Formic acid (HCOOH) has emerged as a promising H2 energy carrier due to its reasonable gravimetric and volumetric H2 densities, low toxicity, low flammability, and ease of handling. Its possible productions from biogenic feedstocks also make it an attractive source to produce H2 on demand. The utilization of HCOOH as a liquid H2 carrier requires catalytic systems to selectively dehydrogenate HCOOH at low temperatures without forming CO products that can act as a poison in fuel cell applications. In this review, we summarize the recent progress in understanding HCOOH decomposition via dehydrogenation (to CO2/H2) and dehydration (to CO/H2O) pathways on transition metals, including Cu, Pt, Pd, and Au. The focus is on discussing the surface chemistry of HCOOH reactions on transition metals, including the types of bound intermediates and the identity and kinetic relevance of elementary steps. In doing so, we review current catalyst design strategies for HCOOH dehydrogenation to facilitate the future development of catalytic processes for H2 storage/utilization.

Catalytic Dehydrogenation Hydrogen Storage Formic Acid Transition Metals Density Functional Theory

Borup R, Krause T, Brouwer J, J. Electrochem. Soc., 30, 79 (2021)
Kawanami H, Himeda Y, Laurenczy G, Adv. Inorg. Chem., 70, 395 (2017)
Mao WL, Mao HK, Proc. Natl. Acad. Sci. U. S. A., 101, 708 (2004)
Colόn YJ, Fairen-Jimenez D, Wilmer CE, Snurr RQ, J. Phys. Chem., 118, 5383 (2014)
Suh MP, Park HJ, Prasad TK, Lim DW, Chem. Rev., 112, 782 (2012)
Murray LJ, Dincă M, Long JR, Chem. Soc. Rev., 38, 1294 (2009)
Lim WX, Thornton AW, Hill AJ, Cox BJ, Hill JM, Hill MR, Langmuir, 29, 8524 (2013)
Viswanathan B, Energy Sources, 185 (2017)
Andersson J, Grönkvist S, Int. J. Hydrog. Energy, 44, 11901 (2019)
Kim S, Chen J, Cheng T, Gindulyte A, He J, He S, Li Q, Shoemaker BA, Thiessen PA, Yu B, Zaslavsky L, Zhang J, Bolton EE, PubChem, 49, 971 (2022)
Guo J, Yin CK, Zhong DL, Wang YL, Qi T, Liu GH, Shen LT, Zhou QS, Peng ZH, Yao H, Li ZB, Chem. Sus. Chem., 14, 2655 (2021)
Kothandaraman J, Kar S, Sen R, Goeppert A, Olah GA, Prakash GKS, J. Am. Chem. Soc., 139, 2549 (2017)
Aziz M, Oda T, Kashiwagi T, Energy Procedia, 158, 4086 (2019)
Aziz M, Wijayanta AT, Nandiyanto ABD, Energies, 13, 3062 (2020)
Sanchez F, Motta D, Roldan A, Hammond C, Villa A, Dimitratos N, Top. Catal., 61, 254 (2018)
Ahn Y, Byun J, Kim D, Kim BS, Lee CS, Han J, Green Chem., 21, 3442 (2019)
Vermaak L, Neomagus HWJP, Bessarabov DG, Membranes, 11, 670 (2021)
Hoshi N, Kida K, Nakamura M, Nakada M, Osada K, J. Phys. Chem. B, 110, 12480 (2006)
Hu S, Munoz F, Noborikawa J, Haan J, Scudiero L, Ha S, Appl. Catal. B: Environ., 180, 758 (2016)
Hu S, Scudiero L, Ha S, Electrochem. Commun., 38, 107 (2014)
Yang J, Yang S, Chung Y, Kwon Y, Korean J. Chem. Eng., 37, 176 (2020)
Rahbari A, Ramdin M, van de Broeke LJP, Vlugt TJH, Ind. Eng. Chem. Res., 57, 10663 (2018)
Yoo JS, Abild-Pedersen F, Nørskov JK, Studt F, ACS Catal., 4, 1226 (2014)
Bowker M, Rowbotham E, Leibsle FM, Haq S, Surf. Sci., 349, 97 (1996)
Bowker M, Haq S, Holroyd R, Parlett PM, Poulston S, Richardson N, J. Chem. Soc.-Faraday Trans., 92, 4683 (1996)
Shiozawa Y, Koitaya T, Mukai K, Yoshimoto S, Yoshinobu J, J. Chem. Phys., 143, 234707 (2015)
Ying DHS, Madix RJ, J. Catal., 61, 48 (1980)
Hayden BE, Prince K, Woodruff DP, Bradshaw AM, Surf. Sci., 133, 589 (1983)
Dubois LH, Ellis TH, Zegarski BR, Kevan SD, Surf. Sci., 172, 385 (1986)
Madix RJ, Telford SG, Surf. Sci., 277, 246 (1992)
Yao Y, Zaera F, Surf. Sci., 646, 37 (2016)
Li S, Scaranto J, Mavrikakis M, Top. Catal., 59, 1580 (2016)
Chen BWJ, Mavrikakis M, ACS Catal., 10, 10812 (2020)
Iglesia E, Boudart M, J. Phys. Chem., 90, 5272 (1986)
Lin TC, Torre UDL, Hejazi A, Kwon S, Iglesia E, J. Catal., 404, 814 (2021)
Iglesia E, Boudart M, J. Catal., 81, 214 (1983)
Tang Y, Roberts CA, Perkins RT, Wachs IE, Surf. Sci., 650, 103 (2016)
Jensen MB, Myler U, Thiel PA, Surf. Sci. Lett., 290, L655 (1993)
Avery NR, Appl. Surf. Sci., 11, 774 (1982)
Abbas N, Madix RJ, Appl. Surf. Sci., 16, 424 (1983)
Scaranto J, Mavrikakis M, Surf. Sci., 648, 201 (2016)
Herron JA, Scaranto J, Ferrin P, Li S, Mavrikakis M, ACS Catal., 4, 4434 (2014)
Ojeda M, Iglesia E, Angew. Chem.-Int. Edit., 48, 4800 (2009)
Columbia MR, Thiel PA, Surf. Sci., 235, 53 (1990)
Becker E, Skoglundh M, Andersson M, Spetz AL, IEEE Sensors (2007).
Columbia MR, Crabtree AM, Thiel PA, J. Electroanal. Chem., 345, 93 (1993)
Bhandari S, Rangarajan S, Maravelias CT, Dumesic JA, Mavrikakis M, ACS Catal., 10, 4112 (2020)
Kim Y, Kim S, Ham HC, Kim DH, J. Catal., 389, 506 (2020)
Li J, Chen W, Zhao H, Zheng X, Wu L, Pan H, Zhu J, Chen Y, Lu J, J. Catal., 352, 371 (2017)
Jones S, Kolpin A, Tsang SCE, Catal. Struct. React., 1, 19 (2014)
Kim Y, Lee H, Yang S, Lee J, Kim H, Hwang S, Jeon SW, Kim DH, J. Catal., 404, 324 (2021)
Hu C, Pulleri JK, Ting SW, Chan KY, Int. J. Hydrog. Energy, 39, 381 (2014)
Bulut A, Yurderi M, Karatas Y, Zahmakiran M, Kivrak H, Gulcan M, Kaya M, Appl. Catal. B: Environ., 164, 324 (2015)
Jorgensen SW, Madix RJ, J. Am. Chem. Soc., 110, 397 (1988)
Davis JL, Barteau MA, Surf. Sci., 256, 50 (1991)
Scaranto J, Mavrikakis M, Surf. Sci., 650, 111 (2016)
Zhang R, Liu H, Wang B, Ling L, J. Phys. Chem. C, 116, 22266 (2012)
Li S, Rangarajan S, Scaranto J, Mavrikakis M, Surf. Sci., 709, 121846 (2021)
Wang Y, Qi Y, Zhang D, Comput. Theor. Chem., 1049, 51 (2014)
Jiang K, Xu K, Zou S, Cai WB, J. Am. Chem. Soc., 136, 4861 (2014)
Zhu QL, Tsumori N, Xu Q, J. Am. Chem. Soc., 137, 11743 (2015)
Song FZ, Zhu QL, Tsumori N, Xu Q, ACS Catal., 5, 5141 (2015)
Ruthven DM, Upadhye RS, J. Catal., 21, 39 (1971)
Kim Y, Kim DH, Appl. Catal. B: Environ., 244, 684 (2019)
Zhou X, Huang Y, Xing W, Liu C, Liao J, Lu T, Chem. Commun., 30, 3540 (2008)
Huang Y, Zhou X, Yin M, Liu C, Xing X, Chem. Mater., 22, 5122 (2010)
Zhang S, Metin O, Su D, Sun S, Angew. Chem.-Int. Edit., 52, 3681 (2013)
Mandal K, Bhattacharjee D, Dasgupta S, Int. J. Hydrog. Energy, 40, 4786 (2015)
Gazsi A, Bánsági T, Solymosi F, J. Phys. Chem. C, 115, 15459 (2011)
Singh S, Li S, Carrasquillo-Flores R, Alba-Rubio AC, Dumesic JA, Mavrikakis M, AIChE J., 60, 1303 (2014)
Chen BWJ, Stamatakis M, Mavrikakis M, ACS Catal., 9, 9446 (2019)
Deng QF, Zhang ZF, Cui FJ, Jia LH, Int. J. Hydrog. Energy, 42, 14865 (2017)
Bi QY, Lin JD, Liu YM, He HY, Huang FQ, Cao Y, Angew. Chem.-Int. Edit., 55, 11849 (2016)
Bi QY, Lin JD, Liu YM, He HY, Huang FQ, Cao Y, J. Power Sources, 328, 463 (2016)
Xu LX, Yao F, Luo JL, Wan C, Ye MF, Cui P, An Y, RSC Adv., 7, 4746 (2017)
Qin Y, Wang J, Meng F, Wang L, Zhang X, Chem. Commun., 49, 10028 (2013)
Mars P, Scholten JJF, Zwietering P, Adv. Catal., 14, 35 (1963)
Trillo JM, Munuera G, Criado JM, Catal. Rev.-Sci. Eng., 7, 51 (1972)
Noto Y, Fukuda K, Onishi T, Tamaru K, Trans. Faraday Soc., 63, 3081 (1967)
Fukuda K, Noto Y, Onishi T, Tamaru K, Trans. Faraday Soc., 63, 3072 (1967)
Kwon S, Lin TC, Iglesia E, J. Phys. Chem. C, 124, 20161 (2020)
Rajadurai S, Catal. Rev.-Sci. Eng., 36, 385 (1994)
Álvarez A, Bansode A, Urakawa A, Bavykina AV, Wezendonk TA, Makkee M, Gascon J, Kapteijn F, Chem. Rev., 117, 9804 (2017)
Zhao G, Huang X, Wang X, Wang X, J. Mater. Chem. A, 5, 21625 (2017)
Whang HS, Lim J, Choi MS, Lee J, Lee H, BMC Chem. Eng., 1, 9 (2019)
Sun R, Liao Y, Bai ST, Zheng M, Zhou C, Zhang T, Sels BF, Energy Environ. Sci., 14, 1247 (2021)
Yan N, Philippot K, Curr. Opin. Chem. Eng., 20, 86 (2018)
Onishi N, Iguchi M, Yang X, Kanega R, Kawanami H, Xu Q, Himeda Y, Adv. Energy Mater., 9, 1801275 (2019)
Chen X, Liu Y, Wu J, Mol. Catal., 483, 110716 (2020)