TY - JOUR
T1 - Computationally guided design of a new Rh catalyst for selective formic acid dehydrogenation: Validation with caution
AU - Guan, Chao
AU - Zhang, Dan-Dan
AU - Zhang, Tonghuan
AU - Huang, Mei-Hui
AU - Chakraborty, Priyanka
AU - Li, Huaifeng
AU - Yao, Changguang
AU - Zhou, Chunhui
AU - Hu, Jinsong
AU - Huang, Kuo-Wei
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work was supported by funding from King Abdullah University of Science and Technology (KAUST).
PY - 2019/4/1
Y1 - 2019/4/1
N2 - Formic acid possesses many desirable properties as a promising hydrogen energy carrier. Density functional theory (DFT) was utilized to design new Rh complexes with 2,2′-biimidazoline ligands to explore their potential as catalysts for formic acid dehydrogenation. These designed complexes were prepared and examined as catalysts under various temperatures and ratios of formic acid to sodium formate. It was found that although our complexes gave a high TOF of 20,000 h−1 at 90 °C under certain formic acid/sodium formate ratios, the dehydrogenation reaction was prematurely deactivated once 30% of the formic acid was consumed. Possible deactivation mechanisms were investigated by NMR and HRMS. Our observations suggest that while guided rational design of catalysts by DFT has much potential, the method does have limitations as evidenced by our experimental comparisons and thus pure DFT design should be conducted with caution.
AB - Formic acid possesses many desirable properties as a promising hydrogen energy carrier. Density functional theory (DFT) was utilized to design new Rh complexes with 2,2′-biimidazoline ligands to explore their potential as catalysts for formic acid dehydrogenation. These designed complexes were prepared and examined as catalysts under various temperatures and ratios of formic acid to sodium formate. It was found that although our complexes gave a high TOF of 20,000 h−1 at 90 °C under certain formic acid/sodium formate ratios, the dehydrogenation reaction was prematurely deactivated once 30% of the formic acid was consumed. Possible deactivation mechanisms were investigated by NMR and HRMS. Our observations suggest that while guided rational design of catalysts by DFT has much potential, the method does have limitations as evidenced by our experimental comparisons and thus pure DFT design should be conducted with caution.
UR - http://hdl.handle.net/10754/653023
UR - https://www.sciencedirect.com/science/article/pii/S0360319919308894
UR - http://www.scopus.com/inward/record.url?scp=85063563703&partnerID=8YFLogxK
U2 - 10.1016/j.ijhydene.2019.02.227
DO - 10.1016/j.ijhydene.2019.02.227
M3 - Article
VL - 44
SP - 28421
EP - 28429
JO - International Journal of Hydrogen Energy
JF - International Journal of Hydrogen Energy
SN - 0360-3199
IS - 53
ER -