Pure-Water-Fed Forward-Bias Bipolar Membrane CO2 Electrolyzer.

Coupling renewable electricity to reduce carbon dioxide (CO2) electrochemically into carbon feedstocks offers a promising pathway to produce chemical fuels sustainably. While there has been success in developing materials and theory for CO2 reduction, the widespread deployment of CO2 electrolyzers has been hindered by challenges in the reactor design and operational stability due to CO2 crossover and (bi)carbonate salt precipitation. Herein, we design asymmetrical bipolar membranes assembled into a zero-gap CO2 electrolyzer fed with pure water, solving both challenges. By investigating and optimizing the anion-exchange-layer thickness, cathode differential pressure, and cell temperature, the forward-bias bipolar membrane CO2 electrolyzer achieves a CO faradic efficiency over 80% with a partial current density over 200 mA cm-2 at less than 3.0 V with negligible CO2 crossover. In addition, this electrolyzer achieves 0.61 and 2.1 mV h-1 decay rates at 150 and 300 mA cm-2 for 200 and 100 h, respectively. Postmortem analysis indicates that the deterioration of catalyst/polymer-electrolyte interfaces resulted from catalyst structural change, and ionomer degradation at reductive potential shows the decay mechanism. All these results point to the future research direction and show a promising pathway to deploy CO2 electrolyzers at scale for industrial applications.

Colloidal Stability of PFSA-Ionomer Dispersions. Part I. Single-Ion Electrostatic Interaction Potential Energies.

Charged colloidal particles neutralized by a single counterion are increasingly important for many emerging technologies. Attention here is paid specifically to hydrogen fuel cells and water electrolyzers whose catalyst layers are manufactured from a perfluorinated sulfonic acid polymer (PFSA) suspended in aqueous/alcohol solutions. Partially dissolved PFSA aggregates, known collectively as ionomers, are stabilized by the electrostatic repulsion of overlapping diffuse double layers consisting of only protons dissociated from the suspended polymer. We denote such double layers containing no added electrolyte as "single ion". Size-distribution predictions build upon interparticle interaction potential energies from the Derjaguin-Landau-Verwey-Overbeek (DLVO) formalism. However, when only a single counterion is present in solution, classical DLVO electrostatic potential energies no longer apply. Accordingly, here a new formulation is proposed to describe how single-counterion diffuse double layers interact in colloidal suspensions. Part II (Srivastav, H.; Weber, A. Z.; Radke, C. J. Langmuir 2024 DOI: 10.1021/acs.langmuir.3c03904) of this contribution uses the new single-ion interaction energies to predict aggregated size distributions and the resulting solution pH of PFSA in mixtures of n-propanol and water. A single-counterion diffuse layer cannot reach an electrically neutral concentration far from a charged particle. Consequently, nowhere in the dispersion is the solvent neutral, and the diffuse layer emanating from one particle always experiences the presence of other particles (or walls). Thus, in addition to an intervening interparticle repulsive force, a backside osmotic force is always present. With this new construction, we establish that single-ion repulsive pair interaction energies are much larger than those of classical DLVO electrostatic potentials. The proposed single-ion electrostatic pair potential governs dramatic new dispersion behavior, including dispersions that are stable at a low volume fraction but unstable at a high volume fraction and finite volume-fraction dispersions that are unstable with fine particles but stable with coarse particles. The proposed single-counterion electrostatic pair potential provides a general expression for predicting colloidal behavior for any charged particle dispersion in ionizing solvents with no added electrolyte.

Colloidal Stability of PFSA-Ionomer Dispersions Part II: Determination of Suspension pH Using Single-Ion Potential Energies.

Perfluorosulfonic acid (PFSA) ionomers serve a vital role in the performance and stability of fuel-cell catalyst layers. These properties, in turn, depend on the colloidal processing of precursor inks. To understand the colloidal structure of fuel-cell catalyst layers, we explore the aggregation of PFSA ionomers dissolved in water/alcohol solutions and relate the predicted aggregation to experimental measurements of solution pH. Not all side chains contribute to measured pH because of burying inside particle aggregates. To account for the measured degree of dissociation, a new description is developed for how PFSA aggregates interact with each other. The developed single-counterion electrostatic repulsive pair potential from Part I is incorporated into the Smoluchowski collision-based kinetics of interacting aggregates with buried side chains. We demonstrate that the surrounding solvent mixture affects the degree of aggregation as well as the pH of the system primarily through the solution dielectric permittivity, which drives the strength of the interparticle repulsive energies. Successful pH prediction of Nafion ionomer dispersions in water/n-propanol solutions validates the numerical calculations. Nafion-dispersion pH measurements serve as a surrogate for Nafion particle-size distributions. The model and framework can be leveraged to explore different ink formulations.

Engineering Bipolar Interfaces for Water Electrolysis Using Earth-Abundant Anodes.

Developing efficient and low-cost water electrolyzers for clean hydrogen production to reduce the carbon footprint of traditional hard-to-decarbonize sectors is a grand challenge toward tackling climate change. Bipolar-based water electrolysis combines the benefits of kinetically more favorable half-reactions and relatively inexpensive cell components compared to incumbent technologies, yet it has been shown to have limited performance. Here, we develop and test a bipolar-interface water electrolyzer (BPIWE) by combining an alkaline anode porous transport electrode with an acidic catalyst-coated membrane. The role of TiO2 as a water dissociation (WD) catalyst is investigated at three representative loadings, which indicates the importance of balancing ionic conductivity and WD activity derived from the electric field for optimal TiO2 loading. The optimized BPIWE exhibits negligible performance degradation up to 500 h at 400 mA cm-2 fed with pure water using earth-abundant anode materials. Our experimental findings provide insights into designing bipolar-based electrochemical devices.

Ionomer-free and recyclable porous-transport electrode for high-performing proton-exchange-membrane water electrolysis.

Clean hydrogen production requires large-scale deployment of water-electrolysis technologies, particularly proton-exchange-membrane water electrolyzers (PEMWEs). However, as iridium-based electrocatalysts remain the only practical option for PEMWEs, their low abundance will become a bottleneck for a sustainable hydrogen economy. Herein, we propose high-performing and durable ionomer-free porous transport electrodes (PTEs) with facile recycling features enabling Ir thrifting and reclamation. The ionomer-free porous transport electrodes offer a practical pathway to investigate the role of ionomer in the catalyst layer and, from microelectrode measurements, point to an ionomer poisoning effect for the oxygen evolution reaction. The ionomer-free porous transport electrodes demonstrate a voltage reduction of > 600 mV compared to conventional ionomer-coated porous transport electrodes at 1.8 A cm-2 and <0.1 mgIr cm-2, and a voltage degradation of 29 mV at average rate of 0.58 mV per 1000-cycles after 50k cycles of accelerated-stress tests at 4 A cm-2. Moreover, the ionomer-free feature enables facile recycling of multiple components of PEMWEs, which is critical to a circular clean hydrogen economy.

Theory and Simulation of Metal-Insulator-Semiconductor (MIS) Photoelectrodes.

A metal-insulator-semiconductor (MIS) structure is an attractive photoelectrode-catalyst architecture for promoting photoelectrochemical reactions, such as the formation of H2 by proton reduction. The metal catalyzes the generation of H2 using electrons generated by photon absorption and charge separation in the semiconductor. The insulator layer between the metal and the semiconductor protects the latter element from photo-corrosion and, also, significantly impacts the photovoltage at the metal surface. Understanding how the insulator layer determines the photovoltage and what properties lead to high photovoltages is critical to the development of MIS structures for solar-to-chemical energy conversion. Herein, we present a continuum model for charge-carrier transport from the semiconductor to the metal with an emphasis on mechanisms of charge transport across the insulator. The polarization curves and photovoltages predicted by this model for a Pt/HfO2/p-Si MIS structure at different HfO2 thicknesses agree well with experimentally measured data. The simulations reveal how insulator properties (i.e., thickness and band structure) affect band bending near the semiconductor/insulator interface and how tuning them can lead to operation closer to the maximally attainable photovoltage, the flat-band potential. This phenomenon is understood by considering the change in tunneling resistance with insulator properties. The model shows that the best MIS performance is attained with highly symmetric semiconductor/insulator band offsets (e.g., BeO, MgO, SiO2, HfO2, or ZrO2 deposited on Si) and a low to moderate insulator thickness (e.g., between 0.8 and 1.5 nm). Beyond 1.5 nm, the density of filled interfacial trap sites is high and significantly limits the photovoltage and the solar-to-chemical conversion rate. These conclusions are true for photocathodes and photoanodes. This understanding provides critical insight into the phenomena enhancing and limiting photoelectrode performance and how this phenomenon is influenced by insulator properties. The study gives guidance toward the development of next-generation insulators for MIS structures that achieve high performance.

Anion-exchange membranes with internal microchannels for water control in CO2 electrolysis.

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.

Influence of Mesoscale Interactions on Proton, Water, and Electrokinetic Transport in Solvent-Filled Membranes: Theory and Simulation.

Transport of protons and water through water-filled, phase-separated cation-exchange membranes occurs through a network of interconnected nanoscale hydrophilic aqueous domains. This paper uses numerical simulations and theory to explore the role of the mesoscale network on water, proton, and electrokinetic transport in perfluorinated sulfonic acid (PFSA) membranes, pertinent to electrochemical energy-conversion devices. Concentrated-solution theory describes microscale transport. Network simulations model mesoscale effects and ascertain macroscopic properties. An experimentally consistent 3D Voronoi-network topology characterizes the interconnected channels in the membrane. Measured water, proton, and electrokinetic transport properties from literature validate calculations of macroscopic properties from network simulations and from effective-medium theory. The results demonstrate that the hydrophilic domain size affects the various microscale, domain-level transport modes dissimilarly, resulting in different distributions of microscale coefficients for each mode of transport. As a result, the network mediates the transport of species nonuniformly with dissimilar calculated tortuosities for water, proton, and electrokinetic transport coefficients (i.e., 4.7, 3.0, and 6.1, respectively, at a water content of 8 H2O molecules per polymer charge equivalent). The dominant water-transport pathways across the membrane are different than those taken by the proton cation. Finally, the distribution of transport properties across the network induces local electrokinetic flows that couple water and proton transport; specifically, local electrokinetic transport induces water chemical-potential gradients that decrease macroscopic conductivity by up to a factor of 3. Macroscopic proton, water, and electrokinetic transport coefficients depend on the collective microscale transport properties of all modes of transport and their distribution across the hydrophilic domain network.

Impact of Platinum Primary Particle Loading on Fuel Cell Performance: Insights from Catalyst/Ionomer Ink Interactions.

A variety of electrochemical energy conversion technologies, including fuel cells, rely on solution-processing techniques (via inks) to form their catalyst layers (CLs). The CLs are heterogeneous structures, often with uneven ion-conducting polymer (ionomer) coverage and underutilized catalysts. Various platinum-supported-on-carbon colloidal catalyst particles are used, but little is known about how or why changing the primary particle loading (PPL, or the weight fraction of platinum of the carbon-platinum catalyst particles) impacts performance. By investigating the CL gas-transport resistance and zeta (ζ)-potentials of the corresponding inks as a function of PPL, a direct correlation between the CL high current density performance and ink ζ-potential is observed. This correlation stems from likely changes in ionomer distributions and catalyst-particle agglomeration as a function of PPL, as revealed by pH, ζ-potential, and impedance measurements. These findings are critical to unraveling the ionomer distribution heterogeneity in ink-based CLs and enabling enhanced Pt utilization and improved device performance for fuel cells and related electrochemical devices.

Continuum Modeling of Porous Electrodes for Electrochemical Synthesis.

Electrochemical synthesis possesses substantial promise to utilize renewable energy sources to power the conversion of abundant feedstocks to value-added commodity chemicals and fuels. Of the potential system architectures for these processes, only systems employing 3-D structured porous electrodes have the capacity to achieve the high rates of conversion necessary for industrial scale. However, the phenomena and environments in these systems are not well understood and are challenging to probe experimentally. Fortunately, continuum modeling is well-suited to rationalize the observed behavior in electrochemical synthesis, as well as to ultimately provide recommendations for guiding the design of next-generation devices and components. In this review, we begin by presenting an historical review of modeling of porous electrode systems, with the aim of showing how past knowledge of macroscale modeling can contribute to the rising challenge of electrochemical synthesis. We then present a detailed overview of the governing physics and assumptions required to simulate porous electrode systems for electrochemical synthesis. Leveraging the developed understanding of porous-electrode theory, we survey and discuss the present literature reports on simulating multiscale phenomena in porous electrodes in order to demonstrate their relevance to understanding and improving the performance of devices for electrochemical synthesis. Lastly, we provide our perspectives regarding future directions in the development of models that can most accurately describe and predict the performance of such devices and discuss the best potential applications of future models.

Engineering Catalyst-Electrolyte Microenvironments to Optimize the Activity and Selectivity for the Electrochemical Reduction of CO2 on Cu and Ag.

The electrochemical reduction of carbon dioxide (CO2R) driven by renewably generated electricity (e.g., solar and wind) offers a promising means for reusing the CO2 released during the production of cement, steel, and aluminum as well as the production of ammonia and methanol. If CO2 could be removed from the atmosphere at acceptable costs (i.e., <$100/t of CO2), then CO2R could be used to produce carbon-containing chemicals and fuels in a fully sustainable manner. Economic considerations dictate that CO2R current densities must be in the range of 0.1 to 1 A/cm2 and selectivity toward the targeted product must be high in order to minimize separation costs. Industrially relevant operating conditions can be achieved by using gas diffusion electrodes (GDEs) to maximize the transport of species to and from the cathode and combining such electrodes with a solid-electrolyte membrane by eliminating the ohmic losses associated with liquid electrolytes. Additionally, high product selectivity can be attained by careful tuning of the microenvironment near the catalyst surface (e.g., the pH, the concentrations of CO2 and H2O, and the identities of the cations in the double layer adjacent to the catalyst surface).We begin this Account with a discussion of our experimental and theoretical work aimed at optimizing catalyst microenvironments for CO2R. We first examine the effects of catalyst morphology on the production of multicarbon (C2+) products over Cu-based catalysts and then explore the role of mass transfer combined with the kinetics of buffer reactions in the local concentration of CO2 and pH at the catalyst surface. This is followed by a discussion of the dependence of the local CO2 concentration and pH on the dynamics of CO2R and the formation of specific products over both Cu and Ag catalysts. Next, we explore the impact of electrolyte cation identity on the rate of CO2R and the distribution of products. Subsequently, we look at utilizing pulsed electrolysis to tune the local pH and CO2 concentration at the catalyst surface. The last part of the discussion demonstrates that ionomer-coated catalysts in combination with pulsed electrolysis can enable the attainment of very high (>90%) selectivity to C2+ products over Cu in an aqueous electrolyte. This part of the Account is then extended to consider the difference in the catalyst-nanoparticle microenvironment, present in the catalyst layer of a membrane electrode assembly (MEA), with respect to that of a planar electrode immersed in an aqueous electrolyte.

Gas Mass-Transport Coefficients in Ionomer Membranes Using a Microelectrode.

Gas permeability, the product of gas diffusivity and Henry's gas-absorption constant, of ionomer membranes is an important transport parameter in fuel cell and electrolyzer research as it governs gas crossover between electrodes and perhaps in the catalyst layers as well. During transient operation, it is important to divide the gas permeability into its constituent properties as they are individually important. Although transient microelectrode measurements have been used previously to separate the gas permeability into these two parameters, inconsistencies remain in the interpretation of the experimental techniques. In this work, a new interpretation methodology is introduced for determining independently diffusivity and Henry's constant of hydrogen and oxygen gases in ionomer membranes (Nafion 211 and Nafion XL) as a function of relative humidity using microelectrodes. Two time regimes are accounted for. At long times, gas permeability is determined from a two-dimensional numerical model that calculates the solubilized-gas concentration profiles at a steady state. At short times, permeability is deconvoluted into diffusivity and Henry's constant by analyzing transient data with an extended Cottrell equation that corrects for actual electrode surface area. Gas permeability and diffusivity increase as relative humidity increases for both gases in both membranes, whereas Henry's constants for both gases decrease with increasing relative humidity. In addition, results for Nafion 211 membranes are compared to a simple phase-separated parallel-diffusion transport theory with good agreement. The two-time-regime analysis and the experimental methodology can be applied to other electrochemical systems to enable greater precision in the calculation of transport parameters and to further understanding of gas transport in fuel cells and electrolyzers.

Linking Perfluorosulfonic Acid Ionomer Chemistry and High-Current Density Performance in Fuel-Cell Electrodes.

Transport phenomena are key in controlling the performance of electrochemical energy-conversion technologies and can be highly complex, involving multiple length scales and materials/phases. Material designs optimized for one reactant species transport however may inhibit other transport processes. We explore such trade-offs in the context of polymer-electrolyte fuel-cell electrodes, where ionomer thin films provide the necessary proton conductivity but retard oxygen transport to the Pt reaction site and cause interfacial resistance due to sulfonate/Pt interactions. We examine the electrode overall gas-transport resistance and its components as a function of ionomer content and chemistry. Low-equivalent-weight ionomers allow better dissolved-gas and proton transport due to greater water uptake and low crystallinity but also cause significant interfacial resistance due to the high density of sulfonic acid groups. These effects of equivalent weight are also observed via in situ ionic conductivity and CO displacement measurements. Of critical importance, the results are supported by ex situ ellipsometry and X-ray scattering of model thin-film systems, thereby providing direct linkages and applicability of model studies to probe complex heterogeneous structures. Structural and resultant performance changes in the electrode are shown to occur above a threshold sulfonic-group loading, highlighting the significance of ink-based interactions. Our findings and methodologies are applicable to a variety of solid-state energy-conversion devices and material designs.

Pathway to Complete Energy Sector Decarbonization with Available Iridium Resources using Ultralow Loaded Water Electrolyzers.

We present ultralow Ir-loaded (ULL) proton exchange membrane water electrolyzer (PEMWE) cells that can produce enough hydrogen to largely decarbonize the global natural gas, transportation, and electrical storage sectors by 2050, using only half of the annual global Ir production for PEMWE deployment. This represents a significant improvement in PEMWE's global potential, enabled by careful control of the anode catalyst layer (CL), including its mesostructure and catalyst dispersion. Using commercially relevant membranes (Nafion 117), cell materials, electrocatalysts, and fabrication techniques, we achieve at peak a 250× improvement in Ir mass activity over commercial PEMWEs. An optimal Ir loading of 0.011 mgIr cm-2 operated at an Ir-specific power of ∼100 MW kgIr-1 at a cell potential of ∼1.66 V versus RHE (85% higher heating value efficiency). We further evaluate the performance limitations within the ULL regime and offer new insights and guidance in CL design relevant to the broader energy conversion field.

Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes.

Bipolar membranes (BPMs) have the potential to become critical components in electrochemical devices for a variety of electrolysis and electrosynthesis applications. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-electrolyzers. In this study, a continuum model of multi-ion transport in a BPM is developed and fit to experimental data. Specifically, concentration profiles are determined for all ionic species, and the importance of a water-dissociation catalyst is demonstrated. The model describes internal concentration polarization and co- and counter-ion crossover in BPMs, determining the mode of transport for ions within the BPM and revealing the significance of salt-ion crossover when operated with pH gradients relevant to electrolysis and electrosynthesis. Finally, a sensitivity analysis reveals that the performance and lifetime of BPMs can be improved substantially by using of thinner dissociation catalysts, managing water transport, modulating the thickness of the individual layers in the BPM to control salt-ion crossover, and increasing the ion-exchange capacity of the ion-exchange layers in order to amplify the water-dissociation kinetics at the interface.

Highly Permeable Perfluorinated Sulfonic Acid Ionomers for Improved Electrochemical Devices: Insights into Structure-Property Relationships.

Rapid improvements in polymer-electrolyte fuel-cell (PEFC) performance have been driven by the development of commercially available ion-conducting polymers (ionomers) that are employed as membranes and catalyst binders in membrane-electrode assemblies. Commercially available ionomers are based on a perfluorinated chemistry comprised of a polytetrafluoroethylene (PTFE) matrix that imparts low gas permeability and high mechanical strength but introduces significant mass-transport losses in the electrodes. These transport losses currently limit PEFC performance, especially for low Pt loadings. In this study, we present a novel ionomer incorporating a glassy amorphous matrix based on a perfluoro(2-methylene-4-methyl-1,3-dioxolane) (PFMMD) backbone. The novel backbone chemistry induces structural changes in the ionomer, restricting ionomer domain swelling under hydration while disrupting matrix crystallinity. These structural changes slightly reduce proton conductivity while significantly improving gas permeability. The performance implications of this trade-off are assessed, which reveal the potential for substantial performance improvement by incorporation of highly permeable ionomers as the functional catalyst binder. These results underscore the significance of tailoring material chemistry to specific device requirements, where ionomer chemistry should be rationally designed to match the local transport requirements of the device architecture.

Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application.

In situ electrochemical diagnostics designed to probe ionomer interactions with platinum and carbon were applied to relate ionomer coverage and conformation, gleaned from anion adsorption data, with O2 transport resistance for low-loaded (0.05 mgPt cm-2) platinum-supported Vulcan carbon (Pt/Vu)-based electrodes in a polymer electrolyte fuel cell. Coupling the in situ diagnostic data with ex situ characterization of catalyst inks and electrode structures, the effect of ink composition is explained by both ink-level interactions that dictate the electrode microstructure during fabrication and the resulting local ionomer distribution near catalyst sites. Electrochemical techniques (CO displacement and ac impedance) show that catalyst inks with higher water content increase ionomer (sulfonate) interactions with Pt sites without significantly affecting ionomer coverage on the carbon support. Surprisingly, the higher anion adsorption is shown to have a minor impact on specific activity, while exhibiting a complex relationship with oxygen transport. Ex situ characterization of ionomer suspensions and catalyst/ionomer inks indicates that the lower ionomer coverage can be correlated with the formation of large ionomer aggregates and weaker ionomer/catalyst interactions in low-water content inks. These larger ionomer aggregates resulted in increased local oxygen transport resistance, namely, through the ionomer film, and reduced performance at high current density. In the water-rich inks, the ionomer aggregate size decreases, while stronger ionomer/Pt interactions are observed. The reduced ionomer aggregation improves transport resistance through the ionomer film, while the increased adsorption leads to the emergence of resistance at the ionomer/Pt interface. Overall, the high current density performance is shown to be a nonmonotonic function of ink water content, scaling with the local gas (H2, O2) transport resistance resulting from pore, thin film, and interfacial phenomena.

Hydrophobic Inorganic Oxide Pigments via Polymethylhydrosiloxane Grafting: Dispersion in Aqueous Solution at Extraordinarily High Solids Concentrations.

Building on the recent demonstration of aqueous-dispersible hydrophobic pigments that retain their surface hydrophobicity even after drying, we demonstrate the synthesis of surface-modified Ti-Pure R-706 (denoted R706) titanium dioxide-based pigments, consisting of a thin (one to three monolayers) grafted polymethylhydrosiloxane (PMHS) coating, which (i) are hydrophobic in the dry state according to capillary rise and dynamic vapor sorption measurements and (ii) form stable aqueous dispersions at solid contents exceeding 75 wt % (43 vol %), without added dispersant, displaying similar rheology to R706 native oxide pigments at 70 wt % (37 vol %) consisting of an optimal amount of conventional polyanionic dispersant (0.3 wt % on pigment basis). The surface-modified pigments have been characterized via 29Si and 13C cross-polarization/magic angle spinning solid-state NMR spectroscopy; infrared spectroscopy; thermogravimetric and elemental analyses; and ζ potential measurements. On the basis of these data, the stability of the surface-modified PMHS-R706 aqueous dispersions is attributed to steric effects, as a result of grafted PMHS strands on the R706 surface, and depends on the chaotropic nature of the base used during PMHS condensation to the pigment/polysiloxane interface. The lack of water wettability of the surface-modified oxide particles in their dry state translates to improved water-barrier properties in coatings produced with these surface-modified pigment particles. The synthetic approach appears general as demonstrated by its application to various inorganic-oxide pigment particles.