Support Engineering in singLe-atoM cAtalysts for light-driven C-X coupling processes

Project Information

SELMA

Grant agreement ID: 101150107

DOI

10.3030/101150107

Project closed

EC signature date 8 March 2024

Start date 1 June 2024

End date 31 May 2026

Funded under

• Marie Skłodowska-Curie Actions (MSCA)

Total cost

No data

EU contribution

€ 181 330,08

Coordinated by

POLITECNICO DI MILANO
Italy

Periodic Reporting for period 1 - SELMA (Support Engineering in singLe-atoM cAtalysts for light-driven C-X coupling processes)

Reporting period: 2024-06-01 to 2026-05-31

Summary of the context and overall objectives of the project

The transition towards a climate-neutral and resource-efficient economy requires the development of innovative catalytic technologies capable of producing chemicals more sustainably while reducing energy consumption and greenhouse gas emissions. Single-atom catalysts (SACs), in which isolated metal atoms are stabilized on solid supports, have emerged as a promising class of catalysts because they maximize metal utilization while combining the selectivity of homogeneous catalysts with the recyclability of heterogeneous systems. However, the practical implementation of SACs is still limited by challenges related to stabilizing isolated metal atoms and controlling the interactions between metals and their supports.

The project addressed these challenges by developing advanced support materials capable of stabilizing isolated metal atoms and tailoring their catalytic properties. The overall objective was to establish rational support engineering strategies for the preparation of stable and efficient Zn- and Cu-based single-atom catalysts and to demonstrate their application in sustainable chemical transformations, including carbon dioxide utilization and carbon–heteroatom bond-forming reactions.

To achieve this objective, three complementary classes of porous materials were investigated as catalyst supports: mesoporous graphitic carbon nitride, covalent organic frameworks (COFs), and hydrogen-bonded organic frameworks (HOFs). These materials provide well-defined coordination environments that enable the stabilization of isolated metal atoms while enhancing catalytic performance.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

During project implementation, significant progress was achieved in the design, synthesis and application of these novel single-atom catalysts.

A zinc single-atom catalyst supported on mesoporous graphitic carbon nitride was successfully developed and applied to the cycloaddition of carbon dioxide with epoxides to produce cyclic carbonates. The catalyst demonstrated high activity under mild reaction conditions and provided new mechanistic understanding of CO2 activation through density functional theory calculations.

A second catalyst consisting of atomically dispersed copper on a covalent organic framework was developed for multicomponent C–N coupling reactions leading to the synthesis of propargylamines. The catalyst exhibited excellent activity, broad substrate scope, high selectivity and good recyclability, demonstrating the potential of COF-based supports for stabilizing isolated metal centres.

The project also developed a hydrogen-bonded organic framework supporting isolated copper atoms for the hydroboration of alkynes. This catalyst enabled the selective synthesis of valuable organoboron compounds with high catalytic efficiency while maintaining stability over repeated reaction cycles.

Beyond catalyst development, the project generated important scientific knowledge on support engineering for single-atom catalysts through a comprehensive review article analysing the historical evolution of support design and coordination environment engineering. A second review focusing on structured and shaped single-atom catalysts further contributed to knowledge dissemination within the catalysis community. The research has already resulted in one published peer-reviewed article, two published review contributions involving the research team, and several additional manuscripts currently under preparation. Results have also been disseminated through international scientific conferences and presentations.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

The project advanced the state of the art by demonstrating that the rational engineering of support materials is an effective strategy for stabilizing isolated metal atoms and tailoring catalytic performance across multiple chemical transformations. Rather than relying on conventional supports, the project introduced new carbon nitride-, COF-, and HOF-based architectures capable of providing well-defined coordination environments for single-atom stabilization.

The developed catalysts combined high atom efficiency, excellent selectivity, recyclability, and reduced metal consumption, thereby contributing to more sustainable catalytic processes. The work provided new mechanistic understanding of metal–support interactions through advanced characterization techniques and theoretical modelling, establishing design principles that can guide the development of next-generation heterogeneous catalysts.

The project opened opportunities for further research towards larger-scale catalyst production, industrial demonstration, and the extension of support engineering concepts to additional catalytic reactions relevant to renewable energy, carbon capture and utilization, and sustainable chemical manufacturing. The continued development of these materials is expected to facilitate future industrial uptake through improved catalyst stability, scalability, and resource efficiency.