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Boettcher, Shannon W

Publications and source records attributed to Boettcher, Shannon W.

9 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Operation-Induced BiVO4 Surface Reconstruction Modulates Photoelectrochemical Glycerol Photooxidation Stability and Activity

Abstract Operation-induced surface reconstruction of photoelectrodes is underexplored as a path to control stability and performance. We show how adaptive junctions form via surface reconstruction of BiVO4 during glycerol photooxidation and how these surfaces affect electrolyte-dependent kinetics and durability. Preferential V dissolution in both acidic and alkaline media forms a Bi-rich layer. In situ measurements through a dual-working-electrode platform quantify the changes in photovoltage and charge-transfer resistance derived from adaptive junction formation, while enabling quantitative separation of the driving forces for charge separation and interfacial catalysis. The reconstructed surface in acidic media improves hole-transfer kinetics, functions as a glycerol-oxidation catalyst, and imparts photostability. Surface reconstruction in alkaline media exhibits the opposite behavior, impeding hole injection. This instability is mitigated by trace Ni2+ ions, which drive in situ surface activation without cocatalyst pre-deposition. This study shows the significance of surface reconstruction in the design of durable photoelectrodes for applications targeting organic electro-oxidation.

Yang, Jin Wook↗
DOE OSTI2026

How Does Water Dissociation Work in Bipolar Membranes?

Bipolar membranes (BPMs) create counteracting spatial gradients of pH and electrostatic potential in electrochemical systems, enabling applications in pH regulation, electrocatalysis, and separations. At the polarized junction of a BPM the water dissociation (WD, 2H2O ⇌ H3O+ + OH-) reaction can be driven, but it remains poorly understood. In this Perspective, we integrate molecular insights from bulk-water autoionization and the associated field effects with continuum descriptions of BPM electrostatics and experimental WD kinetic analyses to describe possible mechanisms of voltage-driven WD. Pristine BPM junctions highlight both the limits of primarily electric-field-driven WD and the practical challenges of junction stability at extreme reverse bias. Introducing heterogeneous catalyst layers, commonly metal oxides and graphene oxides, accelerates WD by orders of magnitude through hypothesized coupled effects in which surface acid-base functionality and high-density hydroxyl sites mediate proton-transfer steps, and catalyst mobile electronic/ionic charges redistribute the junction electric potential drop to shape the local electric fields and reactive microenvironments. Kinetic analyses suggest two regimes of heterogeneous WD mechanism, including field-driven ordering of interfacial water and a Second-Wien-Effect dissociation-barrier lowering. We conclude by defining the key unknown variables (local pH, electrostatic potential, catalyst charge state and relationships among mechanisms) and outlining experimental and multiscale modeling strategies needed for predictive WD catalysis and for controlling related ion-transfer reactions.

Wu, Yifan↗
DOE OSTI2026

Engineering CoO x ‑Based Self-Supported Anodes for Pure-Water-Fed Anion-Exchange-Membrane Electrolysis

Commercial membrane electrolyzers rely on acidic fluorocarbon membranes and ionomers, requiring the use of expensive IrO x -based oxygen-evolution catalysts. Anion-exchange-membrane water electrolyzers (AEMWEs) operate in an alkaline environment, enabling the use of non-precious-metal catalysts. Here, we study and engineer CoO x -based catalyst-coated anodes deposited via hydrothermal synthesis directly onto porous transport layers both with and without thermal annealing. The self-supported, nanoneedle-structured Co3O4 anode, formed by annealing the as-synthesized cobalt carbonate hydroxide, Co­(CO3) x (OH) y , outperforms the baseline Co3O4 nanoparticle ink-based anode in pure-water-fed AEMWE due to the improved catalyst-layer continuity and thus number of electroactive Co species. The as-synthesized and unannealed Co­(CO3) x (OH) y , however, appears to undergo substantial conversion to a more-active CoO x (OH) y phase predominantly at the surface, with nominal Co3+ present and higher electrical conductivity, lowering the cell voltage to ∼200 mV at 1.0 A·cm–2 in pure-water-fed AEMWE compared to the conventional Co3O4 nanoparticle anodes. We analyze the differences in electrode electrochemical response between pure-water and KOH feed modes, finding distinct activation and degradation modes. The Co­(CO3) x (OH) y anode shows significant activation and slower degradation linked to the conversion to oxyhydroxide. We propose catalyst layer designs that promote both hydroxide and electron transport, alongside interfacial engineering strategies to obtain high performance while mitigating anode degradation.

anion-exchange-membrane water electrolysis↗
DOE OSTI2025

Durable, pure water–fed, anion-exchange membrane electrolyzers through interphase engineering

Anion-exchange membrane water electrolyzers (AEMWEs) promise scalable, low-cost hydrogen production but are limited by the electrochemical instability of their anode ionomers. We report interphase engineering using inorganic-containing molecular additives that coassemble with ionomer, enabling pure water-fed AEMWEs to operate with a degradation rate <0.5 millivolt per hour at 2.0 amperes per square centimeter and 70°C-a >20-fold durability improvement. Analysis of different additives and ionomers shows that the stabilization mechanism involves cross-links between metal oxo/hydroxo oligomers and ionomers. Under operation, the inorganic additive enriches, forming an interphase near the water-oxidation catalyst that passivates the anode ionomer against continuous degradation while maintaining mechanical integrity and hydroxide conductivity. This additive-based interphase-engineering strategy provides a path to durable AEMWEs that operate without supporting electrolytes and is adaptable across diverse catalysts and ionomers for electrochemical technologies.

Hou, Shujin↗
DOE OSTI2025

Anion-Exchange-Membrane Electrolysis with Alkali-Free Water Feed

Hydrogen is a green and sustainable energy vector that can facilitate the large-scale integration of intermittent renewable energy, renewable fuels for heavy transport, and deep decarbonization of hard-to-abate industries. Anion-exchange-membrane water electrolyzers (AEM-WEs) have several achieved or expected competitive advantages over other electrolysis technologies, including the use of precious metal-free electrocatalysts at both electrodes, fluorine-free hydrocarbon-based ionomeric membranes and bipolar plates based on inexpensive materials. Contrasting the analogous proton-exchange-membrane system (PEM-WE), where pure water is circulated (no support electrolyte), the current generation of AEM-WEs necessitates the circulation of a dilute aqueous alkaline electrolyte for reaching high energy efficiency and durability. For several reasons, including but not limited to lower cost of balance-of-plant, lower operating cost and improved device's lifetime, achieving high cell efficiency and performance using an alkali-free water feed is highly desirable. In this review, we develop and build a foundational understanding of AEM-WEs operating with pure water, as well as discuss the effects of operating with natural water feeds like seawater. After a discussion of the possible advantages of pure-water-fed AEM-WEs, we cover the thermodynamic and kinetic processes involved in AEM-WE, followed by a detailed review of materials and components and their integration in the device. We highlight the influence of electrolyte composition and alkali/electrolyte-free feed on the membrane-electrode assembly, ionomers, electrocatalysts, porous transport layer, bipolar plates and operating configuration. We provide evidence for how the pure water feed engenders several issues related to the degradation of device components and propose mitigation strategies.

Electrodes↗
DOE OSTI2025

Perovskite Catalysts for Pure-Water-Fed Anion-Exchange-Membrane Electrolyzer Anodes: Co-design of Electrically Conductive Nanoparticle Cores and Active Surfaces

Anion-exchange-membrane water electrolyzers (AEMWEs) are a possible low-capital-expense, efficient, and scalable hydrogen-production technology with inexpensive hardware, earth-abundant catalysts, and pure water. However, pure-water-fed AEMWEs remain at an early stage of development and suffer from inferior performance compared with proton-exchange-membrane water electrolyzers (PEMWEs). One challenge is to develop effective non-platinum-group-metal (non-PGM) anode catalysts and electrodes in pure-water-fed AEMWEs. We show how LaNiO3-based perovskite oxides can be tuned by cosubstitution on both A- and B-sites to simultaneously maintain high metallic electrical conductivity along with a degree of surface reconstruction to expose a stable Co-based active catalyst. The optimized perovskite, Sr0.1La0.9Co0.5Ni0.5O3, yielded pure-water AEMWEs operating at 1.97 V at 2.0 A cm-2 at 70 °C with a pure-water feed, thus illustrating the utility of the catalyst design principles.

Zhai, Tingting↗
DOE OSTI2025

Comparing Advanced Bipolar Membranes for High-Current Electrodialysis and Membrane Electrolysis

Advanced bipolar membranes (BPMs) with low water-dissociation overpotential (ηwd) may enable new electrochemical technologies for electrolysis, fuel cells, acid–base synthesis, brine remediation, lithium-battery recycling, and cement production. However, these advanced BPMs have only been demonstrated in BPM water electrolysis (BPMWE) configurations where the BPM is under static compression by the porous-transport layers. It is important to study these BPMs in applications like electrodialysis where large degrees of static compression are not possible. We present a BPM electrodialysis (BPMED) platform to measure water-dissociation overpotential (ηwd) and compare BPMWE and BPMED systems. We show advanced BPMs with half the ηwd compared to commercial BPMs for BPMED while maintaining ∼90% current efficiency from 0.05–0.5 A cm–2. The BPMED ηwd values are, however, about 0.2 V higher at 0.5 A cm–2 than those for BPMWE. Regardless, these results show that BPMs developed and optimized in BPMWE applications are well-suited for next-generation high-current-density BPMED technologies.

Vulpin, Olivia T↗
DOE OSTI2024

Local Electric Field Effects on Water Dissociation in Bipolar Membranes Studied Using Core–Shell Catalysts

The local electric field strength is thought to affect the rate of water dissociation (WD) in bipolar membranes (BPMs) at the catalyst–nanoparticle surfaces. Here, we study core–shell nanoparticles, where the core is metallic, semiconducting, or insulating, to understand this effect. The nanoparticle cores were coated with a WD catalyst layer (TiO2 or HfO2) via atomic layer deposition (ALD), and the morphology was imaged with transmission electron microscopy. Irrespective of the core material, these core–shell catalysts displayed comparable WD overpotentials at optimal mass loading, despite the hypothesized differences in the electric field strength across the catalyst particle suggested by continuum electrostatic simulations. Substantial atomic interdiffusion between the core and shell was ruled out by X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and diffuse reflectance optical measurements. However, the optimal mass loading of catalyst was roughly 1 order of magnitude higher for the conductive and high dielectric core materials than for the low dielectric insulating cores. These findings are consistent with the hypothesis that electric field screening within the core material focuses the electric field drop between particles such that larger film thicknesses can be tolerated. Collectively, these data support the idea that it is the local electric field at the molecular level that controls proton-transfer rates and that the metal core/dielectric-shell constructs introduced here modulate that field. Further materials and synthetic design may enable optimization of the electric field strength across the proton-transfer trajectory at the material surface.

Sarma, Prasad V↗