Title: Effects of Cu–Ni Bimetallic Catalyst Composition and Support on Activity, Selectivity, and Stability for Furfural Conversion to 2-Methyfuran

Abstract

Supported bimetallic catalysts have been shown to enhance catalytic activity, product selectivity, and catalyst stability over supported monometallic catalysts for a range of catalytic reactions. Yet, the surface structure and composition of bimetallic particles can differ significantly from the bulk due to variations in surface energies and interactions with adsorbates, making the design of bimetallic catalysts with targeted properties and reactivities challenging. We report here the influence of catalyst support (Al₂O₃ and TiO₂) on the surface composition and structure of bimetallic Cu-Ni nanoparticles with varying Ni weight loading (0, 0.5, 1.5, 3, 5, &10 wt%) at a constant Cu loading of 5 wt% and a correlation to catalytic reactivity and stability in furfural (FF) hydrodeoxygenation (HDO). Analysis via depth-profiling X-Ray Photoelectron Spectroscopy suggested that over a range of Ni compositions in Cu-Ni/Al₂O₃ catalysts, Cu and Ni were distributed evenly within bimetallic particles, although Cu and Ni segregated into contiguous monometallic domains at the particle surfaces. In contrast, on Cu-Ni/TiO₂ catalysts near surface alloys formed, which were enriched in Cu at the particle surfaces and exposed only dispersed Ni species. The difference in compositional structure of the Cu-Ni particles on TiO₂ and Al₂O₃ was attributed to strong and specific interactions betweenmore » Ni and TiO₂. On both supports the addition of Ni to Cu catalysts resulted in significant enhancements in the rate of FF HDO, although Al₂O₃ supported bimetallic catalysts promoted hydrogenation of the furan ring, forming mostly furfural alcohol and tetrahydrofurfuryl alcohol, while TiO₂ supported catalysts mostly resulted in carbonyl hydrogenolysis to form methyl furan (MF). Through optimization of support and bimetallic compositions, low cost bimetallic catalysts were developed that demonstrated >90% MF yields in FF HDO with good stability and regenerability.« less

Authors:

Seemala, Bhogeswararao ^[1]; Cai, Charles M. ^[1]; Kumar, Rajeev ^[1]; Wyman, Charles E. ^[1]; Christopher, Phillip  ^[1]

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+ Show Author Affiliations

1. Univ. of California, Riverside, CA (United States)

Publication Date:

Tue Dec 05 00:00:00 EST 2017

Research Org.:

Univ. of California, Riverside, CA (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office

OSTI Identifier:

1581907

Grant/Contract Number:  

EE0007006

Resource Type:

Accepted Manuscript

Journal Name:

ACS Sustainable Chemistry & Engineering

Additional Journal Information:

Journal Volume: 6; Journal Issue: 2; Journal ID: ISSN 2168-0485

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Hydrodeoxygenation; Bimetallic catalysts; Metal−support interactions; Biofuels; Heterogeneous catalysis