One of the main challenges towards achieving high-efficiency solar-fuel generators performing CO2 reduction are the mass-transport limitations in traditional aqueous systems due to CO2 interactions/solubility and boundary-layer thickness. To circumvent these issues, gas-diffusion electrodes (GDEs) are considered wherein the CO2 is fed in a vapor form into a porous electrode. In this talk, we will explore the various tradeoffs endemic in GDE architectures. This is accomplished through multiphysics modeling of the cells including breakdowns of the various limiting phenomena. In addition, experimental data on the GDEs for CO2 reduction will be presented using both Ag and Cu-based catalysts. Key is understanding the potential distributions with the GDE and how this along with the observed higher current densities impact product selectivity with Cu-based catalysts. Finally, comments will be made concerning the possibilities of light inclusion in GDEs to enable solar CO2 reduction as well as the benefits of GDEs that extend beyond higher current-density operation including unprecedented control of the local environment compared to traditional, aqueous planar designs. Acknowledgements The material is based on work performed at the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, through the Office of Science of the U.S. Department of Energy under award no. DE-SC0004993

Safe and practical solar-driven hydrogen generators must be capable of efficient and stable operation under diurnal cycling with full separation of gaseous H2 and O2 products. In this study, a novel architecture that fulfills all of these requirements is presented. The approach is inherently scalable and provides versatility for operation under diverse electrolyte and lighting conditions. The concept is validated using a 1 cm2 triple-junction photovoltaic cell with its illuminated photocathode protected by a composite coating comprising an organic encapsulant with an embedded catalytic support. The device is compatible with operation under conditions ranging from 1 m H2SO4 to 1 m KOH, enabling flexibility in selection of semiconductor, electrolyte, membrane, and catalyst. Stable operation at a solar-to-hydrogen conversion efficiency of >10% is demonstrated under continuous operation, as well as under diurnal light cycling for at least 4 d, with simulated sunlight. Operational characteristics are validated by extended time outdoor testing. A membrane ensures products are separated, with nonexplosive gas streams generated for both alkaline and acidic systems. Analysis of operational characteristics under different lighting conditions is enabled by comparison of a device model to experimental data.

Gas-diffusion electrodes (GDEs) for electrochemical CO2 reduction allow for an order-of-magnitude increase in obtainable limiting current densities (~100 mA/cm2) compared to planar systems (~10 mA/cm2) due to the increase in CO2 flux, catalyst surface area, and reduction in diffusion length. Despite this improvement, aqueous GDE systems suffer from extensive catalyst dissolution/delamination and membrane degradation under operating conditions, as well as exhibit significant ohmic resistances stemming from their electrolyte layers. These characteristics limit the current densities that can be achieved at applied overpotentials and render them impractical for industrial implementation. Membrane-electrode assemblies (MEAs), consisting of humidified gaseous feeds at one or both electrodes and no aqueous electrolyte between the electrodes (i.e. only using a solid ion-conducting polymer or ionomer as an electrolyte), can overcome the limitations of the aqueous GDE. In this poster, two MEA cell designs will be addressed: Full-MEA (humidified gaseous feeds at both the anode and cathode) and Exchange-MEA (humidified gaseous feed at the cathode and an adjoining water or salt solution, e.g. KHCO3 or KOH, at the anode to provide hydration and a source of ions). The experimental performance results obtained from the near-optimized vapor-fed Full-MEA and H2O Exchange-MEA systems for CO2RR at ambient temperature and pressure conditions and the details of our ongoing work in building a fully integrated, tandem/cascade catalysis device are described. This poster also details plans for future investigations in exploring critical fabrication, operating conditions, and MEA properties. Acknowledgements This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. We would also like to thank Nemanja Danilovic, Kun Jiang, Julie Fornaciari, Yagya Regmi, Douglas Kushner, and Christianna Lininger for their help, discussions, and guidance in the course of this research project.

The rational design of high-performance electrocatalysts requires a detailed understanding of dynamic changes in catalyst properties, including oxidation states, surface area, and morphology under realistic working conditions. Oxide-derived Cu catalysts exhibit a remarkable selectivity toward multicarbon products for the electrochemical CO reduction reaction (CORR), but the exact role of the oxide remains elusive for explaining the performance enhancements. Here, we used operando X-ray absorption spectroscopy (XAS) coupled with simultaneous measurements of the catalyst activity and selectivity by gas chromatography (GC) to study the relationship between oxidation states of Cu-based catalysts and the activity for ethylene (C2H4) production in a CO gas-fed cell. By utilizing a custom-built XAS cell, oxidation states of Cu catalysts can be probed in device-relevant settings and under high current densities (>80 mA cm-2) for the CORR. By employing an electrochemical oxidation process, we found that the Cu oxidation states and specific ion species do not correlate with C2H4 production. The difference in the CORR activity is also investigated in relation to electrochemical surface area (ECSA) changes. While the hydrogen evolution reaction (HER) activity is positively correlated to the ECSA changes, the increased C2H4 activity is not proportional to the ECSA. Ex situ characterization from microscopic techniques suggests that the changes in the C2H4 activity and selectivity may arise from a morphological transformation that evolves into a more active structure. These comprehensive results give rise to the development of a cell regeneration method that can restore the performance of the Cu catalyst without cell disassembly. Our study establishes a basis for the rational design of highly active electrocatalysts for broad-range reactions in a gas-fed device.

A hybrid catalyst-bonded membrane device using gaseous reactants for a carbon monoxide reduction (COR) reaction in the cathode chamber, an aqueous electrolyte for an oxygen evolution reaction (OER) in the anode chamber, and an anion exchange membrane (AEM) for product separation was modeled, constructed, and tested. The Cu electrocatalyst was electrodeposited onto gas diffusion layers (GDLs) and was directly bonded to AEM by mechanical pressing in the hybrid device. The impacts of relative humidity at the cathode inlet on the selectivity and activity of COR were investigated by computational modeling and experimental methods. At a relative humidity of 30%, the Cu-based catalyst in the hybrid device exhibited a total operating current density of 87 mA cm-2 with a -2.0 V vs Ag/AgCl reference electrode, a Faradaic efficiency (FE) for C2H4 generation of 32.6%, and an FE for a liquid-based carbon product of 42.6%. Significant improvements in the partial current densities for COR were observed in relation to planar electrodes or flooded gas diffusion electrodes (GDEs). In addition, a custom test bed was constructed to characterize the oxidation states of the Cu catalysts in real time along with product analysis though the backside of the GDLs via operando X-ray absorption (XAS) measurements.

The activity of polycrystalline thin film photoelectrodes is impacted by local variations of the material properties due to the exposure of different crystal facets and the presence of grain/domain boundaries. Here a multi-modal approach is applied to correlate nanoscale heterogeneities in chemical composition and electronic structure with nanoscale morphology in polycrystalline Mo-BiVO₄ . By using scanning transmission X-ray microscopy, the characteristic structure of polycrystalline film is used to disentangle the different X-ray absorption spectra corresponding to grain centers and grain boundaries. Comparing both spectra reveals phase segregation of V₂ O₅ at grain boundaries of Mo-BiVO₄ thin films, which is further supported by X-ray photoelectron spectroscopy and many-body density functional theory calculations. Theoretical calculations also enable to predict the X-ray absorption spectral fingerprint of polarons in Mo-BiVO₄ . After photo-electrochemical operation, the degraded Mo-BiVO₄ films show similar grain center and grain boundary spectra indicating V₂ O₅ dissolution in the course of the reaction. Overall, these findings provide valuable insights into the degradation mechanism and the impact of material heterogeneities on the material performance and stability of polycrystalline photoelectrodes.

Electrochemical reduction of carbon dioxide (CO₂R) poses substantial promise to convert abundant feedstocks (water and CO₂) to value-added chemicals and fuels using solely renewable energy. However, recent membrane-electrode assembly (MEA) devices that have been demonstrated to achieve high rates of CO₂R are limited by water management within the cell, due to both consumption of water by the CO₂R reaction and electro-osmotic fluxes that transport water from the cathode to the anode. Additionally, crossover of potassium (K⁺) ions poses concern at high current densities where saturation and precipitation of the salt ions can degrade cell performance. Herein, a device architecture incorporating an anion-exchange membrane (AEM) with internal water channels to mitigate MEA dehydration is proposed and demonstrated. A macroscale, two-dimensional continuum model is used to assess water fluxes and local water content within the modified MEA, as well as to determine the optimal channel geometry and composition. The modified AEMs are then fabricated and tested experimentally, demonstrating that the internal channels can both reduce K⁺ cation crossover as well as improve AEM conductivity and therefore overall cell performance. This work demonstrates the promise of these materials, and operando water-management strategies in general, in handling some of the major hurdles in the development of MEA devices for CO₂R.

Ion transport is a fundamental process in many physical, chemical, and biological phenomena, and especially in electrochemical energy conversion and storage. Despite its immense importance, demonstrations of label-free, spatially and temporally resolved ion imaging in the solution phase under operando conditions are not widespread. Here we spatiotemporally map ion concentration gradient evolution in solution and yield ion transport parameters by refining interferometric reflection microscopy, obviating the need for absorptive or fluorescent labels. As an example, we use an electrochemical cell with planar electrodes to drive concentration gradients in a ferricyanide-based aqueous redox electrolyte, and we observe the lateral spatiotemporal evolution of ions via concentration-dependent changes to the refractive index. Analysis of an evolving spatiotemporal ion distribution directly yields the diffusivity of the redox-active species. The simplicity of this approach makes it amenable to probing local ion transport behavior in a wide range of electrochemical, bioelectronic, and electrophysiological systems.

Confinement of metal centers is a powerful tool to manipulate reactivity and tune selectivity in chemical transformations. While aluminum as a foil is inactive for carbon dioxide reduction and shows high selectivity for the hydrogen evolution reaction, here we show that aluminum confined in a metal-organic framework (MOF), MIL-53(Al), suppresses hydrogen evolution reaction activity and enhances carbon dioxide reduction. This aluminum MOF can produce up to 40% faradaic efficiency for carbon monoxide and formic acid. This study demonstrates that the unique reaction environment created by the MOF enables changes in reaction selectivity and can impart atypical catalytic capabilities to metals.

Conversion of CO₂ to reduced products is a promising route to alleviate irreversible climate change. Here we report the synthesis of a Co-based phthalocyanine with pyridine moieties (CoPc-Pyr), which is supported on a carbon electrode and shows Faradaic efficiency ∼90% for CO at 490 mV of overpotential (-0.6 V vs reversible hydrogen electrode (RHE)). In addition, its catalytic activity at -0.7 V versus RHE surpasses other Co-based molecular and metal-organic framework catalysts for CO₂ reduction at this bias. Density functional theory calculations show that pyridine moieties enhance CO₂ adsorption and electron affinity of the Co center by an inductive effect, thus lowering the overpotential necessary for CO₂ conversion. Our study shows that CoPc-Pyr reduces CO₂ at lower overpotential and with higher activity than noble metal electrodes, such as silver.