The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input.

Biological and heterogenous catalysts for the electrochemical CO2 Reduction Reaction (CO2RR) often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over the hydrogen evolution reaction (HER). Here, we report a molecular iron(II) system that captures this design concept in a homogeneous setting through the use of a redox non-innocent terpyridine-based pentapyridine ligand (tpyPY2Me). As a result of strong metal-ligand exchange coupling between the Fe(II) center and ligand, [Fe(tpyPY2Me)] 2+ exhibits redox behavior at potentials 640 mV more positive than the isostructural [Zn(tpyPY2Me)] 2+ analog containing the redox-inactive Zn(II) ion. This shift in redox potential is attributed to the requirement for both an open-shell metal ion and a redox non-innocent ligand. The metalligand cooperativity in [Fe(tpyPY2Me)] 2+ drives the electrochemical reduction of CO2 to CO at low overpotentials with high selectivity for CO2RR (> 90%) and turnover frequencies of 100,000 s -1 with no degradation over 20 h. The decrease in the thermodynamic barrier engendered by this coupling also enables homogeneous CO2 reduction catalysis in water without compromising selectivity or rates. Synthesis of the two-electron reduction product, [Fe(tpyPY2Me)] 0 , and characterization by X-ray crystallography, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), variable temperature NMR, and density functional theory (DFT) calculations, support assignment of an open-shell singlet electronic structure that maintains a formal Fe(II) oxidation state with a doubly-reduced ligand system. This work provides a starting point for the design of systems that exploit metal-ligand cooperativity for electrocatalysis where the electrochemical potential of redox non-innocent ligands can be tuned through secondary metal-dependent interactions.

A porous organic cage composed of six iron tetraphenylporphyrins was used as a supramolecular catalyst for electrochemical CO -to-CO conversion. This strategy enhances active site exposure and substrate diffusion relative to the monomeric catalyst, resulting in CO generation with near-quantitative Faradaic efficiency in pH 7.3 water, with activities reaching 55 250 turnovers. These results provide a starting point for the design of supramolecular catalysts that can exploit the properties of the surrounding matrix yet retain the tunability of the original molecular unit.

Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO reduction. Palladium functionalized with a chelating tris-N-heterocyclic carbene (NHC) ligand (Pd-timtmb ) exhibits a 32-fold increase in activity for electrochemical reduction of CO to C1 products with high Faradaic efficiency (FE =86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC-ligated Pd electrode (Pd-mimtmb ). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular-materials interfaces enabled by surface organometallic chemistry.

We report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co‐TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co‐PB‐1(6) bearing six Co‐TPP subunits connected through twenty‐four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co‐rPB‐1(6). Both Co‐PB‐1(6) and Co‐rPB‐1(6) cages produce 90–100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co‐TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.

Stimulus-triggered protein synthesis is critical for brain health and function. However, due to technical hurdles, de novo neuronal translation is predominantly studied in cultured cells, whereas electrophysiological and circuit analyses often are performed in brain slices. The different properties of these two experimental systems create an information gap about stimulus-induced alterations in the expression of new proteins in mature circuits. To address this, we adapted two existing techniques, BONCAT and SILAC, to a combined proteomic technique, BONLAC, for use in acute adult hippocampal slices. Using BDNF-induced protein synthesis as a proof of concept, we found alterations in expression of proteins involved in neurotransmission, trafficking, and cation binding that differed from those found in a similar screen in cultured neurons. Our results indicate important differences between cultured neurons and slices, and suggest that BONLAC could be used to dissect proteomic changes underlying synaptic events in adult circuits.

Conspectus Increasing demand for sustainable energy sources continues to motivate the development of new catalytic processes that store intermittent energy in the form of chemical bonds. In this context, photosynthetic organisms harvest light to drive dark reactions reducing carbon dioxide, an abundant and accessible carbon source, to store solar energy in the form of glucose and other biomass feedstocks. Inspired by this biological process, the field of artificial photosynthesis aims to store renewable energy in chemical bonds spanning fuels, foods, medicines, and materials using light, water, and CO2 as the primary chemical feedstocks, with the added benefit of mitigating the accumulation of CO2 as a greenhouse gas in the atmosphere. As such, devising new catalyst platforms for transforming CO2 into value-added chemical products is of importance. Historically, catalyst design for artificial photosynthesis has been approached from the three traditional fields of catalysis: molecular, materials, and biological. In this Account, we show progress from our laboratory in constructing new hybrid catalysts for artificial photosynthesis that draw upon design concepts from all three of these traditional fields of catalysis and blur the boundaries between them. Starting with molecular catalysis, we incorporated biological design elements that are prevalent in enzymes into synthetic systems. Specifically, we demonstrated that proper positioning of intramolecular hydrogen bond donors or addition of intermolecular multipoint hydrogen bond donors with classic iron porphyrin and nickel cyclam platforms can substantially increase rates of CO2 reduction and break electronic scaling relationships. In parallel, we incorporated a key materials design element, namely, high surface area and porosity for maximizing active site exposure, into molecular systems. A supramolecular porous organic cage molecule was synthesized with iron porphyrin building blocks, and the porosity was observed to facilitate substrate and charge transport through the catalyst film. In turn, molecular design elements can be incorporated into materials catalysts for CO2 reduction. First, we utilized molecular synthons in a bottom-up reticular approach to drive polymerization/assembly into a bulk framework material. Second, we established an organometallic approach in which molecular ligands, including chelating ones, are adsorbed onto a bulk inorganic solid to create and tune new active sites on surfaces. Finally, we describe two examples in which molecular, materials, and biological design elements are all integrated to catalyze the reduction of CO2 into CH4 using a hybrid biological-materials interface with sustainably generated H2 as the reductant or to reduce CO into value-added C2 products acetate and ethanol using a hybrid molecular-materials interface to construct a biomimetic, bimetallic active site. Taken together, our program in catalysis for energy and sustainability has revealed that combining more conventional design strategies in synergistic ways ...

Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon–carbon coupled products via self-assembly of supramolecular cages at molecular–materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiol-terminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm2) at a potential of −0.40 V vs RHE. The cage-functionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation.