High-Performance Iridium-Molybdenum Oxide Electrocatalysts for Water Oxidation in Acid: Bayesian Optimization Discovery and Experimental Testing.

Ir oxides are costly and scarce catalysts for oxygen evolution reaction (OER) in acid. There has been extensive interest in developing alternatives that are either Ir-free or require smaller amounts of Ir to drive the reactions at acceptable rates. One design strategy is to identify Ir-based mixed oxides that achieve similar performance while requiring smaller amounts of Ir. The obstacle to this strategy has been a very large phase space of the Ir-based mixed metal oxides, in terms of the metals combined with Ir and the different crystallographic structures of the mixed oxides, which prevents a thorough exploration of possible materials. In this work, we developed a workflow that uses machine-learning-aided Bayesian optimization in combination with density functional theory to make the exploration of this phase space plausible. This screening identified Mo as a promising dopant for forming acid-tolerant Ir-based oxides for the OER. We synthesized and characterized the Ir-Mo mixed oxides in the form of thin-film electrocatalysts with a known surface area. We show that these mixed oxides exhibited overpotentials ∼30 mV lower than a pure Ir control while maintaining 24% lower Ir dissolution rates than the Ir control. These findings suggest that Mo is a promising dopant and highlight the promise of machine learning to guide the experimental exploration and optimization of catalytic materials.

Optimizing hierarchical membrane/catalyst systems for oxidative coupling of methane using additive manufacturing.

The advantage of a membrane/catalyst system in the oxidative coupling of methane compared with conventional reactive systems is that by introducing oxygen into the catalytic sites through a membrane, the parasitic gas-phase reactions of O2(g)-responsible for lowering product selectivity-can be avoided. The design and fabrication of membrane/catalyst systems has, however, been hampered by low volumetric chemical conversion rates, high capital cost and difficulties in co-designing membrane and catalyst properties to optimize the performance. Here we solve these issues by developing a dual-layer additive manufacturing process, based on phase inversion, to design, fabricate and optimize a hollow-fibre membrane/catalyst system for the oxidative coupling of methane. We demonstrate the approach through a case study using BaCe0.8Gd0.2O3-δ as the basis of both catalyst and separation layers. We show that by using the manufacturing approach, we can co-design the membrane thickness and catalyst surface area so that the flux of oxygen transport through the membrane and methane activation rates in the catalyst layer match each other. We demonstrate that this 'rate matching' is critical for maximizing the performance, with the membrane/catalyst system substantially overperforming conventional reactor designs under identical conditions.

Elucidating the Roles of Local and Nonlocal Rate Enhancement Mechanisms in Plasmonic Catalysis.

Plasmonic metal nanoparticles (e.g., Ag, Au, and Cu) constitute a class of materials that interact with light via the excitation of localized surface plasmon resonance (LSPR). Numerous studies have reported substantial enhancements in the rates of chemical reactions on illuminated plasmonic nanoparticle catalysts compared to corresponding systems in the absence of illumination. There are two mechanisms that have been proposed to explain the LSPR-induced chemical reactivity. One mechanism assumes a local plasmon-induced hot charge-carrier-mediated activation of the reactants, while the other assumes an LSPR-induced equilibrium heating of the catalyst, which leads to energy transfer to and chemical reaction of the adsorbed reactants. In this contribution, we developed a setup amenable to accurate in situ catalyst temperature and kinetic reaction rate measurements. We employed this setup to study the LSPR-induced rate enhancement in a case study of the CO oxidation reaction on plasmonic, monometallic Ag nanoparticle catalysts supported on α-Al2O3. We explored various Ag loadings and clustering levels. Our data show that the equilibrium heating of the catalyst cannot fully explain the illumination-induced plasmonic rate enhancements. This is the case even for high loading and clustering of Ag nanoparticles, where the equilibrium heating significantly increases. Based on the analysis, we propose that local effects, related to the plasmon-induced activation of adsorbates (reactants) via electronic excitation of the reactant or photothermal heating of the reactants that is highly localized to the individual nanoparticles, play a critical role in driving LSPR-induced chemical reactions.

Flow and extraction of energy and charge carriers in hybrid plasmonic nanostructures.

Strong interactions of electromagnetic fields with plasmonic nanomaterials have been exploited in various applications. These applications have centred on plasmon-enhanced scattering rates in nearby molecules or plasmon-induced heating. A question that has emerged recently is whether it is possible to use plasmonic nanostructures in a range of hot electron (hole) applications, including photocatalysis, photovoltaics and photodetection. These applications require coupling of a plasmonic component, which amplifies the interaction of light with the material, to an attached non-plasmonic component that extracts this energy in the form of electronic excitations to perform a function. In this Perspective, we discuss recent work in the emerging field of hybrid plasmonics. We focus on fundamental questions related to the nanoscopic flow of energy and excited charge carriers in these multicomponent materials. We also address critical misconceptions, challenges and opportunities that require more attention.

Design Principles for Efficient and Stable Water Splitting Photoelectrocatalysts.

ConspectusPhotoelectrochemical water splitting is a promising avenue for sustainable production of hydrogen used in the chemical industry and hydrogen fuel cells. The basic components of most photoelectrochemical water splitting systems are semiconductor light absorbers coupled to electrocatalysts, which perform the desired chemical reactions. A critical challenge for the design of these systems is the lack of stability for the majority of desired semiconductors under operating water splitting conditions. One strategy to address this issue is to protect the semiconductor by covering it with a stabilizing insulator layer, creating a metal-insulator-semiconductor (MIS) architecture, which has demonstrated improved stability. In addition to enhanced stability, the insulator layer may significantly affect the electron and hole transfer, which governs the recombination rates. Furthermore, the insertion of an insulator layer leads to the introduction of additional insulator/electrocatalyst and insulator/semiconductor interfaces. These interfaces can impact the system's performance significantly, and they need to be carefully engineered to optimize the efficiencies of MIS systems. In this Account, we describe our recent progress in shedding light on the critical role of the insulator and the interfaces on the performance of MIS systems. We discuss our findings by focusing on the concrete example of planar n-type Si protected by a HfO2 insulator layer and coupled to a Ni or Ir electrocatalyst that performs the oxygen evolution reaction, one of the water splitting half-reactions. To improve our fundamental understanding of the insulator layer, we precisely control the HfO2 insulator thickness using atomic layer deposition (ALD), and we perform a series of rigorous electrochemical experiments coupled with theory and modeling. We demonstrate that by tuning the insulator thickness, we can control the flux and recombination of photogenerated electrons and holes to optimize the generated photovoltage. Despite optimizing the thickness, we find that the maximum generated photovoltage in MIS systems is often significantly lower than the upper performance limit, i.e., there are additional losses in the system that could not be addressed by optimizing the insulator thickness. We identify the sources of these losses and describe strategies to minimize them by a combination of improving the semiconductor light absorption, removing nonidealities associated with interfacial defects, and finding alternative insulators with improved charge carrier selectivity. Finally, we quantify the improvements that can be obtained by implementing these specific strategies. Our collective work outlines strategies to analyze MIS systems, identify the sources of efficiency losses, and optimize the design to approach the fundamental performance limits. These general approaches are broadly applicable to photoelectrochemical materials that utilize sunlight to produce value-added chemicals.

Chemical Requirement for Extracting Energetic Charge Carriers from Plasmonic Metal Nanoparticles to Perform Electron-Transfer Reactions.

Performing electron-transfer reactions on metal nanoparticles requires separation of charge carriers at the nanoparticle and their transfer to the reacting molecules. Inducing these reactions using light is challenging due to the exceedingly short lifetimes of energetic charge carriers formed in metal nanoparticles under light illumination. The results described here show that certain conditions must be met to drive these electron-transfer reactions on plasmonic nanoparticles. One critical requirement is that the process of electronic excitation takes place at the nanoparticle/molecule interface. This is accomplished by high plasmonic electric fields at the surface of plasmonic nanoparticles. Furthermore, it is also evident from our study that the electron (or hole)-donating capacity of the hole (or electron) scavengers needs to be high enough to allow for the extraction of holes (or electrons) from the nanoparticle/molecule complex, therefore completing the catalytic cycle. We discuss these findings through a case study of the conversion of methylene blue (MB) into a reduced MB ion radical on the surface of plasmonic Ag and Ag-Pt core-shell nanoparticles. To directly monitor the reduction reaction of MB on the nanoparticle surfaces, we have used time-dependent in situ surface-enhanced Raman scattering measurement, which also informs us about the underlying mechanistic details of plasmon-driven charge transfer.

Unearthing the factors governing site specific rates of electronic excitations in multicomponent plasmonic systems and catalysts.

We use experimental and computational studies of core-shell metal-semiconductor and metal-molecule systems to investigate the mechanism of energy flow and energetic charge carrier generation in multicomponent plasmonic systems. We demonstrate that the rates of plasmon decay through the formation of energetic charge carriers are governed by two factors: (1) the intensity of the local plasmon induced electric fields at a specific location in the multicomponent nanostructure, and (2) the availability of direct, momentum conserved electronic excitations in the material located in that specific location. We propose a unifying physical framework that describes the flow of energy in all multicomponent plasmonic systems and leads us towards molecular control of the energy flow and excited charge carrier generation in these systems.

Photochemical transformations on plasmonic metal nanoparticles.

The strong interaction of electromagnetic fields with plasmonic nanomaterials offers opportunities in various technologies that take advantage of photophysical processes amplified by this light-matter interaction. Recently, it has been shown that in addition to photophysical processes, optically excited plasmonic nanoparticles can also activate chemical transformations directly on their surfaces. This potentially offers a number of opportunities in the field of selective chemical synthesis. In this Review we summarize recent progress in the field of photochemical catalysis on plasmonic metallic nanostructures. We discuss the underlying physical mechanisms responsible for the observed chemical activity, and the issues that must be better understood to see progress in the field of plasmon-mediated photocatalysis.

Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111).

Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

Catalytic and photocatalytic transformations on metal nanoparticles with targeted geometric and plasmonic properties.

Heterogeneous catalysis by metals was among the first enabling technologies that extensively relied on nanoscience. The early intersections of catalysis and nanoscience focused on the synthesis of catalytic materials with high surface to volume ratio. These synthesis strategies mainly involved the impregnation of metal salts on high surface area supports. This would usually yield quasi-spherical nanoparticles capped by low-energy surface facets, typically with closely packed metal atoms. These high density areas often function as the catalytically active surface sites. Unfortunately, strategies to control the functioning surface facet (i.e., the geometry of active sites that performs catalytic turnover) are rare and represent a significant challenge in our ability to fine-tune and optimize the reactive surfaces. Through recent developments in colloidal chemistry, chemists have been able to synthesize metallic nanoparticles of both targeted size and desired shape. This has opened new possibilities for the design of heterogeneous catalytic materials, since metal nanoparticles of different shapes are terminated with different surface facets. By controlling the surface facet exposed to reactants, we can start affecting the chemical transformations taking place on the metal particles and changing the outcome of catalytic processes. Controlling the size and shape of metal nanoparticles also allows us to control the optical properties of these materials. For example, noble metals nanoparticles (Au, Ag, Cu) interact with UV-vis light through an excitation of localized surface plasmon resonance (LSPR), which is highly sensitive to the size and shape of the nanostructures. This excitation is accompanied by the creation of short-lived energetic electrons on the surface of the nanostructure. We showed recently that these energetic electrons could drive photocatalytic transformations on these nanostructures. The photocatalytic, electron-driven processes on metal nanoparticles represent a new family of chemical transformations exhibiting fundamentally different behavior compared with phonon-driven thermal processes, potentially allowing selective bond activation. In this Account, we discuss both the impact of the shape of metal nanoparticles on the outcome of heterogeneous catalytic reactions and the direct, electron-driven photocatalysis on plasmonic metal nanostructures of noble metals. These two phenomena are important examples of taking advantage of physical properties of metal materials that are controlled at nanoscales to affect chemical transformations.

Overcoming limitations in propane dehydrogenation by codesigning catalyst-membrane systems.

Propylene production through propane dehydrogenation (PDH) is endothermic, and high temperatures required to achieve acceptable propane conversions lead to low selectivity and severe carbon-induced deactivation of conventional catalysts. We developed a catalyst-membrane system that removes the hydrogen by-product and can thus achieve propane conversions that exceed equilibrium limits. In this codesigned system, a silica/alumina (SiO2/Al2O3) hollow-fiber hydrogen membrane was packed with a selective platinum-tin (Pt1Sn1/SiO2) PDH catalyst on the tube side with hydrogen diffusing from the tube to the shell side. We demonstrate that the catalyst-membrane system can achieve propane conversions >140% of the nominal equilibrium conversion with a propylene selectivity >98% without deactivation of the system components. We also show that by introducing oxygen on the shell side of the catalyst-membrane system, we can couple the endothermic PDH reaction on the tube side with exothermic hydrogen oxidation on the shell side. This coupling results in higher rates of hydrogen transport, leading to further enhancements in the propane conversion as well as desired thermoneutral system operation.

Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures.

The field of heterogeneous photocatalysis has almost exclusively focused on semiconductor photocatalysts. Herein, we show that plasmonic metallic nanostructures represent a new family of photocatalysts. We demonstrate that these photocatalysts exhibit fundamentally different behaviour compared with semiconductors. First, we show that photocatalytic reaction rates on excited plasmonic metallic nanostructures exhibit a super-linear power law dependence on light intensity (rate ∝ intensity(n), with n > 1), at significantly lower intensity than required for super-linear behaviour on extended metal surfaces. We also demonstrate that, in sharp contrast to semiconductor photocatalysts, photocatalytic quantum efficiencies on plasmonic metallic nanostructures increase with light intensity and operating temperature. These unique characteristics of plasmonic metallic nanostructures suggest that this new family of photocatalysts could prove useful for many heterogeneous catalytic processes that cannot be activated using conventional thermal processes on metals or photocatalytic processes on semiconductors.

Plasma-Induced Selective Propylene Epoxidation Using Water as the Oxygen Source.

Propylene oxide (PO) is a critical gateway chemical used in large-scale production of plastics and many other compounds. In addition, PO is also used in many smaller-scale applications that require lower PO concentrations and volumes. These include its usage as a fumigant and disinfectant for food, a sterilizer for medical equipment, as well as in producing modified food such as starch and alginate. While PO is currently mostly produced in a large-scale propylene epoxidation chemical process, due to its toxic nature and high transport and storage costs, there is a strong incentive to develop PO production strategies that are well-suited for smaller-scale on-site applications. In this contribution, we designed a plasma-liquid interaction (PLI) catalytic process that uses only water and C3H6 as reactants to form PO. We show that hydrogen peroxide (H2O2) generated in the interactions of water with plasma serves as a critical oxidizing agent that can epoxidize C3H6 over a titanium silicate-1 (TS-1) catalyst dispersed in a water solution with a carbon-based selectivity of more than 98%. As the activity of this plasma C3H6 epoxidation system is limited by the rate of H2O2 production, strategies to improve H2O2 production were also investigated.

Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy.

Recent years have seen a renewed interest in the harvesting and conversion of solar energy. Among various technologies, the direct conversion of solar to chemical energy using photocatalysts has received significant attention. Although heterogeneous photocatalysts are almost exclusively semiconductors, it has been demonstrated recently that plasmonic nanostructures of noble metals (mainly silver and gold) also show significant promise. Here we review recent progress in using plasmonic metallic nanostructures in the field of photocatalysis. We focus on plasmon-enhanced water splitting on composite photocatalysts containing semiconductor and plasmonic-metal building blocks, and recently reported plasmon-mediated photocatalytic reactions on plasmonic nanostructures of noble metals. We also discuss the areas where major advancements are needed to move the field of plasmon-mediated photocatalysis forward.

Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface.

A critical factor limiting the rates of photocatalytic reactions, including water splitting, on oxide semiconductors is the high rate of charge-carrier recombination. In this contribution, we demonstrate that this issue can be alleviated significantly by combining a semiconductor photocatalyst with tailored plasmonic-metal nanostructures. Plasmonic nanostructures support the formation of resonant surface plasmons in response to a photon flux, localizing electromagnetic energy close to their surfaces. We present evidence that the interaction of localized electric fields with the neighboring semiconductor allows for the selective formation of electron/hole (e(-)/h(+)) pairs in the near-surface region of the semiconductor. The advantage of the formation of e(-)/h(+) pairs near the semiconductor surface is that these charge carriers are readily separated from each other and easily migrate to the surface, where they can perform photocatalytic transformations.

High activity carbide supported catalysts for water gas shift.

Nanostructured carbides are refractory materials with high surface areas that could be used as alternatives to the oxide materials that are widely used as support materials for heterogeneous catalysts. Carbides are also catalytically active for a variety of reactions, offering additional opportunities to tune the overall performance of the catalyst. In this paper we describe the synthesis of molybdenum carbide supported platinum (Pt/Mo(2)C) catalysts and their rates for the water gas shift reaction. The synthesis method allowed interaction of the metal precursor with the native, unpassivated support. The resulting materials possessed very high WGS rates and atypical Pt particle morphologies. Under differential conditions, rates for these catalysts were higher than those for the most active oxide-supported Pt catalysts and a commercial Cu-Zn-Al catalyst. Experimental and computational results suggested that active sites on the Pt/Mo(2)C catalysts were located on the perimeter of the Pt particles and that strong interactions between Pt and the Mo(2)C surface gave rise to raft-like particles.

Stable and selective catalysts for propane dehydrogenation operating at thermodynamic limit.

Intentional ("on-purpose") propylene production through nonoxidative propane dehydrogenation (PDH) holds great promise for meeting the increasing global demand for propylene. For stable performance, traditional alumina-supported platinum-based catalysts require excess tin and feed dilution with hydrogen; however, this reduces per-pass propylene conversion and thus lowers catalyst productivity. We report that silica-supported platinum-tin (Pt1Sn1) nanoparticles (<2 nanometers in diameter) can operate as a PDH catalyst at thermodynamically limited conversion levels, with excellent stability and selectivity to propylene (>99%). Atomic mixing of Pt and Sn in the precursor is preserved upon reduction and during catalytic operation. The benign interaction of these nanoparticles with the silicon dioxide support does not lead to Pt-Sn segregation and formation of a tin oxide phase that can occur over traditional catalyst supports.

Communications: Exceptions to the d-band model of chemisorption on metal surfaces: The dominant role of repulsion between adsorbate states and metal d-states.

We show that there is a family of adsorbate-substrate systems that do not follow the trends in adsorption energies predicted by the d-band model. A physically transparent model is used to analyze this phenomenon. We found that these adsorbate-substrate pairs are characterized by the repulsive interaction of the substrate d-band with the renormalized adsorbate states. The exceptions to the d-band model are mainly associated with the adsorbates having almost completely filled valence shell, and the substrates with nearly fully occupied d-band, e.g., OH, F, or Cl adsorption on metals and alloys characterized by d(9) or d(10) substrate surface atoms.

Communications: Developing relationships between the local chemical reactivity of alloy catalysts and physical characteristics of constituent metal elements.

We have used X-ray absorption spectroscopy and quantum chemical density functional theory calculations to identify critical features in the electronic structure of different sites in alloys that govern the local chemical reactivity. The measurements led to a simple model relating local geometric features of a site in an alloy to its electronic structure and chemical reactivity. The central feature of the model is that the formation of alloys does not lead to significant charge transfer between the constituent metal elements in the alloys, and that the local electronic structure and chemical reactivity can be predicted based on physical characteristics of constituent metal elements in their unalloyed form.