Magnetism and Optics for Nanoparticle Catalysis

Informations projet

MONACAT

N° de convention de subvention: 694159

DOI

10.3030/694159

Projet clôturé

Date de signature de la CE 13 Mai 2016

Date de début 1 Juin 2016

Date de fin 31 Mai 2021

Financé au titre de

• EXCELLENT SCIENCE - European Research Council (ERC)

Coût total

€ 2 472 222,54

Contribution de l’UE

€ 2 472 222,54

Coordonné par

CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE CNRS
France

Periodic Reporting for period 4 - MONACAT (Magnetism and Optics for Nanoparticle Catalysis)

Période du rapport: 2020-12-01 au 2021-05-31

Résumé du contexte et des objectifs généraux du projet

The development of renewable energies is an essential requirement for a future sustainable world. Presently, most of the countries announce a development of both solar and wind power. However, both energies are intermittent and raise questions regarding their real efficiency since energy production can oscillate between shortage and over-production. The present solution to this problem is the use of the “smart grid” associated to a complex power management. The result is nevertheless a loss of ca.10% of the electrical energy produced in France (25 to 70 TWh). An interesting alternative would involve local electrical energy storage but it is costly and still displays a low efficiency. The power-to-gas approach is another alternative for which the first natural candidate would be hydrogen produced by water electrolysis but despite impressive progresses, its local storage, transport and massive use still presents safety, technology and cost issues. In light of these facts, the most relevant answer appears to be hydrocarbons since they display the largest energy density on a Ragone plot and could be used locally for heating and transport applications or be carried on long distances using existing systems.
MONACAT proposed a novel approach to address the challenge of intermittent energy storage. Specifically, the purpose is to conceive and synthesize novel complex nano-objects displaying both physical and chemical properties that enable catalytic transformations with a fast and optimum energy conversion upon magnetic or optical excitation. In this respect, MONACAT reported first a process of magnetically induced CO2 hydrogenation for chemical storage of intermittent energies which is now developed at the pilot scale with an industrial partner. The applications can however be much broaader since magnetically induced catalysis has further been applied to higher temperature reactions such as propane and methane dry reforming and propane dehydrogenation as well as in solution for biomass molecules transformations.
The new process of magnetically induced catalysis has two main advantages : i) the possibility to trigger a catalytic reaction within a time scale of a second. This is fully adapted to intermittent energies. ii) the energy efficiency, expected to be the highest for heating a ferromagnetic material. The results were excellent in terms of both catalytic activity and selectivity for methane as well as in terms of energy efficiency observed at the lab scale and expected on a large facility. This led to the design and realization of a pilot delivered in july 2021. The first use of this pilot will be to enrich biogas (ca. 1/3 CO2, 2/3 CH4) into pure methane and to inject it into existing gas delivery pipes. This pilot construction and pilot operation are financed by ToulouseTechTransfer and Téréga (https://www.toulouse-tech-transfer.com/wp-content/uploads/2020/12/cp-terega-ttt.pdf).
In addition MONACAT explored a new concept of high temperature catalysis in solution thanks to the "overheating" of the catalyst by magnetic induction. This allows to perform at moderate temperature and pressure reactions traditionally carried out in much more severe conditions such as those involving the transformations of biomass derived molecules. But the concepts resulting from MONACAT also led us to develop in collaboration electrolysis assisted by magnetic induction where significant gains were observed.

Travail effectué depuis le début du projet jusqu’à la fin de la période considérée dans le rapport et principaux résultats atteints jusqu’à présent

The 6 tasks present in the proposal have been fullfilled and are described in detail in the scientific report. Task 1 ("Monitoring and optimization of methanation at the surface of complex nanoparticles") and Task 2 (Optimization of heating capacities of magnetic nano-objects and energy efficiency) led to the construction of a pilot in collaboration with Téréga for the enrichment of biogas into methane and to a collaboration with GRDF to enrich wastewater plant gas into methane. Task 3 (Real-time temperature and heating power monitoring) proposed different alternatives for the monitoring of the real temperature at the surface of magnetically heated nanoparticles and for the electronic control of the catalytic process and allowed to demonstrate the presence of very high temperatures at the surface of magnetically heated nanoparticles, even in solution iin low boiling point solvents. Together with Task 2, Task 3 led to a collaboration with an industrial of electromagnetic coils (ID-Partner) to develop commercial set-up for magnetic catalysis. A thesis is starting in collaboration on this subject. Task 4 proved deceiving, the heating capacity of plasmonic materials being found too low for catalysis although one paper was published. Task 5 led to the preparation of a variety of complex materials displaying various Curie temperature and hence allowing optimization of the methanation catalyst (FeNi3@Ni) as well as different reactions including propane dehydrogenation and methane dry reforming using e.g. FeCo nanoparticles. This research permitted to develop new catalysts for unprecedented reactions such as the selective transformation of waste plastics into methane, aromatic and unsaturated molecules (close to Diesel) or into linear saturated hydrocarbons (close to kerosene).
Task 6 led to unprecedented reactions such as hydrodeoxygenation of biomass platform molecules in solution. These results were at the origin of two research contracts and to a proposal of collaboration within an international ANR program. Finally the results of Monacat inspired an ANR program on electrochemistry which was funded, a research contract on hydrogen storage and two projects in discussion with two other industrial partners.
Overall the results of Monacat produced so far 32 publications, 2 patents, 7 publications which are directly related to Monacat but do not involve temporary personnel paid by Monacat and over 10 papers in which Monacat will be acknowledged to be published within the next year. Furthermore Monacat raised an academic and industrial interest. Concerning the academic part, proposals of collaborations on magnetic catalysis originated from leading catalysis and nanoscience institutions in Germany, Italy, Spain and france. Concerning the industrial part this led to collaborations and contracts with 4 major industrial companies and two SMEs.

Progrès au-delà de l’état des connaissances et impact potentiel prévu (y compris l’impact socio-économique et les conséquences sociétales plus larges du projet jusqu’à présent)

Progress beyond the state-of-the-art:
- a catalytic process for enrichment of biogas adapted to intermittency and small and dispersed gas supplies.
- new inductors, more energy efficient
- a collection of complex nano-objects displaying various catalytic properties and Curie temperatures for regulating their activity.
- new methods for measuring the real temperature at the surface of a magnetically activated catalyst; new cadmium free quantum dots and their exploitation for temperature measurements.
- a new concept of "overheating" in solution allowing to perform difficult reactions in mild conditions such as hydrodeoxygenation of biomass platform molecules or hydrogenolysis or aryl ethers, models of lignin derived molecules. Further applications in organic chemistry and in the field of biomass.
- transposition of the concept of magnetic heating / magnetic catalysis to other research areas such as electrochemistry, hydrogen storage and waste plastic treatment

Scheme of the Monacat process