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Anderson, Gagliardi and Wuttig groups collaborate on CD4DC Initiative

Anderson, Gagliardi and Wuttig groups collaborate on CD4DC Initiative

The John Anderson and Laura Gagliardi groups, working together as part of Catalyst Design for Decarbonization Center, have been focused on developing novel sulfur-based metal-organic frameworks and have recently made significant progress in their research. This past month, their collaborative efforts resulted in two significant publications in the Journal of the American Chemical Society.

According to Dr. Ningxin Jiang and Dr. Andrea Darù, two key members of the group:

Sulfur is a crucial element that plays critical roles in chemistry and materials sentence. The integration of sulfur into coordination polymers has garnered increasing interest due to its energy matching with transition metals. This alignment facilitates better bonding and more effective transport of electrons. While these features have been explored for tuning the physical properties of coordination polymers, the effect of sulfur substitution on reactivity and catalysis is less well understood.

Exploring the properties and reactivity of sulfur-based coordination polymers, and particularly leveraging these characteristics for the storage of renewably sourced hydrogen towards decarbonization, is a major goal of the recently awarded Energy Frontier Research Center (EFRC), the Catalyst Design for Decarbonization Center (CD4DC). The Anderson and Gagliardi groups from the University of Chicago, working as part of CD4DC, have focused on developing these goals, and have made considerable progress.

In the first of two papers published, titled “Aliovalent Substitution Tunes Physical Properties in a Conductive Bis(dithiolene) Two-Dimensional Metal−Organic Framework,” Drs. Lei Wang and Andrea Daru investigated a series of two-dimensional conductive metal−organic frameworks (MOFs) that have shown promise as electronic materials for applications in electronic, thermoelectric, magnetic, electrocatalytic, and energy storage devices. While several protocols have been developed to synthesize these materials or to modify their electronic properties, a notable absence is aliovalent substitution wherein a metal ion with a different charge is substituted into a material. This approach is commonly used to tune the properties of semiconductors.

Drs. Wang and Daru found that substituting Fe(III) from a 2D MOF with Ni(II) framework enables the isolation of a pure Ni based material. Detailed characterization confirmed that this substitution of a 3+ ion for a 2+ ion results in an in-situ change in the charge of the organic linker which leads to significant physical changes such as increased electrical conductivity and stability. These platforms are now exciting candidates for catalytic or electrocatalytic applications.

In the second paper published in the Journal of the American Chemical Society, “Catalytic, Spectroscopic, and Theoretical studies of Fe4S4-based Coordination Polymers as Heterogenous CPET Mediators for Electrocatalysis,” Drs. Ningxin Jiang and Andrea Darù, along with doctoral student Špela Kunstelj, collaborated to investigate coordination polymers featuring iron-sulfur clusters. Iron-sulfur clusters, particularly cuboidal Fe4S4 clusters, are ubiquitous in nature and play essential roles in electron transport. Recent studies have revealed that synthetic molecular Fe4S4 clusters can act as effective proton-electron charge transfer (PCET) mediators, enhancing the activity and selectivity of homogeneous CO2 reduction electrocatalysts.

In this study, the Anderson and Gagliardi groups, along with the Anna Wuttig lab,  developed a method to anchor [Fe4S4]-based coordination polymers on electrode surfaces. These coordination polymers can be dissolved in organic solvents, enabling their deposition onto electrodes for electrocatalysis. These [Fe4S4]-modified electrodes, along with a soluble co-catalysis, result in a system with a strong selectivity for the formation of formic acid.

Notably, formic acid is an appealing H2 storage candidate. Moreover, these modified electrodes demonstrate excellent recyclability with no significant activity loss. The heterogenization process also allows for detailed mechanistic studies on the electrode surface. Using in-situ surface-enhanced infrared spectroscopy and density functional theory calculations, key reaction intermediates involved in formic acid production were identified. This research represents one of the first examples of a heterogenized PCET mediator and paves the way for the application of this and related systems in energy-relevant catalysis.

The CD4DC fosters invaluable collaboration among the Anderson, Gagliardi, and Wuttig labs, significantly advancing their scientific endeavors. This synergy has been instrumental in producing such publications. (Jiang, Darù)

The group additionally says that many collaborations are already ongoing in various projects, both related and unrelated to CD4DC. The synergy they’ve developed promises to speed up further research and current projects and they anticipate an increase of collaborative opportunities in the future, with the prospect of inviting more research groups to be included into their work.

(Summary text provided by Dr. Ningxin Jiang and Dr. Andrea Darù)

Citation – “Aliovalent Substitution Tunes Physical Properties in a Conductive Bis(dithiolene) Two-Dimensional Metal–Organic Framework”, Lei Wang, Andrea Daru, Bhavnesh Jangid, Jie-Hao Chen, Ningxin Jiang, Shrayesh N. Patel, Laura Gagliardi, and John S. Anderson, Journal of the American Chemical Society 2024 146 (17), 12063-12073, DOI: 10.1021/jacs.4c01860 

Citation – “Catalytic, Spectroscopic, and Theoretical Studies of Fe4S4-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis”, Ningxin Jiang, Andrea Darù, Špela Kunstelj, Jenny G. Vitillo, Maia E. Czaikowski, Alexander S. Filatov, Anna Wuttig, Laura Gagliardi, and John S. Anderson, Journal of the American Chemical Society 2024 146 (17), 12243-12252, DOI: 10.1021/jacs.4c03726