Applying Nuclear Forward Scattering as In Situ and Operando Tool for the Characterization of FeN4 Moieties in the Hydrogen Evolution Reaction.

Nuclear forward scattering (NFS) is a synchrotron-based technique relying on the recoil-free nuclear resonance effect similar to Mössbauer spectroscopy. In this work, we introduce NFS for in situ and operando measurements during electrocatalytic reactions. The technique enables faster data acquisition and better discrimination of certain iron sites in comparison to Mössbauer spectroscopy. It is directly accessible at various synchrotrons to a broad community of researchers and is applicable to multiple metal isotopes. We demonstrate the power of this technique with the hydrogen evolution mechanism of an immobilized iron porphyrin supported on carbon. Such catalysts are often considered as model systems for iron-nitrogen-carbon (FeNC) catalysts. Using in situ and operando NFS in combination with theoretical predictions of spectroscopic data enables the identification of the intermediate that is formed prior to the rate-determining step. The conclusions on the reaction mechanism can be used for future optimization of immobilized molecular catalysts and metal-nitrogen-carbon (MNC) catalysts.

FeN4 Environments upon Reduction: A Computational Analysis of Spin States, Spectroscopic Properties, and Active Species.

FeN4 motifs, found, for instance, in bioinorganic chemistry as heme-type cofactors, play a crucial role in man-made FeNC catalysts for the oxygen reduction reaction. Such single-atom catalysts are a potential alternative to platinum-based catalysts in fuel cells. Since FeNC catalysts are prepared via pyrolysis, the resulting materials are amorphous and contain side phases and impurities. Therefore, the geometric and electronic nature of the catalytically active FeN4 site remains to be clarified. To further understand the behavior of FeN4 centers in electrochemistry and their expected spectroscopic behavior upon reduction, we investigate two FeN4 environments (pyrrolic and pyridinic). These are represented by the model complexes [Fe(TPP)Cl] and [Fe(phen2N2)Cl], where TPP = tetraphenylporphyrin and phen = 1,10-phenanthroline. We predict their Mössbauer, UV-vis, and NRV spectral data using density functional theory as windows into their electronic structure differences. By varying the axial ligand, we further show how well small chemical changes in both complexes can be discerned. We find that the differences in ligand field strength in pyrrolic and pyridinic coordination result in different spin ground states, which in turn leads to distinct Mössbauer spectroscopic properties. As a result, pyrrolic nitrogen donors with a weaker ligand field are predicted to show more pronounced spectroscopic differences under in situ and operando conditions, while pyridinic nitrogen donors are expected to show less pronounced spectroscopic changes upon reduction and/or ligand loss. We therefore suggest that a weaker ligand field leads to better detectability of catalytic intermediates in in situ and operando experiments.

Substituent Effects in Iron Porphyrin Catalysts for the Hydrogen Evolution Reaction.

For a future hydrogen economy, non-precious metal catalysts for the water splitting reactions are needed that can be implemented on a global scale. Metal-nitrogen-carbon (MNC) catalysts with active sites constituting a metal center with fourfold coordination of nitrogen (MN4 ) show promising performance, but an optimization rooted in structure-property relationships has been hampered by their low structural definition. Porphyrin model complexes are studied to transfer insights from well-defined molecules to MNC systems. This work combines experiment and theory to evaluate the influence of porphyrin substituents on the electronic and electrocatalytic properties of MN4 centers with respect to the hydrogen evolution reaction (HER) in aqueous electrolyte. We found that the choice of substituent affects their utilization on the carbon support and their electrocatalytic performance. We propose an HER mechanism for supported iron porphyrin complexes involving a [FeII (P⋅)]- radical anion intermediate, in which a porphinic nitrogen atom acts as an internal base. While this work focuses on the HER, the limited influence of a simultaneous interaction with the support and an aqueous electrolyte will likely be transferrable to other catalytic applications.

Identification of the Catalytically Dominant Iron Environment in Iron- and Nitrogen-Doped Carbon Catalysts for the Oxygen Reduction Reaction.

For large-scale utilization of fuel cells in a future hydrogen-based energy economy, affordable and environmentally benign catalysts are needed. Pyrolytically obtained metal- and nitrogen-doped carbon (MNC) catalysts are key contenders for this task. Their systematic improvement requires detailed knowledge of the active site composition and degradation mechanisms. In FeNC catalysts, the active site is an iron ion coordinated by nitrogen atoms embedded in an extended graphene sheet. Herein, we build an active site model from in situ and operando 57Fe Mössbauer spectroscopy and quantum chemistry. A Mössbauer signal newly emerging under operando conditions, D4, is correlated with the loss of other Mössbauer signatures (D2, D3a, D3b), implying a direct structural correspondence. Pyrrolic N-coordination, i.e., FeN4C12, is found as a spectroscopically and thermodynamically consistent model for the entire catalytic cycle, in contrast to pyridinic nitrogen coordination. These findings thus overcome the previously conflicting structural assignments for the active site and, moreover, identify and structurally assign a previously unknown intermediate in the oxygen reduction reaction at FeNC catalysts.

Spectroscopic discernibility of dopants and axial ligands in pyridinic FeN4 environments relevant to single-atom catalysts.

Single-atom catalysts (SACs) activate small molecules, e.g. the oxygen reduction reaction is catalysed by FeNC materials. Because the nature of active site(s) in this type of SAC is unclear, spectroscopic and computational insights are needed to clarify the atomistic composition and electronic structure. Using quantum chemistry, we show that key features of [Fe{phen2A2}L]n+ complexes (A = CH, N with n = 0, A = O with n = 0, 2; L = OH-, Cl-) can be differentiated spectroscopically.

Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center.

Molecular catalysis of carbon dioxide reduction using earth-abundant metal complexes as catalysts is a key challenge related to the production of useful products--the "solar fuels"--in which solar energy would be stored. A direct approach using sunlight energy as well as an indirect approach where sunlight is first converted into electricity could be used. A Co(II) complex and a Fe(III) complex, both bearing the same pentadentate N5 ligand (2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene), were synthesized, and their catalytic activity toward CO2 reduction was investigated. Carbon monoxide was formed with the cobalt complex, while formic acid was obtained with the iron-based catalyst, thus showing that the catalysis product can be switched by changing the metal center. Selective CO2 reduction occurs under electrochemical conditions as well as photochemical conditions when using a photosensitizer under visible light excitation (λ > 460 nm, solvent acetonitrile) with the Co catalyst. In the case of the Fe catalyst, selective HCOOH production occurs at low overpotential. Sustained catalytic activity over long periods of time and high turnover numbers were observed in both cases. A catalytic mechanism is suggested on the basis of experimental results and preliminary quantum chemistry calculations.