基于NiZn层状双金属氢氧化物制备高效电催化CO2还原的原子分散Ni-N-C催化剂

doi:10.1016/S1872-2067(22)64188-3

催化学报 ›› 2023, Vol. 45: 152-161.DOI: 10.1016/S1872-2067(22)64188-3

基于NiZn层状双金属氢氧化物制备高效电催化CO₂还原的原子分散Ni-N-C催化剂

张平^a, 陈浩^a^,^*(), 陈林^a, 熊鹰^a, 孙子其^b, 杨浩宇^b, 付莹珂^a, 张亚萍^a, 廖婷^c^,^*(), 李斐^d^,^*()

^a西南科技大学材料科学与工程学院, 环境友好能源材料国家重点实验室, 四川绵阳621010, 中国
^b昆士兰科技大学物理化学学院, 澳大利亚
^c昆士兰科技大学机械、医学与化学过程学院, 澳大利亚
^d大连理工大学精细化工国家重点实验室, 辽宁大连116024, 中国

收稿日期:2022-07-14 接受日期:2022-10-19 出版日期:2023-02-18 发布日期:2023-01-10
通讯作者: 陈浩,廖婷,李斐
基金资助:
国家自然科学基金(U20A20125)

Atomically dispersed Ni-N-C catalyst derived from NiZn layered double hydroxides for efficient electrochemical CO₂ reduction

Ping Zhang^a, Hao Chen^a^,^*(), Lin Chen^a, Ying Xiong^a, Ziqi Sun^b, Haoyu Yang^b, Yingke Fu^a, Yaping Zhang^a, Ting Liao^c^,^*(), Fei Li^d^,^*()

^aState Key Laboratory of Environment-friendly Energy Materials, School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China
^bSchool of Chemistry and Physics, Faculty of Science, Queensland University of Technology, Brisbane, Qld 4000, Australia
^cSchool of Mechanical, Medical and Process Engineering, Faculty of Engineering, Queensland University of Technology, Brisbane, Qld 4000, Australia
^dState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2022-07-14 Accepted:2022-10-19 Online:2023-02-18 Published:2023-01-10
Contact: Hao Chen, Ting Liao, Fei Li
Supported by:
National Natural Science Foundation of China(U20A20125)

摘要/Abstract

摘要：

大气中CO₂浓度不断上升导致大量的环境问题, 如冰川融化、温室效应、极端天气等, 利用电化学方法将CO₂经还原反应(CO₂RR)转化为有价值的燃料或化学品是解决该问题的可行策略. 由于CO₂具有稳定的化学键(C=O, 806 kJ mol^-1), 需设计具有优异活性和高选择性的催化剂. 近年研究结果表明, 过渡金属锚定在N掺杂碳载体上而制得的催化剂(M-N-C)具有较高的原子利用率、独特的活性金属中心电子结构以及存储量丰富, 因而被认为是CO₂还原为CO的理想电催化剂. 目前已经提出了多种方法来制备M-N-C催化剂, 包括原子层沉积、基于金属-有机骨架的离子交换、基于载体修饰策略的吸附固化和受限热解. 然而, 这些方法存在制备过程繁琐或难以大规模生产的问题. 同时, 采用高温热解制备的M-N-C催化剂, 金属活性位点易被其致密的结构包裹, 难以完全暴露出来. 但有效的活性位点对M-N-C的催化性能起着至关重要的作用, 因此有必要研制一种简便、高效的方法来抑制金属原子聚集. 超薄二维碳骨架已被证明可以缩短反应物的扩散路径并有利于暴露催化剂活性位点.
本文将NiZn层状双金属氢氧化物(NiZn-LDHs)在多羟基化合物中进行剥离形成单层, 同时通过控制单层NiZn-LDHs、多羟基化合物和三聚氰胺共同热解, 宏量化制得Ni-N-C催化剂. X射线衍射(XRD)和透射电子显微镜(TEM)结果表明, 在焙烧过程中, 可通过改变单层NiZn-LDHs在多羟基化合物中的含量控制Ni-N-C材料中镍纳米颗粒的生成; 焙烧过程中Zn挥发能使Ni-N-C材料形成更多中孔, 增加碳骨架比表面积和孔径. 中孔通道和碳基底超薄特性结合可以促进CO₂向内部活性位点扩散, 增加反应物与活性位点的接触. XPS结果表明, Ni-N-C材料中Ni原子通过与N配位, 锚定在超薄碳骨架上, 且存在Ni^δ⁺中心(0<δ<2). X射线近边吸收和扩展X射线吸收精细结构分析表明, Ni-N-C-1中的Ni处于低价态(0<δ<2), 这与XPS分析一致, 且Ni为原子级分散; 小波变换分析表明, Ni和N的配位数为3.9. 利用H型电解池评估Ni-N-C材料电催化CO₂还原性能表明, Ni-N-C-1具有优异的CO₂还原活性, 在-0.6至-1.0 V电位范围内, FE_CO都大于90%, 且在-0.9 V时, FE_CO为95.2%, CO电流密度为24 mA cm^-2; 在-0.8 V电位, 工作25 h后Ni-N-C-1的CO电流密度基本保持不变, 说明Ni-N-C-1为稳定的CO₂RR催化剂. 通过密度泛函理论计算研究了Ni-N-C材料电催化CO₂还原为CO的电化学演化历程, 结果表明, 该反应过程分四个步骤: CO₂吸附到单个Ni原子位点上; 转移形成*COOH的质子/电子对; *COOH在释放H₂O的同时获得质子形成*CO; *CO从Ni位点解吸. 相应步骤的吉布斯自由能分别为0.54, 1.69, -0.99和-0.98 eV. Ni-N-C中Ni原子与配位N原子之间的强相互作用导致Ni原子的电子损失, Ni原子有0.85 e缺陷, 周围的N原子有0.15 e堆积, 这有利于CO₂的吸附. 总之, 本文采用单层NiZn-LDHs为金属源, 开发了一种简便且可宏量化制备CO₂RR单原子催化剂的新方法.

关键词: NiZn层状双金属氢氧化物, CO₂还原, Ni-N-C催化剂, 活性位点, 高效制备

Abstract:

Atomically dispersed catalytic metal sites anchored on N-doped carbon support catalysts (M-N-C) show great prospects for CO₂ electroreduction. Here, single-layer NiZn layered double hydroxides (NiZn-LDHs) was used as a sacrificial assistant to fabricate single-Ni atom anchored on ultrathin porous carbon catalyst. NiZn-LDHs were exfoliated to single-layer by polyhydroxy compounds which took as the carbon resource in Ni-N-C, and single layer NiZn LDHs taking as the Ni resource could avoid the agglomeration of Ni atoms during calcining. The CO Faradaic efficiency (FE_CO) of the synthesized Ni-N-C catalyst exceeded 90% at -0.6 to -1.0 V and a FE_CO of 95.2% with a current density of 24 mA cm^-2 at -0.9 V. This work not only provides a new method for preparing M-N-C catalysts, but also offers an effective and controllable strategy for large-scale production of high-performance single-atom catalysts.

Key words: NiZn-Layered double hydroxides, CO2 reduction, Ni-N-C Catalyst, Active site, Efficient preparation

张平, 陈浩, 陈林, 熊鹰, 孙子其, 杨浩宇, 付莹珂, 张亚萍, 廖婷, 李斐. 基于NiZn层状双金属氢氧化物制备高效电催化CO₂还原的原子分散Ni-N-C催化剂[J]. 催化学报, 2023, 45: 152-161.

Ping Zhang, Hao Chen, Lin Chen, Ying Xiong, Ziqi Sun, Haoyu Yang, Yingke Fu, Yaping Zhang, Ting Liao, Fei Li. Atomically dispersed Ni-N-C catalyst derived from NiZn layered double hydroxides for efficient electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2023, 45: 152-161.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64188-3

https://www.cjcatal.com/CN/Y2023/V45/I2/152

图/表 6

Scheme 1. Schematic illustration of the synthesis of Ni-N-C.

Fig. 1. XRD patterns of NiZn-LDHs (a), NiZn-LDHs/PHC (b), and Ni-N-C and CN (c). (d) Raman spectra of CN and Ni-N-C.

Fig. 2. TEM images (a-c) and HR-TEM image (d) of Ni-N-C-1. (e) HAADF-TEM image and corresponding EDS element mapping of Ni-N-C-1. AFM image (f) and the height profile (i) of Ni-N-C-1. (g) BET surface area and (inset) pore-size distribution curve of Ni-N-C-1. (h) Aberration-corrected HAADF-STEM image of Ni-N-C-1.

Fig. 3. (a) Ni K-edge XANES spectra of Ni-N-C-1, Ni foil, NiO and NiPc shown in k2-weighted R space. The wavelet transform of Ni-N-C-1 (b). NiPc (d), and NiO (f). (c) Fourier transformation of EXAFS spectra Ni-N-C-1, Ni foil, and NiO. (e) Ni K-edge EXAFS fitting result of Ni-N-C-1 shown in k2-weighted R space and Ni-N4 coordination environment.

Fig. 4. (a) LSV in CO2-saturated. (b) FECO at different potentials. (c) CO current density. (d) Tafel plots. (e) Nyquist plots. (f) Charging current density differences plotted against scan rates of CN, Ni-N-C-1NPs, and Ni-N-C-1. FECO (g) and current densities (h) of CO of Ni-N-C-0.5, Ni-N-C-1, and Ni-N-C-2 at different potentials. (i) Durability of Ni-N-C-1 at ?0.8 V (vs. RHE).

Fig. 5. (a) Free-energy diagram of CO2RR reaction on Ni-N co-doped graphite and the schematic of the reaction steps of the electrocatalytic CO2 to CO reaction. (b) The charge density difference of NiN4 configurations. The isosurface is selected at 0.0025 e ?-3 and the yellow and cyan regions represent electron accumulation and depletion, respectively.

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基于NiZn层状双金属氢氧化物制备高效电催化CO₂还原的原子分散Ni-N-C催化剂

Atomically dispersed Ni-N-C catalyst derived from NiZn layered double hydroxides for efficient electrochemical CO₂ reduction

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