1st Period - SCOPE

Catalyse the transformation to a more sustainable and innovative society requires to develop innovative technologies in chemical and energy transformation/utilization areas which use directly renewable energy to substitute the use of fossil fuels. To implement this vision it is necessary to develop novel technologies for the production of chemicals, fuels and chemical energy storage vectors that allow to overcome the current limitations in the production of renewable energy.

The ambition of SCOPE proposal is to develop the scientific bases for a ground-breaking approach (based on catalysis-plasma symbiosis) for direct chemical syntheses using renewable energy of large-volume key chemicals or energy vectors. Although the core of the project is plasma-catalysis, we include also some comparative analysis of photo- and electro-catalysis to have a better understanding of how design effective "reactive" catalysts, because several aspects common to these three approaches, as outlined above. We have thus the ambitious aim to put the scientific bases for this new catalytic chemistry which is at the core of the energy and chemistry transition.

We have three target reactions: (i) N2 fixation. key reaction for production of ammonia (NH3) and NOx-made fertilizers; (ii) CH4 valorization to produce longer C-chain hydrocarbons; CO2 conversion to liquid solar fuels.

SCOPE project started in April 2019 and is now at the end of the second year of the project: Still on-going Covid-19 pandemic situation caused strong delays in all PI labs, and cancellation of the planned mobility and meeting activities. The general project organization is the following:

- at UniME (cPI) are developed the novel catalysts/electrode, as well as comparative testing with also photo- and electro-catalytic conversion, besides to the development of novel reactor concepts for plasma-catalysis,

- at UANT (PI1) is studied the physico-chemical modelling of plasma-catalysis systems, and made experiments on different modalities of plasma generation and interaction with the catalyst

- at UNIWAR (PI2, I3), and associated TUe and UoA, is investigated the reactor optimization and simulation, including the development of a novel approach for spatio-temporal characterization of concentration profiles in plasma-catalysis, and the sustainability-driven assessment of the processes, including distributed manufacturing scenarios, diverse credit accounting for co-valorisation, and supply chain / circularity innovation.

The synergy of the PIs competences is thus realized over the entire dimensional-scale level, from nano-scale (at catalysis level), to micro-scale (at the modelling level), to milli-scale (reactor design) and to mega-scale (plant and technology design).

The project is organized in six workpackages (WPs), of which the first WP (WP1: Identify the mechanisms of controlling the selectivity) and in part WP3 (Fast-modulated operations in the presence of plasma), WP4 (Advanced processes for direct conversion of target small molecules) and WP5 (Intensified process-sustainability opportunities) were active in the first two years, in addition to WP6 (Coordination and Dissemination).

Important actions regarding the implementation of synergy is the realization of two joint international Doctorates:

- the first is the Doctorate ACCESS (Advanced Catalytic Processes for using Renewable Energy Sources), accredited as International and Intersectorial (industrial) Innovative Doctorate Course from the Italian Ministry of University and Research, and stemming directly from the ERC Synergy SCOPE. The Consortium involves UniME, UANT and TUe, and the company NEXTCHEM, while UNIWAR and UoA PIs participate in the Doctorate Board. The procedure necessary to start the Doctorate makes possible to start it only from 1st November 2020.

- the second is a joint Doctorate between UniWAR and UoA for PhD students in co-tutelle

The following progresses beyond the state of the art can be mentioned:

CPI/UniME:

- 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.

PI1/UANT:

- 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.

PI2/UNIWAR, TUe:

- 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.

I3/UNIWAR, UoA:

- 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 plans 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.