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Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO2 to CO (CO2 R), can also selectively catalyze thermal CO2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO2 R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO2 R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2 R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni-N bonding and correlating CO2 reduction (CO2 R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO2 R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.

Unique classes of active-site motifs are needed for improved electrocatalysis. Herein, the activity of a new catalyst motif is engineered and isolated for the oxygen evolution reaction (OER) created by nickel–iron transition metal electrocatalysts confined within a layered zirconium phosphate matrix. It is found that with optimal intercalation, confined NiFe catalysts have an order of magnitude improved mass activity compared to more conventional surface-adsorbed systems in 0.1 m KOH. Interestingly, the confined environments within the layered structure also stabilize Fe-rich compositions (90%) with exceptional mass activity compared to known Fe-rich OER catalysts. Through controls and by grafting inert molecules to the outer surface, it is evidenced that the intercalated Ni/Fe species stay within the interlayer during catalysis and serve as the active site. After determining a possible structure (wycherproofite), density functional theory is shown to correlate with the observed experimental compositional trends. It is further demonstrated that the improved activity of this motif is correlated to the Fe and water content/composition within the confined space. This work highlights the catalytic enhancement possibilities available through zirconium phosphate and isolates the activity from the intercalated species versus surface/edge ones, thus opening new avenues to develop and understand catalysts within unique nanoscale chemical environments.

Methanol is a major fuel and chemical feedstock currently produced from syngas, a CO/CO2/H2 mixture. Herein we identify formate binding strength as a key parameter limiting the activity and stability of known catalysts for methanol synthesis in the presence of CO2. We present a molybdenum phosphide catalyst for CO and CO2 reduction to methanol, which through a weaker interaction with formate, can improve the activity and stability of methanol synthesis catalysts in a wide range of CO/CO2/H2 feeds.

CO2 emissions can be transformed into high-added-value commodities through CO2 electrocatalysis; however, efficient low-cost electrocatalysts are needed for global scale-up. Inspired by other emerging technologies, the authors report the development of a gas diffusion electrode containing highly dispersed Ag sites in a low-cost Zn matrix. This catalyst shows unprecedented Ag mass activity for CO production: -614 mA cm-2 at 0.17 mg of Ag. Subsequent electrolyte engineering demonstrates that halide anions can further improve stability and activity of the Zn-Ag catalyst, outperforming pure Ag and Au. Membrane electrode assemblies are constructed and coupled to a microbial process that converts the CO to acetate and ethanol. Combined, these concepts present pathways to design catalysts and systems for CO2 conversion toward sought-after products.

We report the first synthesis of a fully contiguous large area supported thin film of highly ordered mesoporous Ru and RuO2 and investigate the electrocatalytic properties towards the oxygen evolution reaction (OER). We find that the nanoscale porous network of these catalysts provides significant enhancements in geometric OER activity without any loss in specific activity. This work demonstrates a strategy for engineering materials at the nanoscale that can simultaneously decrease precious metal loading and increase catalytic activity.

We report on CO2 electroreduction activity and selectivity of a polycrystalline AgZn foil in aqueous bicarbonate electrolyte. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) measurements show that the alloy foil was slightly enriched in zinc both at the surface and in the bulk, with a surface alloy composition of 61.3±5.4 at % zinc and with Ag5Zn8 as the most prominent bulk phase. AgZn is active for CO2 reduction; CO is the main product, likely due to the weak CO binding energy of the surface, with methane and methanol emerging as minor products. Compared to pure silver and pure zinc foils, enhancements in activity and selectivity for methane and methanol are observed. A five-fold increase is observed in the combined partial current densities for methane and methanol at −1.43 V vs. the reversible hydrogen electrode (RHE), representing a four- to six-fold increase in faradaic efficiency. Such enhancements indicate the existence of a synergistic effect between silver and zinc at the surface of the alloy that contributes to the enhanced formation of further reduced products.

Porphyrinic metal–organic frameworks (PMOFs) are very appealing electrocatalytic materials, in part, due to their highly porous backbone, well‐defined and dispersed metal active sites, and their long‐range order. Herein a series of (Co)PCN222 (PCN: porous coordination network) (nano)particles with different sizes are successfully prepared by coordination modulation synthesis. These particles exhibit stability in 0.1 m HClO4 electrolyte with no obvious particle size or compositional changes observed after being soaked for 3 days in the electrolyte or during electrocatalysis. This long‐term stability enables the in‐depth investigation into the electrocatalytic oxygen reduction, and it is further demonstrated that the (Co)PCN222 particle size correlates with its catalytic activity. Of the three particle sizes evaluated (characteristic length scales of 200, 500, and 1000 nm), the smallest size demonstrates the highest mass activity while the largest size has the highest surface area normalized activity. Together these results highlight the importance of determining the structural stability of framework catalysts and provide insights into the important roles of particle size, opening new avenues to investigate and improve the electrocatalytic performance of this class of framework material.

The development of low-cost hydrogen evolution reaction (HER) catalysts that can be readily integrated into electrolyzers is critical if H2 from renewable electricity-powered electrolysis is to compete cost effectively with steam reforming. Herein, we report three distinct earth-abundant Mo-based catalysts, namely those based on MoSx , [Mo3 S13 ](2-) nanoclusters, and sulfur-doped Mo phosphide (MoP|S), loaded onto carbon supports. The catalysts were synthesized through facile impregnation-sulfidization routes specifically designed for catalyst-device compatibility. Fundamental electrochemical studies demonstrate the excellent HER activity and stability of the Mo-sulfide based catalysts in an acidic environment, and the resulting polymer electrolyte membrane (PEM) electrolyzers that integrate these catalysts exhibit high efficiency and durability. This work is an important step towards the goal of replacing Pt with earth-abundant catalysts for the HER in commercial PEM electrolyzers.

Photoelectrochemical (PEC) water splitting is a means to store solar energy in the form of hydrogen. Knowledge of practical limits for this process can help researchers assess their technology and guide future directions. We develop a model to quantify loss mechanisms in PEC water splitting based on the current state of materials research and calculate maximum solar-to-hydrogen (STH) conversion efficiencies along with associated optimal absorber band gaps. Various absorber configurations are modeled considering the major loss mechanisms in PEC devices. Quantitative sensitivity analyses for each loss mechanism and each absorber configuration show a profound impact of both on the resulting STH efficiencies, which can reach upwards of 25 % for the highest performance materials in a dual stacked configuration. Higher efficiencies could be reached as improved materials are developed. The results of the modeling also identify and quantify approaches that can improve system performance when working with imperfect materials.

In this work, a methodology is demonstrated to engineer gas diffusion electrodes for nonprecious metal catalysts. Highly active transition metal phosphides are prepared on carbon‐based gas diffusion electrodes with low catalyst loadings by modifying the O/C ratio at the surface of the electrode. These nonprecious metal catalysts yield extraordinary performance as measured by low overpotentials (51 mV at −10 mA cm−2), unprecedented mass activities (>800 A g−1 at 100 mV overpotential), high turnover frequencies (6.96 H2 s−1 at 100 mV overpotential), and high durability for a precious metal‐free catalyst in acidic media. It is found that a high O/C ratio induces a more hydrophilic surface directly impacting the morphology of the CoP catalyst. The improved hydrophilicity, stemming from introduced oxyl groups on the carbon electrode, creates an electrode surface that yields a well‐distributed growth of cobalt electrodeposits and thus a well‐dispersed catalyst layer with high surface area upon phosphidation. This report demonstrates the high‐performance achievable by CoP at low loadings which facilitates further cost reduction, an important part of enabling the large‐scale commercialization of non‐platinum group metal catalysts. The fabrication strategies described herein offer a pathway to lower catalyst loading while achieving high efficiency and promising stability on a 3D electrode.

Molybdenum phosphide (MoP) catalysts have recently attracted attention due to their robust methanol synthesis activity from CO/CO2. Synthesis strategies are used to steer MoP selectivity toward higher alcohols by investigating the promotion effects of alkali (K) and CO-dissociating (Co, Ni) and non-CO-dissociating (Pd) metals. A systematic study with transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy (XAS) showed that critical parameters governing the activity of MoP catalysts are P/Mo ratio and K loading, both facilitating MoP formation. The kinetic studies of mesoporous silica-supported MoP catalysts show a twofold role of K, which also acts as an electronic promoter by increasing the total alcohol selectivity and chain length. Palladium (Pd) increases CO conversion, but decreases alcohol chain length. The use of mesoporous carbon (MC) support has the most significant effect on catalyst performance and yields a KMoP/MC catalyst that ranks among the state-of-the-art in terms of selectivity to higher alcohols.

We outline a systematic approach to develop active catalyst materials for an electrochemical reaction. The strategy allows one to tune binding energies of oxygen reaction intermediates on a catalyst surface by taking advantage of two effects: weakening oxygen binding energies by means of thin-film overlayers, and strengthening oxygen binding energies through nanoscale effects. By engineering a core–shell nanoparticle morphology with the appropriate dimensions, that is, the thickness of the overlayer and the size of the nanoparticle, bonding properties can be modified to improve the catalytic activity of the core–shell system. We demonstrate the application of this strategy for oxygen reduction by identifying Ru@Pt as a candidate material using density functional theory calculations, and then use these calculations to guide the synthesis of active Ru@Pt core–shell catalysts. The Ru@Pt particles, synthesized using a wet chemical method, exhibit ∼2 times higher specific activity (based on electrochemical active surface area) than state-of-the-art Pt/C from TKK.

There have been extensive research efforts focusing on developing technologies for renewable electricity, particularly solar photovoltaics and wind turbines. However, the intermittent and localized nature of wind and solar energy necessitates the development of a cost-effective way to balance energy supply and demand and to deliver electricity from remote places to cities.[1] The short-term option is the electricity grid; however, it can only support intermittent renewable electricity in a stable fashion up to approximately 20 % of grid capacity which means that fossil resources would still account for the remaining 80 % of grid electricity.[2] Clearly, the development of cost-effective energy storage devices is needed to establish a path toward fossil-free energy. Pumped hydro currently dominates grid-scale energy storage due to its low cost but is hindered by a lack of suitable geographical sites.[3] Hence, there has been interest in developing alternative cost-effective energy storage technologies that can be rapidly scaled-up. Regenerative fuel cells (RFCs) are interesting candidates: a RFC is an electrochemical energy storage and conversion device that typically uses H2 as an energy carrier. RFCs possess high specific energies, enjoy economies-of-scale advantages, are modular in nature, and use only environmentally friendly and inexpensive reactants.[4,5] However, RFCs are currently too expensive to compete with existing energy storage technologies.[5] Herein, we demonstrate a prototype alkaline exchange membrane unitized RFC (AEM-URFC) that stores energy based on electrochemical interconversions among H2O, H2, and O2, with the key development of having done so in a low-temperature, precious-metal free device operating at low temperatures while avoiding the use of precious metal catalysts. The prototype device we have developed obtains round trip efficiencies of 34-40 % at 10 mA/cm over 8 cycles, with a peak power density of 17 mW/cm in fuel cell mode. This report of a preciousmetal free AEM-URFC opens up new possibilities for enabling cost-effective and widespread deployment of renewable electricity.

The ability to deposit conformal catalytic thin films enables opportunities to achieve complex nanostructured designs for catalysis. Atomic layer deposition (ALD) is capable of creating conformal thin films over complex substrates. Here, ALD-MnOx on glassy carbon is investigated as a catalyst for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), two reactions that are of growing interest due to their many applications in alternative energy technologies. The films are characterized by X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, ellipsometry, and cyclic voltammetry. The as-deposited films consist of Mn(II)O, which is shown to be a poor catalyst for the ORR, but highly active for the OER. By controllably annealing the samples, Mn2O3 catalysts with good activity for both the ORR and OER are synthesized. Hypotheses are presented to explain the large difference in the activity between the MnO and Mn2O3 catalysts for the ORR, but similar activity for the OER, including the effects of surface oxidation under experimental conditions. These catalysts synthesized though ALD compare favorably to the best MnOx catalysts in the literature, demonstrating a viable way to produce highly active, conformal thin films from earth-abundant materials for the ORR and the OER.

Trends in electrocatalytic activity of the oxygen evolution reaction (OER) are investigated on the basis of a large database of HO* and HOO* adsorption energies on oxide surfaces. The theoretical overpotential was calculated by applying standard density functional theory in combination with the computational standard hydrogen electrode (SHE) model. We showed that by the discovery of a universal scaling relation between the adsorption energies of HOO* vs HO*, it is possible to analyze the reaction free energy diagrams of all the oxides in a general way. This gave rise to an activity volcano that was the same for a wide variety of oxide catalyst materials and a universal descriptor for the oxygen evolution activity, which suggests a fundamental limitation on the maximum oxygen evolution activity of planar oxide catalysts.

Surface-sulfur modified MoP catalyst is prepared by drop casting aliquots of 0.25 M (NH4)6Mo7O24 and (NH4)2HPO4 solutions on a Ti foil support followed by drying, thermal reduction (5% H2/N2, 650 °C, 2 h), and thermal sulfidation (10% H2S/H2, 400 °C, 15 min).

Automated electrochemical synthesis was used to create combinatorial libraries of mesoporous materials using tri-block copolymers as structure directing agents (SDA). An example library of 56 ZnO samples was synthesized, varying concentrations (0-15 wt.-%) of poly(ethylene oxide) -block-poly(propylene oxide)-block-poly(ethylene oxide) - EO20PO70EO20. High-throughput photoelectrochemical screening for the measurement of water-splitting photocatalysis identified peak performance at 3 wt.-% of the SDA. Lamellar structures and disordered mesopores were observed by TEM and XRD.

The use of thin Ta3N5 films in tandem Si-Ta3N5 photoelectrochemical (PEC) devices motivates understanding of the surface Ta3N­5 properties, as they may have a strong effect on the device performance. The bulk and surface properties can change as a function of nitridation temperature; thus its effect is studied, ranging from 700 to 1000 °C, on the PEC performance, morphology, and composition of thin (10 nm) Ta3N5 films deposited on planar and nanostructured Si substrates. Scanning electron microscopy (SEM), scanning Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) are employed to gain fundamental understanding in the differences of the Ta­3N5 films. By controlling Ta3N­5 morphology and composition with nitridation temperature, it is determined that Ta3N5 with high crystallinity and surface N/Ta ratio, synthesized at 800 °C, yields the highest PEC performance with the earliest photocurrent onset and highest photocurrent. Samples nitrided at 700 °C have lower crystallinity and that likely leads to lower performance. For samples nitrided at temperatures above 800 °C, the N/Ta ratio decreases forming chemically reduced tantalum nitride phases, as well as N-deficient and correspondingly O-rich morphological domains that can adversely affect the PEC performance as hole-blocking layers or O trap-mediated recombination centers at the surface of Ta3N5.

Tandem photoelectrochemical water splitting cells utilizing crystalline Si and metal oxide photoabsorbers are promising for low-cost solar hydrogen production. This study presents a device design and a scalable fabrication scheme for a tandem heterostructure photoanode: p+n black silicon (Si)/SnO2 interface/W-doped bismuth vanadate (BiVO4)/cobalt phosphate (CoPi) catalyst. The black-Si not only provides a substantial photovoltage of 550 mV, but it also serves as a conductive scaffold to decrease charge transport pathlengths within the W-doped BiVO4 shell. When coupled with cobalt phosphide (CoP) nanoparticles as hydrogen evolution catalysts, the device demonstrates spontaneous water splitting without employing any precious metals, achieving an average solar-to-hydrogen efficiency of 0.45% over the course of an hour at pH 7. This fabrication scheme offers the modularity to optimize individual cell components, e.g., Si nanowire dimensions and metal oxide film thickness, involving steps that are compatible with fabricating monolithic devices. This design is general in nature and can be readily adapted to novel, higher performance semiconducting materials beyond BiVO4 as they become available, which will accelerate the process of device realization.

One of the crucial parameters dictating the efficiency of photoelectrochemical water-splitting is the semiconductor band edge alignment with respect to hydrogen and oxygen redox potentials. Despite the importance of metal oxides in their use as photoelectrodes, studies to control the band edge alignment in aqueous solution have been limited predominantly to compound semiconductors with modulation ranges limited to a few hundred mV. The ability to modulate the flat band potential of oxide photoanodes by as much as 1.3 V, using the insertion of subsurface electrostatic dipoles near a Nb-doped SrTiO3/aqueous electrolyte interface is reported. Lastly, the tunable range achieved far exceeds previous reports in any semiconductor/aqueous electrolyte system and suggests a general design strategy for highly efficient oxide photoelectrodes.

Herein, a high surface area electrode (HSE) consisting of indium tin oxide (ITO) as a scaffold and ultrathin Ti-doped hematite (α-Fe2O3) as the absorber material is developed. The HSE exhibits sixfold improvement in photoactivity over an analogous photoelectrode with a flat morphology. Interfacial recombination due to dopant impurities and shunting resulting from a high pinhole density in the hematite layer limit the device performance. These limitations are mitigated by introducing a tin oxide barrier layer, which reduces recombination at the solid–solid interface and mitigates shunting. Employing the HSE with an appropriate barrier layer improves charge separation efficiency and catalytic activity compared to conventional planar devices. This strategy can potentially be extended to other light absorber materials whose performance is affected by charge transport limitations.

The energy infrastructure for fossil fuels is well-established, accounting for approximately 87% of the 16 TW of power consumed globally. For renewable and sustainable energy conversion technologies to play a relevant role at the terrestrial scale, they must be able to scale to the TW level of deployment. This would place a significant demand on the current and future supply of raw materials (chemical elements) used by those technologies. Oftentimes, the average crustal abundance of a chemical element is cited as a measure of its scalability, however another important metric for scalability is the existence (of lack thereof) of mineable ores with a high concentration of the targeted element. This paper aims to provide an overview of the availability of all elements. This is accomplished via a compilation of data for global primary production rates for each element, as a measure of availability at the present time. This work also addresses the potential future availability based on current and possible future primary sources.

A high-throughput screening system and methodology were developed for libraries of hydrogen (H2) producing catalytic materials. The system is based on the chemo-optical properties of WO3, which give rise to reflectance changes in the presence of H2. Pd-coated WO3 sensors were synthesized and examined for their hydrogen sensitivity, wavelength-dependent reflectance, and performance in the presence of water vapor. For high-throughput screening, a polypropylene reactor block was designed and constructed to house 8 × 12 catalyst libraries deposited as thin films. When the library and reactor block are assembled together, 96 independent microreactor units are formed. A large-area Pd/WO3 sensor film covers and seals all microreactors, forming a 96-element 2-D H2 sensor array. As H2 is produced differentially across the library, the reflectance changes of the Pd/WO3 film are monitored by reflectivity sensors that scan the surface every 30 s. The time-dependent changes in reflectance indicate relative rates of H2...

Automated systems for electrochemical synthesis and high-throughput screening of photoelectrochemical materials were developed and used to prepare tungsten-based mixed-metal oxides, W(n)O(m)M(x) [M = Ni, Co, Cu, Zn, Pt, Ru, Rh, Pd, and Ag], specifically for hydrogen production by photoelectrolysis of water. Two-dimensional arrays (libraries) of diverse metal oxides were synthesized by automated cathodic electrodeposition of the oxides on Ti foil substrates. Electrolytes for the mixed oxides were prepared from various metal salts added to a solution containing tungsten stabilized as a peroxo complex. Electrodeposition of the peroxo-stabilized cations gave rise to three distinguishable oxide groups: (1) mixed-metal oxides [Ni], (2) metal-doped tungsten oxides [Pt, Ru, Rh, Pd, Ag], and (3) metal-metal oxide composites [Co, Cu, Zn]. The oxides typically showed n-type semiconducting behavior. Automated measurement of photocurrent using a scanning photoelectrochemical cell showed the W-Ni mixed oxide had the largest relative zero bias photocurrent, particularly at a low Ni concentration (5-10 atomic percent Ni). Pt and Ru were also found to increase the photoactivity of bulk tungsten oxide at relatively low concentrations; however, at concentrations above 5 atomic percent, crystallization of WO(3) was inhibited and photoactivity was diminished. Addition of Co, Cu, and Zn to WO(3) was not found to improve the photoelectrochemical activity.

Silicon is a promising photocathode for tandem photoelectrochemical water splitting devices, but efficient catalysis and long term stability remain key challenges. Here, it is demonstrated that with appropriately engineered interfaces, molybdenum sulfide nanomaterials can provide both corrosion protection and catalytic activity in silicon photocathodes. Using a thin MoS2 surface protecting layer, MoS2-n+p Si electrodes that show no loss in performance after 100 h of operation are created. Transmission electron microscopy measurements show the atomic structure of the device surface and reveal the characteristics of the MoS2 layer that provide both catalytic activity and excellent stability. In spite of a low concentration of exposed catalytically active sites, these electrodes possess the best performance of any precious metal-free silicon photocathodes with demonstrated long term stability to date. To further improve efficiency, a second molybdenum sulfide nanomaterial, highly catalytically active [Mo3S13]2− clusters, is incorporated. These photocathodes offer a promising pathway towards sustainable hydrogen production.