Periodic Reporting for period 1 - SOLBIOCHEM (Solar-driven Electrocatalytic Biomass Upgrading to Value-added Chemicals)
Periodo di rendicontazione: 2020-07-01 al 2022-06-30
Modern society in the European Union and around the world is currently highly dependent on the large-scale production of chemicals from fossil resources in conventional refineries, which contributes to make the chemical industry one of the most CO2 intensive industry on the planet. Therefore, in the context of the current energy transition, it is necessary to develop alternative ways to generate carbon-based molecules with a reduced CO2 footprint. In particular, using lignoceelulose as a contemporary, renewable source of carbon in biorefineries powered with renewable energy is seen as a promising path forward. One possible model for these biorefineries is the coupling of a first unit dedicated to the depolymerisation/break down of polymeric biomass molecules with a second unit capable of upgrading the molecules obtained in the first step to value-added chemicals and fuels. Moreover, the use of electrocatalysis to perform this chemical upgrading is attractive due to its operation at ambient conditions of temperature and pressure, its ability to be directly powered by renewable electricity and its reliance on water as a source of protons and oxygen atoms (as opposed to molecular H2 and O2 in thermocatalytic processes).
SOLBIOCHEM proposed the development of earth-abundant electrocatalysts for the valorisation of biomass-derived platform-compounds, and in particular the furanic furfural and 5-hydroxymethylfurfural (HMF) molecules extracted from celullose and hemicellulose respectively. Moreover the ultimate goal of the project was to couple this electrocatalytic upgrading with electricity generated from sunlight by a photovoltaic device or inside a photoelectrochemical cell. Over the course of the action, we were able to develop micro-structured copper-based cathodes capable of converting furfural selectively into furufryl alcohol or methylfuran in aqueous electrolytes with significantly improved activity compared to state-of-the-art reports. Moreover, efficient CuInxGa(1-x)S2 photocathodes were produced, in order to be coupled with the aforementioned copper electrocatalyst. The investigation of HMF oxidation on Ni-based anodes was also started within the framework of this action, with preliminary results on the influence of the calcination temperature of the catalysts on its selectivity towards different oxidation products of HMF.
SOLBIOCHEM proposed the development of earth-abundant electrocatalysts for the valorisation of biomass-derived platform-compounds, and in particular the furanic furfural and 5-hydroxymethylfurfural (HMF) molecules extracted from celullose and hemicellulose respectively. Moreover the ultimate goal of the project was to couple this electrocatalytic upgrading with electricity generated from sunlight by a photovoltaic device or inside a photoelectrochemical cell. Over the course of the action, we were able to develop micro-structured copper-based cathodes capable of converting furfural selectively into furufryl alcohol or methylfuran in aqueous electrolytes with significantly improved activity compared to state-of-the-art reports. Moreover, efficient CuInxGa(1-x)S2 photocathodes were produced, in order to be coupled with the aforementioned copper electrocatalyst. The investigation of HMF oxidation on Ni-based anodes was also started within the framework of this action, with preliminary results on the influence of the calcination temperature of the catalysts on its selectivity towards different oxidation products of HMF.
SOLBIOCHEM allowed the following work to be performed over the two years of the action:
(i) Setup of a reproducible two-compartment electrocatalysis H-cell for biomass valorisation with in-line gas product analysis.
(ii) Synthesis and performance analysis of a range of earth-abundant metal-based electrocatalysts for furanic compounds conversion.
(iii) Development and optimisation of micro-structured copper electrodes capable of reducing furfural at potentials as low as -0.2 V vs RHE and with current densities in the order of 10 mA.cm-2 for a 0.01M furfural solution. These electrodes are capable of converting furfural to furfuryl alcohol at neutral pH with a 100% selectivity, and ro methylfuran in acidic pH with a 80% selectivity (the remaining 20% being furfuryl alcohol). Due to the volatility and non-solubility of methylfuran in water it is however readily separated from the alcohol and can be recovered selectively in a cold trap at the outlet of the electrolyser.
(iv) Testing of CIGS photocathodes with state-of-the-art performances for future coupling with copper-based reduction electrocatalysts for furfural reduction (reaching 30 mA.cm-2 at 0V vs RHE).
(v) Preliminary exploration of HMF oxidation on nano-structured nickel anodes for future coupling with furfural reduction.
(vi) Performance of in-situ NAP-XPS (unprecedented for biomass electrolysis) and Raman spectroscopy experiments to gain mechanistic insight in the processes at hand. In particular, in-situ NAP-XPS allows to analyse the evolution of the carbon signal related to adsorbed molecules on the surface of the electrodes as a function of the applied potential. This signal can be deconvoluted into the different oxidation states of the carbon corresponding to different functional groups of the molecule.
The results obtained on furfural reduction on structured copper electrodes will be the object of a scientific publication shortly. Other results will serve as a strong basis for a second study corresponding to the development of a solar-powered device for the conversion of biomass-derived furanic compounds.
Moreover, dissemination towards young researchers and student and the genereal public was performe during the action, in particular with:
(i) The participation in the organisation of the Winter School CatEnerChem (https://catenerchem.cpe.fr/(si apre in una nuova finestra)) with high-profile scientific guests from the research fields of catalysis, but also experts from social sciences (economists, philosophers, sociologists) to discuss in-depth the place of chemistry in the energy transition and what are realistic avenues for the decarbonation of the chemical industry.
(ii) The participation the festival Yggdrasil "Demain mais en mieux" (translation: "tomorrow, but better", https://demainmaisenmieux.festivalyggdrasil.fr/(si apre in una nuova finestra)) where 25000 people from the general public were able to communicate with researchers of different french institution on their profession and the impact of their work on society and how it can benefit them.
(i) Setup of a reproducible two-compartment electrocatalysis H-cell for biomass valorisation with in-line gas product analysis.
(ii) Synthesis and performance analysis of a range of earth-abundant metal-based electrocatalysts for furanic compounds conversion.
(iii) Development and optimisation of micro-structured copper electrodes capable of reducing furfural at potentials as low as -0.2 V vs RHE and with current densities in the order of 10 mA.cm-2 for a 0.01M furfural solution. These electrodes are capable of converting furfural to furfuryl alcohol at neutral pH with a 100% selectivity, and ro methylfuran in acidic pH with a 80% selectivity (the remaining 20% being furfuryl alcohol). Due to the volatility and non-solubility of methylfuran in water it is however readily separated from the alcohol and can be recovered selectively in a cold trap at the outlet of the electrolyser.
(iv) Testing of CIGS photocathodes with state-of-the-art performances for future coupling with copper-based reduction electrocatalysts for furfural reduction (reaching 30 mA.cm-2 at 0V vs RHE).
(v) Preliminary exploration of HMF oxidation on nano-structured nickel anodes for future coupling with furfural reduction.
(vi) Performance of in-situ NAP-XPS (unprecedented for biomass electrolysis) and Raman spectroscopy experiments to gain mechanistic insight in the processes at hand. In particular, in-situ NAP-XPS allows to analyse the evolution of the carbon signal related to adsorbed molecules on the surface of the electrodes as a function of the applied potential. This signal can be deconvoluted into the different oxidation states of the carbon corresponding to different functional groups of the molecule.
The results obtained on furfural reduction on structured copper electrodes will be the object of a scientific publication shortly. Other results will serve as a strong basis for a second study corresponding to the development of a solar-powered device for the conversion of biomass-derived furanic compounds.
Moreover, dissemination towards young researchers and student and the genereal public was performe during the action, in particular with:
(i) The participation in the organisation of the Winter School CatEnerChem (https://catenerchem.cpe.fr/(si apre in una nuova finestra)) with high-profile scientific guests from the research fields of catalysis, but also experts from social sciences (economists, philosophers, sociologists) to discuss in-depth the place of chemistry in the energy transition and what are realistic avenues for the decarbonation of the chemical industry.
(ii) The participation the festival Yggdrasil "Demain mais en mieux" (translation: "tomorrow, but better", https://demainmaisenmieux.festivalyggdrasil.fr/(si apre in una nuova finestra)) where 25000 people from the general public were able to communicate with researchers of different french institution on their profession and the impact of their work on society and how it can benefit them.
The project allowed to produced electrodes showing improvment over the state-of-the-art for Furfural reduction, while retaining high selectivity and durability.
Pennakem, an industrial actor of the valoridation of biomass waste, is interested in the conversion and furfural and will be approached to discuss potential collaboration to bring the results developed in SOLBIOCHEM closer to application, and therefore closer to benefit society.
Pennakem, an industrial actor of the valoridation of biomass waste, is interested in the conversion and furfural and will be approached to discuss potential collaboration to bring the results developed in SOLBIOCHEM closer to application, and therefore closer to benefit society.