Insights into Electrochemical CO2 Reduction on Metallic and Oxidized Tin Using Grand-Canonical DFT and In Situ ATR-SEIRA Spectroscopy.

Electrochemical CO2 reduction (CO2R) to formate is an attractive carbon emissions mitigation strategy due to the existing market and attractive price for formic acid. Tin is an effective electrocatalyst for CO2R to formate, but the underlying reaction mechanism and whether the active phase of tin is metallic or oxidized during reduction is openly debated. In this report, we used grand-canonical density functional theory and attenuated total reflection surface-enhanced infrared absorption spectroscopy to identify differences in the vibrational signatures of surface species during CO2R on fully metallic and oxidized tin surfaces. Our results show that CO2R is feasible on both metallic and oxidized tin. We propose that the key difference between each surface termination is that CO2R catalyzed by metallic tin surfaces is limited by the electrochemical activation of CO2, whereas CO2R catalyzed by oxidized tin surfaces is limited by the slow reductive desorption of formate. While the exact degree of oxidation of tin surfaces during CO2R is unlikely to be either fully metallic or fully oxidized, this study highlights the limiting behavior of these two surfaces and lays out the key features of each that our results predict will promote rapid CO2R catalysis. Additionally, we highlight the power of integrating high-fidelity quantum mechanical modeling and spectroscopic measurements to elucidate intricate electrocatalytic reaction pathways.

Layered Sn-Au Thin Films for Increased Electrochemical ATR-SEIRAS Enhancement.

Operando electrochemical attenuated total reflection surface-enhanced infrared absorption spectroscopy (EC ATR-SEIRAS) is a valuable method for a fundamental understanding of electrochemical interfaces under real operating conditions. The applicability of this method depends on the ability to tune the optical and catalytic properties of an electrode film, and it thus requires unique optimization for any given material. Motivated by the growing interest in Sn-based electrocatalysts for selective reduction of CO2 to formate species, we investigate several Sn thin-film synthesis routes for the resulting SEIRA signal response. We compare the SEIRA performance of thermally evaporated metallic Sn to a series of Sn-based films on top of a SEIRA-active Au substrate (metallic Sn, oxide-derived metallic Sn, and metal oxide SnOx). Using alkanethiol self-assembled monolayers as a probe, we find that electrodepositing metallic catalyst films on top of SEIRA-active Au substrates yield higher signal relative to thermal evaporation as well as higher signal than the independent SEIRA-active Au underlayer. These observations come despite the fact that thermally evaporated Sn has a significantly higher surface roughness (and thus higher adsorbate population), suggesting specific SEIRA-magnifying effects for the stacked films. Finally, we applied these films to observe the electrochemical conversion of CO2. Differences are observed in spectral features based on the composition of the electrode being either metallic or oxide-derived metallic Sn, implying differences in their respective reaction pathways.

Combining Renewable Electricity and Renewable Carbon: Understanding Reaction Mechanisms of Biomass-Derived Furanic Compounds for Design of Catalytic Nanomaterials.

ConspectusDespite the growing deployment of renewable energy conversion technologies, a number of large industrial sectors remain challenging to decarbonize. Aviation, heavy transport, and the production of steel, cement, and chemicals are heavily dependent on carbon-containing fuels and feedstocks. A hopeful avenue toward carbon neutrality is the implementation of renewable carbon for the synthesis of critical fuels, chemicals, and materials. Biomass provides an opportune source of renewable carbon, naturally capturing atmospheric CO2 and forming multicarbon linkages and useful chemical functional groups. The constituent molecules nonetheless require various chemical transformations, often best facilitated by catalytic nanomaterials, in order to access usable final products.Catalyzed transformations of renewable biomass compounds may intersect with renewable energy production by offering a means to utilize excess intermittent electricity and store it within chemical bonds. Electrochemical catalytic processes can often offer advantages in energy efficiency, product selectivity, and modular scalability compared to thermal-driven reactions. Electrocatalytic reactions with renewable carbon feedstocks can further enable related processes such as water splitting, where value-adding organic oxidation reactions may replace the evolution of oxygen. Organic electroreduction reactions may also allow desirable hydrogenations of bonds without intermediate formation of H2 and need for additional reactors.This Account highlights recent work aimed at gaining a fundamental understanding of transformations involving biomass-derived molecules in electrocatalytic nanomaterials. Particular emphasis is placed on the oxidation of biomass derived furanic compounds such as furfural and 5-hydroxymethylfurfural (HMF), which can yield value-added chemicals, including furoic acid (FA), maleic acid (MA), and 2,5-furandicarboxylic acid (FDCA) for renewable materials and other commodities. We highlight advanced implementations of online electrochemical mass spectrometry (OLEMS) and vibrational spectroscopies such as attenuated total reflectance surface enhanced infrared reflection absorption spectroscopy (ATR-SEIRAS), combined with microkinetic models (MKMs) and quantum chemical calculations, to shed light on the elementary mechanistic pathways involved in electrochemical biomass conversion and how these paths are influenced by catalytic nanomaterials. Perspectives are given on the potential opportunities for materials development toward more efficient and selective carbon-mitigating reaction pathways.

Electrochemical Stability of Thiolate Self-Assembled Monolayers on Au, Pt, and Cu.

Self-assembled monolayers (SAMs) of thiolates have increasingly been used for modification of metal surfaces in electrochemical applications including selective catalysis (e.g., CO2 reduction, nitrogen reduction) and chemical sensing. Here, the stable electrochemical potential window of thiolate SAMs on Au, Pt, and Cu electrodes is systematically studied for a variety of thiols in aqueous electrolyte systems. For fixed tail-group functionality, the reductive stability of thiolate SAMs is found to follow the trend Au < Pt < Cu; this can be understood by considering the combined influences of the binding strength of sulfur and competitive adsorption of hydrogen. The oxidative stability of thiolate SAMs is found to follow the order: Cu < Pt < Au, consistent with each surface's propensity toward surface oxide formation. The stable reductive and oxidative potential limits are both found to vary linearly with pH, except for reduction above pH ∼10, which is independent of pH for most thiol compositions. The electrochemical stability across different functionalized thiols is then revealed to depend on many different factors including SAM defects (accessible surface metal atom sites decrease stability), intermolecular interactions (hydrophilic groups reduce the stability), and SAM thickness (stability increases with alkanethiol carbon chain length) as well as factors such as SAM-induced surface reconstruction and the ability to directly oxidize or reduce the non-sulfur part of the SAM molecule.

Selective Interactions between Free-Atom-like d-States in Single-Atom Alloy Catalysts and Near-Frontier Molecular Orbitals.

In the limit of dilute alloying-the so-called "single-atom alloy" (SAA) regime-certain bimetallic systems exhibit weak mixing between constituent metal wave functions, resulting in sharp, single-atom-like electronic states localized on the dilute component of the alloy. This work shows that when these sharp states are appropriately positioned relative to given molecular orbitals, selective hybridization is enhanced, in accordance with intuitive principles of molecular orbital theory. We demonstrate the phenomenon for activation pathways of crotonaldehyde, a model α,ß-unsaturated aldehyde relevant to a wide range of chemical manufacturing. This analysis suggests new possible strategies for selectivity control in heterogeneous catalysis.

Investigating the use of conducting oligomers and redox molecules in CdS-MoFeP biohybrids.

In this work we report the effect of incorporating conducting oligophenylenes and a cobaltocene-based redox mediator on photodriven electron transfer between thioglycolic acid (TGA) capped CdS nanorods (NR) and the native nitrogenase MoFe protein (MoFeP) by following the reduction of H+ to H2. First, we demonstrate that the addition of benzidine-a conductive diphenylene- to TGA-CdS and MoFeP increased catalytic activity by up to 3-fold as compared to CdS-MoFeP alone. In addition, in comparing the use of oligophenylenes composed of one (p-phenylenediamine), two (benzidine) or three (4,4''-diamino-p-terphenyl)phenylene groups, the largest gain in H2 was observed with the addition of benzidine and the lowest with phenylenediamine. As a comparison to the conductive oligophenylenes, a cobaltocene-based redox mediator was also tested with the TGA-CdS NRs and MoFeP. However, adding either cobaltocene diacid or diamine caused negligible gains in H2 production and at higher concentrations, caused a significant decrease. Agarose gel electrophoresis revealed little to no detectable interaction between benzidine and TGA-CdS but strong binding between cobaltocene and TGA-CdS. These results suggest that the tight binding of the cobaltocene mediator to CdS may hinder electron transfer between CdS and MoFe and cause the mediator to undergo continuous reduction/oxidation events at the surface of CdS.

Cathode Interface Compatibility of Amorphous LiMn2O4 (LMO) and Li7La3Zr2O12 (LLZO) Characterized with Thin-Film Solid-State Electrochemical Cells.

Solid-state lithium-ion batteries are a hopeful successor to traditional Li-ion cells that use liquid electrolytes. While a growing body of work has characterized the interfaces between various solid electrolytes and the lithium metal, interfaces with common cathode intercalation compounds are comparatively less understood. In this contribution, the influence of polarization and temperature on interfacial stability between LiMn2O4 (LMO) and Li7La3Zr2O12 (LLZO) are investigated. Sputtered thin-film LMO electrodes are utilized to permit high-capacity cycling while retaining a large ratio of interfacial area to electrode bulk. Electrochemical impedance spectroscopy (EIS) is compared across a set of full (LMO|LLZO|Li) and symmetric (LMO|LLZO|LMO, Li|LLZO|Li, and Au|LLZO|Au) cells to delineate impedance features that are specific to the evolution of the cathode interface. Additional X-ray photoelectron spectroscopy (XPS) provides evidence of a limited interfacial reaction between LMO and LLZO that coincides with an increase in the impedance of the LMO-LLZO interface.

Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO2 Capture Applications: A Quasielastic Neutron Scattering Study.

Composite gas sorbents, formed from an active polymer phase and a porous support, are promising materials for the separation of acid gases from a variety of gas streams. Significant changes in sorption performance (capacity, rate, stability etc.) can be achieved by tuning the properties of the polymer and the nature of interactions between polymer and support. Here we utilize quasielastic neutron scattering (QENS) and coarse-grained molecular dynamics (MD) simulations to characterize the dynamic behavior of the most commonly reported polymer in such materials, poly(ethylenimine) (PEI), both in bulk form and when supported in a mesoporous silica framework. The polymer chain dynamics (rotational and translational diffusion) are characterized using two neutron backscattering spectrometers that have overlapping time scales, ranging from picoseconds to a few nanoseconds. Two modes of motion are detected for the PEI molecule in QENS. At low energy transfers, a "slow process" on the time scale of ∼200 ps is found and attributed to jump-mediated, center-of-mass diffusion. A second, "fast process" at ∼20 ps scale is also found and is attributed to a locally confined, jump-diffusion. Characteristic data (time scale and spectral weight) of these processes are compared to those characterized by MD, and reasonable agreement is found. For the nanopore-confined PEI, we observe a significant reduction in the time scale of polymer motion as compared to the bulk. The impacts of silica surface functionalization and of polymer fill fraction in the silica pores (controlling the portion of polymer molecules in contact with the pore walls), are both studied in detail. Hydrophobic functionalization of the silica leads to an increase of the PEI mobility above that in native silanol-terminated silica, but the dynamics are still slower than those in bulk PEI. Sorbents with faster PEI dynamics are also found to be more efficient for CO2 capture, possibly because sorption sites are more accessible than those in systems with slower PEI dynamics. Thus, this work supports the existence of a link between the affinity of the support for PEI and the accessibility of active sorbent functional groups.

Unraveling the Dynamics of Aminopolymer/Silica Composites.

The structure and dynamics of a model branched polymer was investigated through molecular dynamics simulations and neutron scattering experiments. The polymer confinement, monomer concentration, and solvent quality were varied in the simulations and detailed comparisons between the calculated structural and dynamical properties of the unconfined polymer and those confined within an adsorbing and nonadsorbing cylindrical pore, representing the silica based structural support of the composite, were made. The simulations show a direct relationship in the structure of the polymer and the nonmonotonic dynamics as a function of monomer concentration within an adsorbing cylindrical pore. However, the nonmonotonic behavior disappears for the case of the branched polymer within a nonadsorbing cylindrical pore. Overall, the simulation results are in good agreement with quasi-elastic neutron scattering (QENS) studies of branched poly(ethylenimine) in mesoporous silica (SBA-15) of comparable size, suggesting an approach that can be a useful guide for understanding how to tune porous polymer composites for enhancing desired dynamical and structural behavior targeting carbon dioxide adsorption.

Probing the Role of Zr Addition versus Textural Properties in Enhancement of CO2 Adsorption Performance in Silica/PEI Composite Sorbents.

Polymeric amines such as poly(ethylenimine) (PEI) supported on mesoporous oxides are promising candidate adsorbents for CO2 capture processes. An important aspect to the design and optimization of these materials is a fundamental understanding of how the properties of the oxide support such as pore structure, particle morphology, and surface properties affect the efficiency of the guest polymer in its interactions with CO2. Previously, the efficiency of impregnated PEI to adsorb CO2 was shown to increase upon the addition of Zr as a surface modifier in SBA-15. However, the efficacy of this method to tune the adsorption performance has not been explored in materials of differing textural and morphological nature. Here, these issues are directly addressed via the preparation of an array of SBA-15 support materials with varying textural and morphological properties, as well as varying content of zirconium doped into the material. Zirconium is incorporated into the SBA-15 either during the synthesis of the SBA-15, or postsynthetically via deposition of Zr species onto pure-silica SBA-15. The method of Zr incorporation alters the textural and morphological properties of the parent SBA-15 in different ways. Importantly, the CO2 capacity of SBA-15 impregnated with PEI increases by a maximum of ∼60% with the quantity of doped Zr for a "standard" SBA-15 containing significant microporosity, while no increase in the CO2 capacity is observed upon Zr incorporation for an SBA-15 with reduced microporosity and a larger pore size, pore volume, and particle size. Finally, adsorbents supported on SBA-15 with controlled particle morphology show only modest increases in CO2 capacity upon inclusion of Zr to the silica framework. The data demonstrate that the textural and morphological properties of the support have a more significant impact on the ability of PEI to capture CO2 than the support surface composition.

Linking CO2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering.

Composites of poly(ethylenimine) (PEI) and mesoporous silica are effective, reversible adsorbents for CO2, both from flue gas and in direct air-capture applications. The morphology of the PEI within the silica can strongly impact the overall carbon capture efficiency and rate of saturation. Here, we directly probe the spatial distribution of the supported polymer through small-angle neutron scattering (SANS). Combined with textural characterization from physisorption analysis, the data indicate that PEI first forms a thin conformal coating on the pore walls, but all additional polymer aggregates into plug(s) that grow along the pore axis. This model is consistent with observed trends in amine-efficiency (CO2/N binding ratio) and pore size distributions, and points to a trade-off between achieving high chemical accessibility of the amine binding sites, which are inaccessible when they strongly interact with the silica, and high accessibility for mass transport, which can be hampered by diffusion through PEI plugs. We illustrate this design principle by demonstrating higher CO2 capacity and uptake rate for PEI supported in a hydrophobically modified silica, which exhibits repulsive interactions with the PEI, freeing up binding sites.

High-performance Ag-Co alloy catalysts for electrochemical oxygen reduction.

The electrochemical oxygen reduction reaction is the limiting half-reaction for low-temperature hydrogen fuel cells, and currently costly Pt-based electrocatalysts are used to generate adequate rates. Although most other metals are not stable in typical acid-mediated cells, alkaline environments permit the use of less costly electrodes, such as silver. Unfortunately, monometallic silver is not sufficiently active for economical fuel cells. Herein we demonstrate the design of low-cost Ag-Co surface alloy nanoparticle electrocatalysts for oxygen reduction. Their performance relative to that of Pt is potential dependent, but reaches over half the area-specific activity of Pt nanoparticle catalysts and is more than a fivefold improvement over pure silver nanoparticles at typical operating potentials. The Ag-Co electrocatalyst was initially identified with quantum chemical calculations and then synthesized using a novel technique that generates a surface alloy, despite bulk immiscibility of the constituent materials. Characterization studies support the hypothesis that the activity improvement comes from a ligand effect, in which cobalt atoms perturb surface silver sites.

Controlling carbon surface chemistry by alloying: carbon tolerant reforming catalyst.

Steam reforming is a process where a hydrocarbon is converted into hydrogen and oxygenated carbon species. Ni is often used as catalyst for the reaction. Long term stability of steam reforming catalysts is governed by their ability to selectively oxidize C atoms while preventing C-C bond formation. In this communication we demonstrate that C atom chemistry over Ni surfaces can be controlled by surface alloying. We show that bimetallic Sn/Ni catalyst is much more carbon-tolerant that monometallic Ni. The main reason for this is that Sn alloying results in dramatically lower rates of C-C bond formation as compared to C-oxidation. The bimetallic catalyst was identified in quantum computational studies of the underlying atomic-scale phenomena that govern C atom surface chemistry. The catalysts were also characterized with various electron- and X-ray-based microscopies and spectroscopies.