An Update on Formic Acid Dehydrogenation by Homogeneous Catalysis

Abstract

Formic acid (FA) has been extensively studied as one of the most promising hydrogen energy carriers today. The catalytic decarboxylation of FA ideally leads to the formation of CO2 and H2 that can be applied in fuel cells. A large number of transition‐metal based homogeneous catalysts with high activity and selectivity have been reported for the selective FA dehydrogentaion. In this review, we discussed the recent development of C,N/N,N‐ligand and pincer ligand‐based homogeneous catalysts for the FA dehydrogenation reaction. Some representative catalysts are further evaluated by the CON/COF assessment (catalyst on‐cost number)/(catalyst on‐cost frequency). Conclusive remarks are provided with future challenges and opportunities.

Enabling storage and utilization of low-carbon electricity: power to formic acid

“…3) describes the contribution of the catalyst in the cost of the product, formic acid. 12,19 Hence, a large TON value and the low production cost of the catalyst are advantageous. Any CON value greater than 1 suggests that the catalyst is more expensive than the product and will not be suitable for large scale application.…”

“…Significant progress in the catalyst development for the selective dehydrogenation of FA was witnessed in the last two decades. [14][15][16]19 The FA to power concept has been successfully demonstrated by a number of groups in FA-based electricity generation devices. 20,21 One potential drawback of FA is its corrosiveness, but such situations can be managed by a proper design of suitable containers and pipelines, 22,23 and thus the existing gasoline infrastructure may be employed for FA distribution after minor modifications.…”

Resin-supported iridium complex for low-temperature vanillin hydrogenation using formic acid in water

“…14 Moreover, the 21 mol% conversion of FA at room temperature is a comparable value to similar studies conducted with homogeneous Ircatalyst, 37 but here obtained with immobilized IrPYA which can potentially open new application in the eld of heterogeneous catalysis and fuel cells. [38][39][40] As this catalyst uniquely contains the IrPYA supported on Merrield resin (the catalyst is in solid form) and the IrPYA not used as homogenous catalyst, as well as the reaction conditions is mild (T ¼ 50 C and autogenous pressure), we anticipate that no difference in the catalytic performance should be observed. In addition, research on this issue coupled with advanced characterization techniques are ongoing at our laboratory to further understand the unique performance and its potential scalability.…”

Additive-Free Formic Acid Dehydrogenation Catalyzed by a Cobalt Complex

“…Yet, this substitution often comes at the price of a decrease reactivity and stability. 21 Beller et al pioneered the use of iron complexes in 2010, and a number of PNP pincer ligands chelated to an iron centre have been reported since. [22][23][24][25][26][27][28][29][30][31] Manganese complexes have also been reported to be active in this reaction, as reported by Boncella, Tondreau, et al and Beller et al.…”