CoNi-MOF-74/泡沫镍衍生的CoNi@C/NF复合物用于高效有机电合成

doi:10.6023/A24010040

摘要/Abstract

电催化有机合成作为一种绿色可持续的合成方法, 是替代工业上传统化学品合成的最佳选择, 但目前大多以半反应为主. 为了实现能源投资效益最大化, 两电极同时进行有机物的电转化是行之有效的解决方案. 电极材料需要满足两端反应同步高效进行, 并总电子转移数保持一致. 因此, 合成廉价、高效以及高稳定性的多功能电催化剂是十分必要的. 此研究中, 以泡沫镍(NF)为镍源和模板, 通过一步溶剂热法, 原位生长CoNi-MOF获得CoNi-MOF-74/NF材料. 以CoNi-MOF-74/NF为前驱体, 在20%H₂/Ar混合气、400 ℃下煅烧得到NF负载的碳包裹CoNi合金纳米颗粒(CoNi@C/NF). 该杂化材料不仅在三电极体系中对苯甲醇氧化成苯甲酸和硝基苯还原制苯胺这些半反应表现出优异的催化性能, 对两电极体系即阳极的电氧化苯甲醇和阴极的电还原硝基苯都能实现99%产率. 利用有限的催化剂及电量生产更多的高附加值产品, 从而创建可持续的有机合成体系, 为设计多功能电极材料在精细化学品的绿色合成领域开辟了新的思路.

关键词: 金属有机框架, 过渡金属, 电催化, 苯甲醇氧化, 硝基苯还原

Electrocatalytic organic synthesis as a green and sustainable synthesis method, has a great potential to replace traditional synthetic method of fine chemicals in industry. To maximize the energy investment, achieving simultaneous conversion of organics at two electrodes is an effective solution. The required electrocatalysts should be effective on two reactions at both anode and cathode, and balance the total electron transfer numbers. However, most reported catalysts are monofunctional and high selectivity of target products is difficult to control. Therefore, it is necessary to develop multi-functional electrocatalysts with low-cost, high efficiency and long-life. In this work, CoNi-MOF-74/NF composite was obtained by in-situ growth of bimetallic metal-organic framework (CoNi-MOF) on nickel foam (NF) via one-step solvothermal method. NF provided nickel source and template. Then the CoNi-MOF-74/NF was calcined to give nickel foam stabilized CoNi alloy nanoparticles coated with graphite carbon layer under 20%H₂/Ar atmosphere at 400 ℃. The CoNi@C/NF hybrid shown excellent catalytic performance for the isolated electrooxidation of benzyl alcohol to benzoic acid and the electroreduction of nitrobenzene (NP) to aniline using three-electrode system. Furthermore, the hybrid achieved 99% conversion for the pairing reaction constructed by the electrocatalytic oxidation of alcohol at anode coupling with the electroreduction of nitrobenzene at cathode. Thus, more value-added organic products could be obtained using limited catalyst and electricity, creating a sustainable organic synthesis system. Furthermore, the CoNi@C/NF performs good catalytic stability at two electrodes even after six cycles. For comparison, various contrast catalysts including monometallic Ni@C/NF, Co@C, and CoNi@C have been also synthesized. The optimal activity of CoNi@C/NF mainly attributes to the synergistic catalysis between Co and Ni, good electric conductivity of NF and graphitic carbon, as well as the porous porosity from NF and porous carbon framework. This study opens up a novel way for designing multifunctional electrode materials in the green synthesis of fine chemicals from MOFs.

Key words: metal-organic framework, transition metal, electrocatalysis, benzyl alcohol oxidation, nitrobenzene reduction

引用此文

王南南, 陈玉贞. CoNi-MOF-74/泡沫镍衍生的CoNi@C/NF复合物用于高效有机电合成[J]. 化学学报, 2024, 82(6): 621-628.

Nannan Wang, Yuzhen Chen. CoNi-MOF-74/NF Derived CoNi@C/NF Hybrid for Efficient Electrosynthesis of Organics[J]. Acta Chimica Sinica, 2024, 82(6): 621-628.

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图/表 7

图1. CoNi-MOF-74/NF及CoNi@C/NF的合成示意图

Figure 1. Schematic illustration of constructing the CoNi-MOF-74/NF and CoNi@C/NF

图2. 各种样品的PXRD谱图

Figure 2. Powder X-ray diffraction patterns of different samples

图3. (a) CoNi-MOF-74和(b) CoNi-MOF-74/NF的扫描电镜图像; CoNi@C的(c) TEM图像及(d) HRTEM图像

Figure 3. SEM images of CoNi-MOF-74 (a) and CoNi-MOF-74/NF (b); TEM (c) and HRTEM images (d) of CoNi@C

图4. (a) Ni 2p和(b) Co 2p 的XPS谱图

Figure 4. XPS spectra of Ni 2p (a) and Co 2p (b)

图5. (a) CoNi@C/NF在1 mol/L KOH电解液中不同浓度苯甲醇的LSV曲线; (b)不同电解时间下苯甲醇、苯甲醛和苯甲酸的HPLC数据; (c)苯甲醇氧化转化率随电解时间的变化; (d)硝基苯还原转化率随电解时间的变化

Figure 5. (a) LSV curves of CoNi@C/NF upon different concentrations of benzyl alcohol in 1 mol/L KOH electrolyte; (b) HPLC data of benzyl alcohol, benzaldehyde and benzoic acid at different electrolysis time; (c) the conversion of benzyl alcohol oxidation vs. electrolysis time; (d) the conversion of nitrobenzene reduction vs. electrolysis time

图6. (a)双电极催化体系; (b)不同电解时间阳极醇氧化反应的HPLC数据; (c)不同电解时间下苯甲醇电氧化的转化率与选择性; (d)不同电解时间下4-溴苯甲醇电氧化的转化率; (e)不同催化剂催化两电极反应中阳极氧化的活性对比; (f) CoNi@C/NF作为双电极催化剂催化苯甲醇氧化循环反应

Figure 6. (a) Two-electrode catalysis system; (b) HPLC data of anodic electrooxidation at different electrolysis time; (c) the conversion and selectivity of benzyl alcohol at different electrolysis time; (d) the conversion and selectivity of 4-bromobenzyl alcohol; (e) the conversion and selectivity comparison of different catalyst; (f) six cycles for benzyl alcohol oxidation by CoNi@C/NF in two-electrode system

图7. (a)硝基苯还原转化率随电解时间的变化; (b)对硝基苯酚还原转化率随电解时间的变化; (c)阴极处硝基苯还原循环测试; (d)不同催化剂两电极反应中阴极还原的活性对比

Figure 7. (a) The conversion of nitrobenzene reduction vs. electrolysis time; (b) the conversion of p-nitrophenol reduction vs. electrolysis time; (c) six cycles for nitrobenzene reduction in two-electrode system; (d) the conversion of different catalysts in cathode reduction

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