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Title: Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica

Abstract

With the increasing attention on single-site heterogeneous catalysts on account of their high specific activity, more effective catalyst design strategies are necessary. We demonstrate a first-principles-calculation-guided active-site design strategy for alkene hydrogenation using silica-supported single-atom single-site heterogeneous catalysts (SSHCs, i.e., M/SiO2). An activity-descriptor relationship for propylene hydrogenation was established using representative catalysts (i.e., Ga3+, Zn2+, Mn2+ and Ti4+/SiO2), correlating the computational activity descriptor (i.e., the reaction free energy of the metal hydride formation) with the experimental reaction rates. Microkinetic modeling confirmed the predicted reaction mechanisms and further explained the rationale of the activity-descriptor relationship. This relationship was then used to predict the trend of activities of a variety of isolated ions on silica, and an In3+/SiO2 catalyst was identified as the most promising candidate based on its predicted activity and synthetic feasibility. The monodispersed In3+/SiO2 catalyst was then synthesized, for the first time, and showed higher propylene hydrogenation activity than the other four single-atom SSHCs, as predicted. Detailed spectroscopic characterization (XAS, XPS, DRIFTS and DRUV-Vis) provided insights into coordination environments and oxidation states of the catalysts, as well as evidence for the hydride intermediate. The successful discovery of the In3+/SiO2 catalyst for propylene hydrogenation using the first-principles-calculations-guided design strategy opensmore » up new opportunities for efficient development of single-atom SSHCs.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1462737
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 152; Journal Issue: C; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
DFT; Hydrogenation; Single-atom catalysis

Citation Formats

Liu, Cong, Camacho-Bunquin, Jeffrey, Ferrandon, Magali, Savara, Aditya, Sohn, Hyuntae, Yang, Dali, Kaphan, David M., Langeslay, Ryan R., Ignacio-de Leon, Patricia A., Liu, Shengsi, Das, Ujjal, Yang, Bing, Hock, Adam S., Stair, Peter C., Curtiss, Larry A., and Delferro, Massimiliano. Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica. United States: N. p., 2018. Web. doi:10.1016/j.poly.2018.06.006.
Liu, Cong, Camacho-Bunquin, Jeffrey, Ferrandon, Magali, Savara, Aditya, Sohn, Hyuntae, Yang, Dali, Kaphan, David M., Langeslay, Ryan R., Ignacio-de Leon, Patricia A., Liu, Shengsi, Das, Ujjal, Yang, Bing, Hock, Adam S., Stair, Peter C., Curtiss, Larry A., & Delferro, Massimiliano. Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica. United States. doi:10.1016/j.poly.2018.06.006.
Liu, Cong, Camacho-Bunquin, Jeffrey, Ferrandon, Magali, Savara, Aditya, Sohn, Hyuntae, Yang, Dali, Kaphan, David M., Langeslay, Ryan R., Ignacio-de Leon, Patricia A., Liu, Shengsi, Das, Ujjal, Yang, Bing, Hock, Adam S., Stair, Peter C., Curtiss, Larry A., and Delferro, Massimiliano. Sat . "Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica". United States. doi:10.1016/j.poly.2018.06.006.
@article{osti_1462737,
title = {Development of activity–descriptor relationships for supported metal ion hydrogenation catalysts on silica},
author = {Liu, Cong and Camacho-Bunquin, Jeffrey and Ferrandon, Magali and Savara, Aditya and Sohn, Hyuntae and Yang, Dali and Kaphan, David M. and Langeslay, Ryan R. and Ignacio-de Leon, Patricia A. and Liu, Shengsi and Das, Ujjal and Yang, Bing and Hock, Adam S. and Stair, Peter C. and Curtiss, Larry A. and Delferro, Massimiliano},
abstractNote = {With the increasing attention on single-site heterogeneous catalysts on account of their high specific activity, more effective catalyst design strategies are necessary. We demonstrate a first-principles-calculation-guided active-site design strategy for alkene hydrogenation using silica-supported single-atom single-site heterogeneous catalysts (SSHCs, i.e., M/SiO2). An activity-descriptor relationship for propylene hydrogenation was established using representative catalysts (i.e., Ga3+, Zn2+, Mn2+ and Ti4+/SiO2), correlating the computational activity descriptor (i.e., the reaction free energy of the metal hydride formation) with the experimental reaction rates. Microkinetic modeling confirmed the predicted reaction mechanisms and further explained the rationale of the activity-descriptor relationship. This relationship was then used to predict the trend of activities of a variety of isolated ions on silica, and an In3+/SiO2 catalyst was identified as the most promising candidate based on its predicted activity and synthetic feasibility. The monodispersed In3+/SiO2 catalyst was then synthesized, for the first time, and showed higher propylene hydrogenation activity than the other four single-atom SSHCs, as predicted. Detailed spectroscopic characterization (XAS, XPS, DRIFTS and DRUV-Vis) provided insights into coordination environments and oxidation states of the catalysts, as well as evidence for the hydride intermediate. The successful discovery of the In3+/SiO2 catalyst for propylene hydrogenation using the first-principles-calculations-guided design strategy opens up new opportunities for efficient development of single-atom SSHCs.},
doi = {10.1016/j.poly.2018.06.006},
journal = {Polyhedron},
issn = {0277-5387},
number = C,
volume = 152,
place = {United States},
year = {2018},
month = {9}
}