Abstract
The development of general strategies for the electronic tuning of a catalyst's active site is an ongoing challenge in heterogeneous catalysis. To this end, herein, we describe the application of Li-ion battery cathode and anode materials as redox non-innocent catalyst supports that can be continuously modulated as a function of lithium intercalation. A zero-valent nickel complex was oxidatively grafted onto the surface of lithium manganese oxide (LixMn2O4) to yield isolated Ni2+ occupying the vacant interstitial octahedral site in the Li diffusion channel on the surface and subsurface of the spinel structure (Ni/LixMn2O4). The activity of Ni/LixMn2O4 for olefin hydrogenation, as a representative probe reaction, was found to increase monotonically as a function of support reductive lithiation. Simulation of Ni/LixMn2O4 reveals the dramatic impact of surface redox states on the viability of the homolytic oxidative addition mechanism for H2 activation. Catalyst control through support lithiation was extended to an organotantalum complex on LixTiO2, demonstrating the generality of this phenomenon.
Original language | English |
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Pages (from-to) | 7233-7242 |
Number of pages | 10 |
Journal | ACS Catalysis |
Volume | 12 |
Issue number | 12 |
DOIs | |
State | Published - Jun 17 2022 |
Externally published | Yes |
Funding
Work at Argonne National Laboratory was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, Catalysis Science Program under Contract No. DE-AC-02-06CH11357. All DFT and XANES calculations were performed using the computational resources provided by the Laboratory Computing Resource Center (LCRC) at Argonne National Laboratory (ANL). Use of the Advanced Photon Source is supported by the U.S. Department of Energy, Office of Science, and Office of the Basic Energy Sciences, under Contract No. DEAC02-06CH11357. MRCAT operations were supported by the Department of Energy and the MRCAT member institutions. Use of the Center for Nanoscale Materials, including TEM, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DEAC02-06CH11357. The ANL Talos and ACAT microscopes are part of the Center for Nanoscale Materials, while the ANL PicoProbe microscope is part of the Photon Sciences Directorate. Work by Chris Johnson was supported as part of the Center for Electrochemical Energy Science (CEES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. The experimental studies carried out at Brookhaven National Laboratory (AP-XPS) were supported by the US Department of Energy under Contract number DE-SC0012704. F.D. acknowledges the support from the Vehicle Technologies Office at the U.S. Department of Energy, Energy Efficiency and Renewable Energy. The EPR work (O.G.P., J.N.) was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract no. DE-AC-02-06CH11357.
Keywords
- catalyst design
- hydrogenation
- nickel
- surface organometallic chemistry
- tunable catalysis