Predication of Selective Ring-opening Hydrogenolysis for Furfuryl Alcohol to Produce Pentanediol over Dual-atom Catalysts

Abstract

Selective activation of C-O bond is of fundamental importance in the precise conversion of oxygenates into value-added compounds in an atom-economic and sustainable manner, and meanwhile, the structurally well-defined dual-atoms catalysts (DACs) have been scarcely investigated in this field. In this study, a series of transition metal DACs anchored on nitrogen-doped graphene (TM₂/NC, TM= Pt, Ir, Rh, Pd, Ru, Co, Ni and Cu) was constructed to make a comprehensive investigation of their selectivity in the hydrogenative transformation of furfuryl alcohol (FAL), an important biomass platform molecule, to 1,2-pentanediol (1,2-PeD) via selective cleavage of furanic C5-O bond, by density functional theory (DFT) calculations and microkinetic modeling. We found that Ir₂/NC demonstrated a high selectivity for the cleavage of furanic C5-O bond to produce 1,2-PeD, while the production of THFAL or 1,5-pentanediol (1,5-PeD) on other TM₂/NC catalysts are more favorable. Furthermore, we found that the selective C-O bond cleavage of FAL furan ring is affected by the orbital overlap between the d-orbitals of the anchored metal atoms and the p-orbitals of the adsorbed C atom in FAL, suggesting that the selectivity of the C-O bond cleavage is inextricably related with the electronic property of the anchored metals.

Keywords

Furfuryl alcohol / Hydrogenation / Dual-atom catalyst / Density functional theory (DFT) calculation

References

[1] De S, Dutta S, Saha B. . Catal. Sci. Technol., 2016, 6(20): 7364,

[2] Delidovich I, Hausoul P J C, Deng L, Pfützenreuter R, Rose M, Palkovits R. . Chem. Rev., 2016, 116(3): 1540,

[3] Cai C M, Zhang T, Kumar R, Wyman C E. . J. Chem. Technol. Biotechnol., 2014, 89(1): 2,

[4] Chen S, Wojcieszak R, Dumeignil F, Marceau E, Royer S. . Chem. Rev., 2018, 118(22): 11023,

[5] Zhao Z, Yang C, Sun P, Gao G, Liu Q, Huang Z, Li F. . ACS Catal., 2023, 13(8): 5170,

[6] Zhao Z, Gao G, Xi Y, Wang J, Sun P, Liu Q, Yan W, Cui Y, Jiang Z, Li F. . Chem, 2022, 8(4): 1034,

[7] Zhang B, Zhu Y, Ding G, Zheng H, Li Y. . Green Chem., 2012, 14(12): 3402,

[8] Wijaya H W, Kojima T, Hara T, Ichikuni N, Shimazu S. . ChemCatChem, 2017, 9(14): 2869,

[9] Zhao Z, Bababrik R, Xue W, Li Y, Briggs N M, Nguyen D-T, Nguyen U, Crossley S P, Wang S, Wang B, Resasco D E. . Nat. Catal, 2019, 2(5): 431,

[10] Delaney H. . Synthesis of the Fungicide Propiconazole a Systemic Foliar Fungicide, 2000 Ireland Technological University Dublin

[11] Southby D. T., Szajewski R. P., Szajewski R., Southby D., Aqueous Inkjet Ink Useful for Printing Photo-Image on Both Photo-Glossy Receiver and Plain Paper Comprises Water, 1,2-Pentanediol, Humectant Distinct from 1,2-Pentanediol, and Dispersed Pigment Colorant, US2009169762-A1; WO2009085168-A1; EP2225335-A1; US8356892-B2; EP2225335-B1, 2009

[12] Liu H, Huang Z, Kang H, Xia C, Chen J. . Chinese Journal of Catalysis, 2016, 37(5): 700,

[13] Mizugaki T, Yamakawa T, Nagatsu Y, Maeno Z, Mitsudome T, Jitsukawa K, Kaneda K. . ACS Sustainable Chem. Eng., 2014, 2(10): 2243,

[14] Zhu Y, Zhao W, Zhang J, An Z, Ma X, Zhang Z, Jiang Y, Zheng L, Shu X, Song H, Xiang X, He J. . ACS Catal., 2020, 10(15): 8032,

[15] Ma R, Wu X-P, Tong T, Shao Z-J, Wang Y, Liu X, Xia Q, Gong X-Q. . ACS Catal., 2017, 7(1): 333,

[16] Jenness G R, Wan W, Chen J G, Vlachos D G. . ACS Catal., 2016, 6(10): 700,

[17] Dai D, Feng C, Wang M, Du Q, Liu D, Pan Y, Liu Y. . Catal. Sci. Technol., 2022, 12(19): 5879,

[18] Ying Y, Luo X, Qiao J, Huang H. . Adv. Funct. Mater., 2021, 31(3): 2007423,

[19] Pan Y, Zhang C, Liu Z, Chen C, Li Y. . Matter, 2020, 2(1): 78,

[20] Cao X, Zhao L, Wulan B, Tan D, Chen Q, Ma J, Zhang J. . Angew. Chem. Int Ed., 2022, 61(6): e202113918,

[21] Li X, Zhong W, Cui P, Li J, Jiang J. . J. Phys. Chem. Lett., 2016, 7(9): 1750,

[22] Chen Z W, Yan J, Jiang Q. . Small Methods., 2019, 3(6): 1800291,

[23] Di Liberto G, Cipriano L A, Pacchioni G. . J. Am. Chem. Soc., 2021, 143(48): 20431,

[24] Cui X, Tang C, Zhang Q. . Advanced Energy Materials, 2018, 8(22): 1800369,

[25] Ren W, Tan X, Yang W, Jia C, Xu S, Wang K, Smith S C, Zhao C. . Angew. Chem. Int. Ed., 2019, 58(21): 6972,

[26] Zhao S, Yi H, Tang X, Gao F, Wang J, Huang Y, Yang Z. . Adsorption, 2017, 23(7/8): 1013,

[27] Blöchl P E. . Phys. Rev. B, 1994, 50(24): 17953,

[28] Kresse G, Joubert D. . Phys. Rev. B, 1999, 59(3): 1758,

[29] Perdew J P, Burke K, Ernzerhof M. . Phys. Rev. Lett., 1996, 77(18): 3865,

[30] Kresse G. . Computational Materials Science, 1996, 6(1): 15,

[31] Kresse G, Furthmüller J. . Phys. Rev. B, 1996, 54(16): 11169,

[32] Grimme S, Antony J, Ehrlich S, Krieg H. . The Journal of Chemical Physics, 2010, 132(15): 154104,

[33] Henkelman G. . The Journal of Chemical Physics, 2000, 113(22): 9901,

[34] Henkelman G, Jónsson H. . The Journal of Chemical Physics, 1999, 111(15): 7010,

[35] Heyden A, Bell A T, Keil F J. . The Journal of Chemical Physics, 2005, 123(22): 224101,

[36] Ribeiro R F, Marenich A V, Cramer C J, Truhlar D G. . J. Phys. Chem. B, 2011, 115(49): 14556,

[37] Ulissi Z W, Medford A J, Bligaard T, Nørskov J K. . Nat. Commun., 2017, 8(1): 14621,

[38] Deringer V L, Tchougréeff A L, Dronskowski R. . J. Phys. Chem. A, 2011, 115(21): 5461,

[39] Maintz S, Deringer V L, Tchougréeff A L, Dronskowski R. . J. Comput. Chem., 2016, 37(11): 1030,

[40] Qian X. . J. Phys. Chem. B, 2013, 117(39): 11460,

[41] Gilkey M J, Mironenko A V, Yang L, Vlachos D G, Xu B. . ChemSusChem, 2016, 9(21): 3113,

[42] Trinh Q T, Chethana B K, Mushrif S H. . J. Phys. Chem. C, 2015, 119(30): 17137,

[43] Banerjee A, Mushrif S H. . ChemCatChem, 2017, 9(14): 2828,