Fundamental Understanding of Chemical Transformations at the Interface between Bimetallic Catalysts and Solvents
EMSL Project ID
48920
Abstract
Production of biofuels from lignocellulosic biomass, a renewable resource, can play a significant role in achieving goals of long term sustainability for the current energy infrastructure while simultaneously introducing new economic opportunities for both nations and individuals. While direct conversion methods such as pyrolysis can utilize all the carbon in lignocellulosic biomass, it creates enormous challenges for the downstream processing. In particular, catalysts developed thus far are inefficient and costly in converting pyrolysis oils to biofuels. This is mainly due to the limited catalytic material choice to precious metals which are efficient in two-electron reactions, and the lack of fundamental understanding of the interactions between catalyst surface and the complex functional groups (ketones, acids, aldehydes, phenolics) as well as the large quantity of water present in the pyrolysis oils. To enable sustainable conversion of lignocellulosic biomass, we propose to address the scientific issues related to the energy and atom efficiency for biomass conversion using earth abundant and non-precious metal based bimetallic catalysts (e.g., Fe, Ni). We particularly aim to provide an atomistic understanding of the surface interactions directly leading to the improved catalytic conversion performance such as hydrodeoxygeantion (HDO) on Fe or Ni based bimetallic surfaces. We expect to identify key predictors in the electronic character of transition metal promoters which can be used to develop new, cheaper, and higher performing HDO catalysts. Our working hypothesis is that promoters can provide long range electronic and structural stabilization of low oxidation states of non-precious and earth abundant metal surfaces (e.g., Fe and Ni) even in the presence of condensed water such that two-electron reactions can undergo on these earth abundant metals just like that on precious metals. We propose to use the critical capabilities available at EMSL (SFG, surface science, STEM, atom probe) coupled with theory to understand the interactions at the liquid-solid interface that are associated with catalytic conversion of lignocellulosic biomass in the condensed phase. Throughout the course of this project, a close correlation between experiment and theory on model catalysts will be performed in order to reduce both the computational expense and experimental efforts in characterizing such complex systems. To reach this goal, we have assembled a team with a wealth of experience in both the application and science of heterogeneous catalysis and track of record in collaborating with EMSL staff in producing high impact science, especially as related to the bimetallic catalysts for hydrodeoxygenation of phenolic compounds, and with outstanding expertise in the diverse tools necessary to achieve the objectives of the proposed studies.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2015-10-01
End Date
2017-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Fu S, C Zhu, D Su, J Song, S Yao, S Feng, MH Engelhard, D Du, and Y Lin. 2018. "Porous Carbon-Hosted Atomically Dispersed Iron–Nitrogen Moiety as Enhanced Electrocatalysts for Oxygen Reduction Reaction in a Wide Range of pH." Small 14(12):Article No. 1703118. doi:10.1002/smll.201703118
Fu S, C Zhu, J Song, MH Engelhard, H Xia, D Du, and Y Lin. 2016. "Kinetically Controlled Synthesis of Pt-Based One-Dimensional Hierarchically Porous Nanostructures with Large Mesopores as Highly Efficient ORR Catalysts." ACS Applied Materials & Interfaces 8(51):35213-35218. doi:10.1021/acsami.6b11537
Fu, Shaofang, Zhu, Chengzhou, Song, Junhua, Engelhard, Mark H., He, Yang, Du, Dan, Wang, Chongmin, Lin, Yuehe. 2016. Journal of Materials Chemistry A (4) 22, 2050-7488. http://dx.doi.org/10.1039/C6TA01801G. Three-dimensional PtNi Hollow Nanochains as Enhanced Electrocatalyst for Oxygen Reduction Reaction.
Hensley A.J., Y. Wang, D. Mei, and J. McEwen. 2018. "Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites." ACS Catalysis 8, no. 3:2200-2208. PNNL-SA-130676. doi:10.1021/acscatal.7b02576
Hong Y, A Hensley, JS McEwen, and Y Wang. 2016. "Perspective on Catalytic Hydrodeoxygenation of Biomass Pyrolysis Oils: Essential Roles of Fe-based Catalysts." Catalysis Letters 146(9):1621-1633. doi:10. 1007/s10562-016-1770-1
Shi Q., C. Zhu, H. Zhong, D. Su, L. Na, M.H. Engelhard, and H. Xia, et al. 2018. "Nanovoid Incorporated IrxCu Metallic Aerogels for Oxygen Evolution Reaction Catalysis." ACS Energy Letters 3, no. 9:2038–2044. PNNL-SA-138184. doi:10.1021/acsenergylett.8b01338
Shi Q, C Zhu, MH Engelhard, D Du, and Y Lin. 2017. "Highly Uniform Distribution of Pt Nanoparticles on N-Doped Hollow Carbon Spheres with Enhanced Durability for Oxygen Reduction Reaction." RSC Advances 7(11):6303-6308. doi:10.1039/c6ra25391a
Shi Q, C Zhu, Y Li, H Xia, MH Engelhard, S Fu, D Du, and Y Lin. 2016. "A Facile Method for Synthesizing Dendritic Core-Shell Structured Ternary Metallic Aerogels and Their Enhanced Electrochemical Performances." Chemistry of Materials 28(21):7928-7934. doi:10.1021/acs.chemmater.6b03549
Therrien A.J., A.J. Hensley, R. Zhang, A. Pronschinske, M.D. Marcinkowski, J. McEwen, and E.H. Sykes. 2017. "Characterizing the Geometric and Electronic Structure of Defects in the “29” Copper." Journal of Chemical Physics. doi:10.1063/1.4996729
Therrien A.J., K.J. Groden, A.J. Hensley, A.C. Schilling, R.T. Hannagan, M.D. Marcinkowski, and A. Pronschinske, et al. 2018. "Water Activation by Single Pt Atoms Supported on a Cu2O Thin Film." Journal of Catalysis 364. doi:10.1016/j.jcat.2018.04.024
Therrien AJ, R Zhang, FR Lucci, MD Marcinkowski, A Hensley, JS McEwen, and ECH Sykes. 2016. "Structurally Accurate Model for the “29”-Structure of CuxO/Cu(111): A DFT and STM Study." Journal of Physical Chemistry C 120(20):10879–10886. doi:10.1021/acs.jpcc.6b01284
Yu N., M.M. Rahman, J. Chen, J. Sun, M.H. Engelhard, X.I. Pereira Hernandez, and Y. Wang. 2018. "Steam reforming of simulated bio-oil on K-Ni-Cu-Mg-Ce-O/Al2O3: The effect of K." Catalysis Today 323. PNNL-SA-135619. doi:10.1016/j.cattod.2018.04.010
Zhu C, S Fu, B Xu, J Song, Q Shi, MH Engelhard, X Li, SP Beckman, J Sun, D Du, and Y Lin. 2017. "Sugar Blowing-induced Porous Cobalt Phosphide/nitrogen-doped Carbon Nanostructures With Enhanced Electrochemical Oxidation Performance Towards Water And Other Small Molecules." Small 13(33):Article No. 1700796. doi:10.1002/smll.201700796