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Surface-COnfined fast-modulated Plasma for process and Energy intensification in small molecules conversion

Periodic Reporting for period 1 - SCOPE (Surface-COnfined fast-modulated Plasma for process and Energy intensification in small molecules conversion)

Reporting period: 2019-04-01 to 2020-09-30

SCOPE addresses the relevant issue of developing novel methodologies to use renewable energy sources to produce solar fuels and chemicals from simple molecules such as CO2, N2 and CH4. The objective is to contribute to accelerate the transition to a defossilized society. Photo-, electro- and plasma-catalysis are the three complementary pillars to reach this objective, and thus to create a system change in energy and chemical production. SCOPE project focuses the activity on plasma-catalysis but extending the study also to photo- and electro-catalysis to have a broader approach and understand synergies in the approach. We have the ambitious aim to put the scientific bases for this new catalytic chemistry which is at the core of the energy and chemistry transition.

The synergy project approach is to integrate complementary and interdisciplinary competences over the entire scale elements necessary for process development, from nano to mega scale, from catalysis and plasma level to plant sustainability and assessment.
In the first reporting period, as originally planned, the activities were focused on WP1 (Identify the mechanisms of controlling the selectivity), besides WP6 (Coordination and Dissemination).
Specifically, in WP1, the tasks active were T1.1 (Modelling the plasma chemistry, PI1), T1.2 (Catalyst development, cPI), T1.3 Plasma-catalytic tests and plasma species characterization (I3), and T1.4 Determination of temporal concentration profiles (PI2). For cPI, activities related to T4.2 Benchmarking, planned for the 2nd reporting period, were anticipated.
The scientific work performed during the 1st reporting period was in line with the planned activities described above. Specifically:
- cPI/UniME: the activities were centred on T1.2 (catalyst development), with the study, synthesis, characterization and testing (in CO2 photoreduction) of nanostructured catalytic electrodes, and the development of a new type of plasma-catalytic reactor. In T4.2 the activities, were focused on N2 direct conversion to NH3 on iron/nanocarbon Ti3C2 MXenes.

- PI1/UANT: the activities were centred on T1.1 (Modelling the plasma chemistry), developing chemical kinetics models for CO2, CH4, N2 and their mixtures, for various plasma reactors, as well as 2D/3D fluid dynamics models for plasma reactor design, density functional theory calculations for studying important plasma-catalytic effects, and microkinetic surface models for studying plasma-catalytic reactions at various catalyst surfaces.

- PI2/UNIWAR, TUe: the activities were centred on (i) T1.4 with the acquisition of the equipment and construction of an apparatus for determination of temporal concentration profiles, by a novel technique (FTIR/FTNIR tomography) for spatiotemporal data acquisition, (ii) T.3.1 by modelling of a photochemical reaction over a plasmonic AuAg/TiO2 catalyst under fast modulation in temperature and light intensity, (iii) T3.2 with several magnetic (nickel ferrite) nanocomposites being developed.

- I3/UNIWAR, UoA: the activities were centred on T1.3 with two different microplasma reactors designed and manufactured, plus a third commercial. Experiments on symbiotic plasma modification by reactor and supports/catalysts have been started. The synthesis of N-doped carbon nanodots was done with a microplasma jet penetrating into an aqueous solution of folic acid (vitamin B9). The thermodynamic potential of a plasma process for the co-production of ammonia and hydrogen was assessed by process modelling. Activities on T4.3 were anticipated with thermochemical equilibrium modelling for the biomass (manure) conversion to ammonia using thermal and non-thermal plasma. Activities on T5.2 were anticipated with the development of a software platform for supply chain-economic modelling.

In WP6, besides project coordination and dissemination, to remark the realization of two International Doctorates stemming from the ERC project and various joint publications between the PIs. Various dissemination activities have been also made, although in the last period pandemic situation has greatly limited participation to conferences and mobility activities.
The following progresses beyond the state of the art can be mentioned:

- A new type of plasma-catalytic reactor is under development, based on confined generation of nanoplasma within a semiconductor TiO2 nanomembrane, to couple nanoconfined plasma with light illumination.
- A new reactor concept of gas-phase photocatalytic conversion of CO2 based on TiO2 nanomembrane.
- Development of novel improve materials (based on iron/nanocarbons and MXene) for the challenging reaction of N2 conversion to NH3 in electrocatalytic conditions (NRR), used as benchmarking. This understanding will be the basis to understand better plasma-catalysis.

- Development of a new 0D chemical kinetics model for i) CO2 and CH4 conversion, ii) plasma-catalytic NH3 synthesis, iii) NOx synthesis, to support experiments in a novel gliding arc plasmatron (GAP), iv) in a CH4/CO2/N2/O2 plasma, to support experiments on dry reforming of methane (DRM) in the GAP in the presence of N2 and O2.
- Development of fluid dynamics models for two different novel gliding arc plasma sources (magnetically stabilized and dual-vortex plasmatron),
- DFT calculations to study for the very first time the combined effect of electric fields, surface morphology, and surface charges, important in plasma catalysis, on CO2 activation over various Cu catalyst surfaces.
- Development of a novel microkinetic surface model for plasma-catalytic non-oxidative coupling of methane.

- development of an IR TDLAS equipment for spatiotemporal data acquisition with a plasma jet reactor
- modelling of a photochemical reaction over a plasmonic AuAg/TiO2 catalyst under fast modulation in temperature and light intensity to explore the effect of transient operation; an optimal frequency and amplitude were identified,
- several magnetic (nickel ferrite) nanocomposites with different heating rates under inductive heating have been developed.
- assessed the thermodynamic potential of a sustainable plasma-assisted nitrogen fixation process for co-production of ammonia and hydrogen.

- New reactors: i) Pyramid-array microplasma reactor with microstructured pyramids, ii) microfluidic plasma reactor with a PFA microtube coiled around an inner electrode, iii) kINPen microjet plasma reactor
- Exploration of jet microplasma modification through exposing the plasma to a ‘microreactor’ and catalyst
- New integrated ammonia process with exergy efficiency of ~60%.; economic evaluation for distributed-production scenarios ì
- New plasma process for co-production of ammonia and hydrogen
- New materials: i) N-doped carbon nanodots of very intense (blue) luminescence, ii) plasma-nanodot approach scores high in green energy metrics, iii) efficient nanodot purification

The progresses are in line with the planned for the 1st period report, notwithstanding the impact of pandemic situation that has greatly limited participation to conferences and mobility, as well as in part access to the labs for experiments. Not critical impact, however, can be indicated on the planned results until the end of the project.