(154h) Electrocatalytic hydrogenation of model bio-oil compounds on Pt and Rh
AIChE Annual Meeting
2020
2020 Virtual AIChE Annual Meeting
Liaison Functions
Undergraduate Research Presentations - Energy, Materials, and Petrochemicals
Monday, November 16, 2020 - 9:45am to 10:00am
Bio-oil is recognized as a sustainable resource to offset fossil fuel demand and reduce green-
house gas emissions. To convert the biomass into valuable fuels or chemicals, catalytic hydro-
genation and deoxygenation of bio-oil compounds such as phenol and benzaldehyde are neces-
sary. The H2 for hydrogenation is typically obtained from methane steam reforming, which is en-
ergy intensive and produces CO2. If instead hydrogen equivalents are provided by the reduction
of protons via aqueous phase electrocatalytic hydrogenation (ECH), biomass hydrogenation
could be driven using renewable electricity, opening an attractive route to produce high-energy
density transportation fuels in a sustainable manner. The main challenge hindering the wide-
spread use of ECH for bio-oil conversion is the high cost relative to fossil fuels. By understanding
and increasing ECH activity and selectivity, the economics can be drastically improved.
In this project, the thermodynamics and kinetics of aqueous-phase ECH of phenol to cyclohexanol
on platinum and rhodium metals are investigated via density functional theory (DFT) calculations
and first-principles microkinetic simulations. The experimentally measured intrinsic rate for ECH
of phenol on Pt/C and Rh/C nanoparticles decreases as the average particle size decreases.
Therefore, we hypothesize that the active sites for phenol hydrogenation are (111) and (100)
terraces, which are more prevalent than step sites on the surfaces of larger particles. To test this
hypothesis, we perform DFT calculations of phenol hydrogenation on the (111) terraces, (100)
terraces, and (553) step of Pt and Rh. All DFT calculations used the Perdew-Burke-Ernzerhof
functional with the semi-empirical D3 dispersion correction (PBE-D3). The effect of applied
potential on the thermodynamics and kinetics was incorporated using the computational hydrogen
electrode and the Butler-Volmer formalism. We predict that the platinum terraces are more active
than the step sites, in agreement with our experimental observations. For Rh, a large dependence
on the phenol hydrogenation kinetics is observed depending on hydrogen coverage. Ultimately,
these findings provide atomistic insight into the activity differences between steps and terraces of
Pt and Rh toward phenol ECH, as well as the impact of hydrogen coverage on ECH
thermodynamics and kinetics.
house gas emissions. To convert the biomass into valuable fuels or chemicals, catalytic hydro-
genation and deoxygenation of bio-oil compounds such as phenol and benzaldehyde are neces-
sary. The H2 for hydrogenation is typically obtained from methane steam reforming, which is en-
ergy intensive and produces CO2. If instead hydrogen equivalents are provided by the reduction
of protons via aqueous phase electrocatalytic hydrogenation (ECH), biomass hydrogenation
could be driven using renewable electricity, opening an attractive route to produce high-energy
density transportation fuels in a sustainable manner. The main challenge hindering the wide-
spread use of ECH for bio-oil conversion is the high cost relative to fossil fuels. By understanding
and increasing ECH activity and selectivity, the economics can be drastically improved.
In this project, the thermodynamics and kinetics of aqueous-phase ECH of phenol to cyclohexanol
on platinum and rhodium metals are investigated via density functional theory (DFT) calculations
and first-principles microkinetic simulations. The experimentally measured intrinsic rate for ECH
of phenol on Pt/C and Rh/C nanoparticles decreases as the average particle size decreases.
Therefore, we hypothesize that the active sites for phenol hydrogenation are (111) and (100)
terraces, which are more prevalent than step sites on the surfaces of larger particles. To test this
hypothesis, we perform DFT calculations of phenol hydrogenation on the (111) terraces, (100)
terraces, and (553) step of Pt and Rh. All DFT calculations used the Perdew-Burke-Ernzerhof
functional with the semi-empirical D3 dispersion correction (PBE-D3). The effect of applied
potential on the thermodynamics and kinetics was incorporated using the computational hydrogen
electrode and the Butler-Volmer formalism. We predict that the platinum terraces are more active
than the step sites, in agreement with our experimental observations. For Rh, a large dependence
on the phenol hydrogenation kinetics is observed depending on hydrogen coverage. Ultimately,
these findings provide atomistic insight into the activity differences between steps and terraces of
Pt and Rh toward phenol ECH, as well as the impact of hydrogen coverage on ECH
thermodynamics and kinetics.