TY - JOUR
T1 - Support Effect of Metal-Organic Frameworks on Ethanol Production through Acetic Acid Hydrogenation
AU - Yoshimaru, Shotaro
AU - Sadakiyo, Masaaki
AU - Maeda, Nobutaka
AU - Yamauchi, Miho
AU - Kato, Kenichi
AU - Pirillo, Jenny
AU - Hijikata, Yuh
N1 - Funding Information:
This work was partly supported by JSPS Grant-in-Aid for Scientific Research No. 17H04890, JSPS Research Fellowship for Young Scientists No. 18J10267, JST-CREST, and JSPS KAKENHI Grant Nos. 18H05517 (Hydrogenomics) and JP19H04570 (Coordination Asymmetry). The synchrotron radiation experiments were performed on BL44B2 beamline in SPring-8 with the approval of RIKEN (Proposal No. 20150058).
Publisher Copyright:
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PY - 2021/5/5
Y1 - 2021/5/5
N2 - We present a systematic study on the support effect of metal-organic frameworks (MOFs), regarding substrate adsorption. A remarkable enhancement of both catalytic activity and selectivity for the ethanol (EtOH) production reaction through acetic acid (AcOH) hydrogenation (AH) was observed on Pt nanoparticles supported on MOFs. The systematic study on catalysis using homogeneously loaded Pt catalysts, in direct contact with seven different MOF supports (MIL-125-NH2, UiO-66-NH2, HKUST-1, MIL-101, Zn-MOF-74, Mg-MOF-74, and MIL-121) (abbreviated as Pt/MOFs), found that MOFs having a high affinity for the AcOH substrate (UiO-66-NH2 and MIL-125-NH2) showed high catalytic activity for AH. This is the first demonstration indicating that the adsorption ability of MOFs directly accelerates catalytic performance using the direct contact between the metal and the MOF. In addition, Pt/MIL-125-NH2 showed a remarkably high EtOH yield (31% at 200 °C) in a fixed-bed flow reactor, which was higher by a factor of more than 8 over that observed for Pt/TiO2, which was the best Pt-based catalyst for this reaction. Infrared spectroscopy and a theoretical study suggested that the MIL-125-NH2 support plays an important role in high EtOH selectivity by suppressing the formation of the byproduct, ethyl acetate (AcOEt), due to its relatively weak adsorption behavior for EtOH rather than AcOH.
AB - We present a systematic study on the support effect of metal-organic frameworks (MOFs), regarding substrate adsorption. A remarkable enhancement of both catalytic activity and selectivity for the ethanol (EtOH) production reaction through acetic acid (AcOH) hydrogenation (AH) was observed on Pt nanoparticles supported on MOFs. The systematic study on catalysis using homogeneously loaded Pt catalysts, in direct contact with seven different MOF supports (MIL-125-NH2, UiO-66-NH2, HKUST-1, MIL-101, Zn-MOF-74, Mg-MOF-74, and MIL-121) (abbreviated as Pt/MOFs), found that MOFs having a high affinity for the AcOH substrate (UiO-66-NH2 and MIL-125-NH2) showed high catalytic activity for AH. This is the first demonstration indicating that the adsorption ability of MOFs directly accelerates catalytic performance using the direct contact between the metal and the MOF. In addition, Pt/MIL-125-NH2 showed a remarkably high EtOH yield (31% at 200 °C) in a fixed-bed flow reactor, which was higher by a factor of more than 8 over that observed for Pt/TiO2, which was the best Pt-based catalyst for this reaction. Infrared spectroscopy and a theoretical study suggested that the MIL-125-NH2 support plays an important role in high EtOH selectivity by suppressing the formation of the byproduct, ethyl acetate (AcOEt), due to its relatively weak adsorption behavior for EtOH rather than AcOH.
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U2 - 10.1021/acsami.1c01100
DO - 10.1021/acsami.1c01100
M3 - Article
C2 - 33877813
AN - SCOPUS:85105973534
SN - 1944-8244
VL - 13
SP - 19992
EP - 20001
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 17
ER -