| 双金属MOF-74与其衍生材料的构筑及其电催化生物质的高效转化性能 |
| Bimetallic MOF-74 and derivatives: Fabrication and efficient electrocatalytic biomass conversion |
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| 摘要: 为开发在温和条件下高效、高选择性氧化5-羟甲基糠醛(HMF)的多功能催化材料和反应体系，构筑了双金属有机框架(BMOF)材料及其衍生材料，用于低电压下的HMF电催化氧化。采用溶剂热法合成了双金属CoNi-MOF-74，并采用2种方式制备相应的催化材料。其一，对CoNi-MOF-74进行热解处理，制得石墨碳层包覆、碳基体稳定的CoNi合金(CoNi@C)纳米颗粒；其二，在电催化过程中，CoNi-MOF-74发生原位水解反应，生成相应的氢氧化物(CoNi (OH)2)，进而将其作为电极材料使用。研究发现，当Co、Ni的物质的量之比设定为1∶3时，所制备的Co1Ni3-MOF-74材料在800℃进行热解处理后，生成的Co1Ni3@C在低电位下对HMF电催化氧化表现出优异的催化活性和高的2,5-呋喃二甲酸(FDCA)选择性(87.26%)。而Co1Ni1-MOF-74(Co、Ni物质的量之比为1∶1)电解时原位生成的Co0.5Ni0.5(OH)2对中间产物5-(羟甲基)呋喃-2-羧酸(HMFCA)具有很高的选择性(88.59%)和高转化率。这主要得益于衍生材料较好的孔隙结构、Co和Ni双金属之间的协同作用和石墨碳的良好导电性。 |
| 关键词: 金属有机框架材料 非贵金属 电催化 生物质转化 5-羟甲基糠醛氧化 |
| 基金项目: 山东省自然科学基金(No.ZR2024MB002)和国家自然科学基金(No.22275108)资助 |
| Abstract: This work focuses on fabricating multifunctional electrode materials and reaction systems for the highly efficient 5-hydroxymethylfurfural (HMF) oxidation under mild conditions. Bimetallic metal-organic framework materials (BMOF) and their derivatives were synthesized for the electrocatalytic oxidation of HMF at low voltage. Bimetallic CoNi-MOF-74 was synthesized using the solvothermal method. Two methods were used to transform the MOF material into electrode materials. Firstly, the CoNi alloy particles stabilized by porous carbon matrix (denoted as CoNi@C) were obtained by pyrolysis of CoNi-MOF-74. Secondly, the CoNi(OH)2 was in situ and obtained through the hydrolysis of CoNi-MOF-74 under an alkaline electrolyte during electrocatalysis. Interestingly, the optimal Co1Ni3@C derived from Co1Ni3-MOF-74 via pyrolysis at 800 ℃ exhibited excellent catalytic activity and high 2,5furandicarboxylic acid (FDCA) selectivity (87.26%) for HMF electrooxidation at low potential. The Co0.5Ni0.5(OH)2 generated in situ during electrolysis of Co1Ni1-MOF-74 displayed high selectivity (88.59%) for the intermediate product of 5-(hydroxymethyl) furano-2-carboxylic acid (HMFCA). The superior performance is mainly attributed to the pore structure of the catalytic materials, the synergistic effect between Co and Ni, and the good electrical conductivity of graphitic carbon. |
| Keywords: metal-organic framework material non-noble metal electrocatalysis biomass conversion 5-hydroxymethylfurfural oxidation |
| 投稿时间：2025-03-15 修订日期：2025-05-08 |
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