Green Synthesis of MOF-Based Materials for Electrochemical Reduction of Carbon Dioxide

abstract

Porous ZIF-8 and ZIF-67 were synthesized via a green steam-assisted dry-gel technique and investigated as potential catalysts for CO2 electroreduction. The synthesis conditions are found to significantly influence the growth of these metal-organic frameworks (MOFs). Notably, the water content employed during synthesis plays a crucial role in shaping the morphological properties of ZIF-8. Specifically, a moderate water content results in the formation of uniform ZIF-8 with a size distribution ranging from 240-440 nm. During CO2 electroreduction, these morphological properties exert substantial effects on the selectivity for CO formation, thereby facilitating the production of syngas with adjustable CO: H2 ratios. This feature holds promise for the widespread adoption of syngas as a clean alternative to fossil fuels, offering potential benefits for electricity generation and liquid fuel production. Despite sharing similar structural properties with ZIF-8, ZIF-67 exhibits distinct performance characterized by its limited selectivity for CO2 electroreduction. This discrepancy is attributed to the different metal centers of the two MOFs, resulting in the distinct activation of CO2 and H2O molecules and their further reduction. This finding highlights the critical role of metal centers in MOF-based materials for electrocatalysis application. This work explores the potentiality of metal organic frameworks as electrocatalysts for the CO2 reduction reaction (CO2RR). Different sized ZIF-8 and its isostructural ZIF-67 were successfully synthesized via a green steam-assisted route. The comprehensive study shows that both particle size and metal center affect the catalytic performance for CO2RR, with the latter playing the central role. image

keywords

ZEOLITIC IMIDAZOLATE FRAMEWORKS; ZIF-8; CO2; ELECTROREDUCTION; CONVERSION; SURFACE

subject category

Chemistry; Science & Technology - Other Topics

authors

Bagheri, M; Lourenco, MAO; Dangbegnon, JK; Monti, NBD; Mafra, L; Pirri, F; Zeng, JQ

Groups

G1 - Porous Materials and Nanosystems

Projects

CICECO - Aveiro Institute of Materials (UIDB/50011/2020)

CICECO - Aveiro Institute of Materials (UIDP/50011/2020)

Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)

Unveiling CO2 chemisorption mechanisms in solid adsorbents via surface-enhanced ex(in)-situ NMR (NMR4CO2)

Rationale design of sustainable porous organosilicas for optimal CO2 uptake from biogas (GRACE)

Collaboratory for Emerging Technologies, CoLab (EMERGING TECHNOLOGIES)

acknowledgements

J.Z. received funds under the National Recovery and Resilience Plan (NRRP), Mission 4 "Education and Research" - Component 2 "From research to business"- Investment 3.1 "Fund for the realization of an integrated system of research and innovation infrastructures" - Call n. 3264 of 28/12/2021 of Italian Ministry of University and Research Award Decree n. 128 (21/06/2022)- Project code: IR0000027, Concession Decree No. 128 of 21/06/2022 adopted by the Italian Ministry of Research, CUP: B33C22000710006, Project title: iENTRANCE. Wenbo Ju received funds under the Introduces Innovative and Entrepreneurial Team Project of Guangdong Province, No. 2021ZT09Z109. This study was also developed in the framework of the research activities carried out within the Project "Network 4 Energy Sustainable Transition-NEST", Spoke 2:6, Project code PE0000021, funded under the National Recovery and Resilience Plan (NRRP), Mission 4, Component 2, Investment 1.3-Call for tender No. 1561 of 11.10.2022 of Ministero dell'Universita e della Ricerca (MUR); funded by the European Union-NextGenerationEU. M.A.O.L. and L.M. contributed to XRD, and N2 and CO2 adsorption-desorption measurements. Their work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 (DOI 10.54499/UIDB/50011/2020), UIDP/50011/2020 (DOI 10.54499/UIDP/50011/2020) & LA/P/0006/2020 (DOI 10.54499/LA/P/0006/2020), financed by national funds through the FCT/MCTES (PIDDAC). Their work has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant Agreement 865974). FCT is also acknowledged by M.A.O.L for a Junior Researcher Position (CEECIND/01158/2021, DOI 10.54499/2021.01158.CEECIND/CP1659/CT0022). M.A.O.L. further acknowledges funding from the European Union's Horizon Europe research and innovation programme under grant agreement No 101090287. Open Access publishing facilitated by Istituto Italiano di Tecnologia, as part of the Wiley- CRUI-CARE agreement.