Bahuguna Ashish, Sasson Yoel
Casali Center of Applied Chemistry, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, 9190401, Israel.
ChemSusChem. 2021 Mar 5;14(5):1258-1283. doi: 10.1002/cssc.202002433. Epub 2020 Dec 9.
In recent years, hydrogen has been considered a promising energy carrier for a sustainable energy economy in the future. An easy solution for the safer storage of hydrogen is challenging and efficient methods are still being explored in this direction. Despite having some progress in this area, no cost-effective and easily applicable solutions that fulfill the requirements of industry are yet to be claimed. Currently, the storage of hydrogen is largely limited to high-pressure compression and liquefaction or in the form of metal hydrides. Formic acid is a good source of hydrogen that also generates CO along with hydrogen on decomposition. Moreover, the hydrogenation of CO is thermodynamically unfavorable and requires high energy input. Alkali metal formates are alternative mild and noncorrosive sources of hydrogen. On decomposition, these metal formates release hydrogen and generate bicarbonates. The generated bicarbonates can be catalytically charged back to alkali formates under optimized hydrogen pressure. Hence, the formate-bicarbonate-based systems being carbon neutral at ambient condition has certain advantages over formic acid. The formate-bicarbonate cycle can be considered as a vehicle for hydrogen and energy storage. The whole process is carbon-neutral, reversible, and sustainable. This Review emphasizes the various catalytic systems employed for reversible formate-bicarbonate conversion. Moreover, a mechanistic investigation, the effect of temperature, pH, kinetics of reversible formate-bicarbonate conversion, and new insights in the field are also discussed in detail.
近年来,氢气被认为是未来可持续能源经济中一种很有前景的能量载体。实现氢气更安全储存的简易解决方案颇具挑战性,目前仍在探索高效方法。尽管在该领域已取得一些进展,但尚未有能满足工业需求的经济高效且易于应用的解决方案。当前,氢气储存主要局限于高压压缩、液化或金属氢化物形式。甲酸是一种良好的氢源,分解时除产生氢气外还会生成一氧化碳。此外,一氧化碳的加氢在热力学上不利,需要高能量输入。碱金属甲酸盐是替代的温和且无腐蚀性的氢源。这些金属甲酸盐分解时会释放氢气并生成碳酸氢盐。在优化的氢气压力下,生成的碳酸氢盐可通过催化作用重新转化为碱金属甲酸盐。因此,基于甲酸盐 - 碳酸氢盐的体系在环境条件下具有碳中性,相较于甲酸具有一定优势。甲酸盐 - 碳酸氢盐循环可被视为一种氢气和能量储存的载体。整个过程是碳中性、可逆且可持续的。本综述着重介绍了用于甲酸盐 - 碳酸氢盐可逆转化的各种催化体系。此外,还详细讨论了机理研究、温度的影响、pH值、甲酸盐 - 碳酸氢盐可逆转化的动力学以及该领域的新见解。