. (g-i) WT-EXAFS images for Co foil, Co Pc, and Co SAs/NPs CNF.

Fig. 3. (a) CV curves for Co SAs/NPs CNF and Pt/C in O2-saturated and Ar-saturated 0.1 mol L?1 KOH. LSV polarization curves (b) and Tafel slopes (c) of Co SAs/NPs CNF, Co3O4/C, CM-SH, and commercial Pt/C. (d) The LSV polarization curves of Co SAs/NPs CNF at different rotating speeds and the K-L curves. (e) The n and H2O2 yield between 0.2-0.8 V of Co SAs/NPs CNF and commercial Pt/C. (f) The i-t test results for Co SAs/NPs CNF and Pt/C in O2-saturated 0.1 mol L?1 KOH with and without 1.0 mol L?1 CH3OH. (g) ORR polarization curves for Co SAs/NPs CNF and Pt/C before and after 5000 cycles. (h) The i-t test results for Co SAs/NPs CNF and Pt/C in O2-saturated 0.1 mol L?1 KOH. (i) The i-t curve of the Co SAs/NPs before and after the addition of EDTA or SCN- ions in 0.1 mol L?1 KOH.

Fig. 4. Models of Co SAs/NPs (a), Co SAs (b), Co(111) (c) and the adsorption geometries of the *O2, *OOH, *O, and *OH intermediates. (d,e) The free energy at each reaction step for Co(111), Co SAs, and Co SAs/NPs was U = 0 V and U = 1.23 V. (f) PDOS for Co SAs/NPs, Co SAs, and Co(111).

Fig. 5. (a) Schematic diagram of a ZAB. (b) OCV of a ZAB assembled with Co SAs/NPs CNF (inset is a photograph showing the OCV). (c) Discharge curves and power density curves. (d) Specific capacity curves. (e) Energy-density curves of ZABs assembled with Pt/C and Co SAs/NPs CNF. (f) Comparison of the energy density of the ZAB assembled with Co SAs/NPs CNF and other recently reported results. (g) Stability of ZABs assembled with Co SAs/NPs CNF and Pt/C.

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碳点衍生的碳纳米花负载钴单原子和纳米颗粒用于高效的氧还原反应

Carbon dots-derived carbon nanoflowers decorated with cobalt single atoms and nanoparticles as efficient electrocatalysts for oxygen reduction

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