Tshuma Piwai, Makhubela Banothile C E, Öhrström Lars, Bourne Susan A, Chatterjee Nabanita, Beas Isaac N, Darkwa James, Mehlana Gift
Department of Chemical Technology, Faculty of Science and Technology, Midlands State University Private Bag 9055, Senga Road Gweru Zimbabwe.
Department of Chemistry, Faculty of Science, University of Johannesburg, Kingsway Campus: C2 Lab 328 Auckland Park 2006 South Africa.
RSC Adv. 2020 Jan 22;10(6):3593-3605. doi: 10.1039/c9ra09938g. eCollection 2020 Jan 16.
The hydrogenation of carbon dioxide (CO) to formic acid is of great importance due to its useful properties in the chemical industry. In this work, we have prepared a novel metal-organic framework (MOF), JMS-1, using bipyridyl dicarboxylate linkers, with molecular formula [La(bpdc)(DMF)] . Network analysis of JMS-1 revealed a new 7-connected topology (). The MOF backbone of the activated phase (JMS-1a) was functionalized by cyclometalation using [RuCl(-cymene)] to produce Ru(ii)@JMS-1a. Both JMS-1a and Ru(ii)@JMS-1a were able to convert CO in the presence of hydrogen to formate. Ru(ii)@JMS-1a displayed outstanding conversion evidenced by a yield of 98% of formate under optimized conditions of total pressure 50 bar (CO/H = 1 : 4, temperature 110 °C, time 24 h, 5 mmol KOH, 8 mL ethanol). This work is significant in providing new strategies of incorporating active catalytic centres in MOFs for efficient and selective conversion of CO to formate.
将二氧化碳（CO₂）加氢生成甲酸在化学工业中因其有用的性质而具有重要意义。在这项工作中，我们使用联吡啶二羧酸酯连接体制备了一种新型金属有机框架（MOF），即JMS - 1，其分子式为[La(bpdc)(DMF)] 。对JMS - 1的网络分析揭示了一种新的7连接拓扑结构（）。通过使用[RuCl(对异丙基苯)]进行环金属化，对活化相（JMS - 1a）的MOF骨架进行功能化，以制备Ru(ii)@JMS - 1a。在氢气存在下，JMS - 1a和Ru(ii)@JMS - 1a都能够将CO₂转化为甲酸盐。在总压力50巴（CO₂/H₂ = 1∶4、温度110℃、时间24小时、5毫摩尔KOH、8毫升乙醇）的优化条件下，甲酸盐产率达到98%，这证明Ru(ii)@JMS - 1a表现出出色的转化率。这项工作对于提供在MOF中引入活性催化中心以实现CO₂高效、选择性转化为甲酸盐的新策略具有重要意义。
