TY - JOUR
T1 - Highly efficient immobilized PN3P-pincer iridium catalyst for dehydrogenation of neat formic acid
AU - Alrais, Lujain
AU - Gholap, Sandeep Suryabhan
AU - Dutta, Indranil
AU - Abou-Hamad, Edy
AU - Chen, Benjamin W.J.
AU - Zhang, Jia
AU - Hedhili, Mohamed Nejib
AU - Basset, Jean Marie
AU - Huang, Kuo Wei
N1 - Publisher Copyright:
© 2023 Elsevier B.V.
PY - 2024/3
Y1 - 2024/3
N2 - Formic acid (FA) has been well recognized as one of the most promising hydrogen carriers. The dehydrogenation of the FA could offer an efficient process to on-demand hydrogen generation with a suitable catalyst. Homogeneous catalysts have demonstrated superior activity and selectivity compared to traditional heterogeneous catalysis. However, the latter is preferred for large-scale applications. By incorporating the homogeneous organometallic complex onto an appropriate support, the unique features of both types of catalysts can be combined and utilized effectively. Herein, we synthesized an immobilized PN3P-Ir pincer catalyst (2) supported onto KCC-1, a 3D fibrous silica nanosphere that exhibits a high surface area and contains a tetracoordinate aluminum site. To reduce the use of volatile additives, the choice of cesium formate (CsO2CH) was found to be crucial as at 80–90 °C, CsO2CH could act as a reaction medium and serve as basic additive. Remarkable reactivities under neat conditions were achieved with a TOF of 13,290 h-1 and a TON of up to 540,000. The comparative study indicates a significant improvement of 2 from its homogenous counterpart, PN3P-IrH3 (1).
AB - Formic acid (FA) has been well recognized as one of the most promising hydrogen carriers. The dehydrogenation of the FA could offer an efficient process to on-demand hydrogen generation with a suitable catalyst. Homogeneous catalysts have demonstrated superior activity and selectivity compared to traditional heterogeneous catalysis. However, the latter is preferred for large-scale applications. By incorporating the homogeneous organometallic complex onto an appropriate support, the unique features of both types of catalysts can be combined and utilized effectively. Herein, we synthesized an immobilized PN3P-Ir pincer catalyst (2) supported onto KCC-1, a 3D fibrous silica nanosphere that exhibits a high surface area and contains a tetracoordinate aluminum site. To reduce the use of volatile additives, the choice of cesium formate (CsO2CH) was found to be crucial as at 80–90 °C, CsO2CH could act as a reaction medium and serve as basic additive. Remarkable reactivities under neat conditions were achieved with a TOF of 13,290 h-1 and a TON of up to 540,000. The comparative study indicates a significant improvement of 2 from its homogenous counterpart, PN3P-IrH3 (1).
KW - Catalysis
KW - Formic acid dehydrogenation
KW - Immobilized catalysts
KW - Pincer complexes
UR - http://www.scopus.com/inward/record.url?scp=85175542617&partnerID=8YFLogxK
U2 - 10.1016/j.apcatb.2023.123439
DO - 10.1016/j.apcatb.2023.123439
M3 - Article
AN - SCOPUS:85175542617
SN - 0926-3373
VL - 342
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
M1 - 123439
ER -