Selective Oxidation Using In Situ-Generated Hydrogen Peroxide.

ConspectusHydrogen peroxide (H2O2) for industrial applications is manufactured through an indirect process that relies on the sequential reduction and reoxidation of quinone carriers. While highly effective, production is typically centralized and entails numerous energy-intensive concentration steps. Furthermore, the overhydrogenation of the quinone necessitates periodic replacement, leading to incomplete atom efficiency. These factors, in addition to the presence of propriety stabilizing agents and concerns associated with their separation from product streams, have driven interest in alternative technologies for chemical upgrading. The decoupling of oxidative transformations from commercially synthesized H2O2 may offer significant economic savings and a reduction in greenhouse gas emissions for several industrially relevant processes. Indeed, the production and utilization of the oxidant in situ, from the elements, would represent a positive step toward a more sustainable chemical synthesis sector, offering the potential for total atom efficiency, while avoiding the drawbacks associated with current industrial routes, which are inherently linked to commercial H2O2 production. Such interest is perhaps now more pertinent than ever given the rapidly improving viability of green hydrogen production.The application of in situ-generated H2O2 has been a long-standing goal in feedstock valorization, with perhaps the most significant interest placed on propylene epoxidation. Until very recently a viable in situ alternative to current industrial oxidative processes has been lacking, with prior approaches typically hindered by low rates of conversion or poor selectivity toward desired products, often resulting from competitive hydrogenation reactions. Based on over 20 years of research, which has led to the development of catalysts for the direct synthesis of H2O2 that offer high synthesis rates and >99% H2 utilization, we have recently turned our attention to a range of oxidative transformations where H2O2 is generated and utilized in situ. Indeed, we have recently demonstrated that it is possible to rival state-of-the-art industrial processes through in situ H2O2 synthesis, establishing the potential for significant process intensification and considerable decarbonization of the chemical synthesis sector.We have further established the potential of an in situ route to both bulk and fine chemical synthesis through a chemo-catalytic/enzymatic one-pot approach, where H2O2 is synthesized over heterogeneous surfaces and subsequently utilized by a class of unspecific peroxygenase enzymes for C-H bond functionalization. Strikingly, through careful control of the chemo-catalyst, it is possible to ensure that competitive, nonenzymatic pathways are inhibited while also avoiding the regiospecific and selectivity concerns associated with current energy-intensive industrial processes, with further cost savings associated with the operation of the chemo-enzymatic approach at near-ambient temperatures and pressures. Beyond traditional applications of chemo-catalysis, the efficacy of in situ-generated H2O2 (and associated oxygen-based radical species) for the remediation of environmental pollutants has also been a major interest of our laboratory, with such technology offering considerable improvements over conventional disinfection processes.We hope that this Account, which highlights the key contributions of our laboratory to the field over recent years, demonstrates the chemistries that may be unlocked and improved upon via in situ H2O2 synthesis and it inspires broader interest from the scientific community.

Electrochemical Polarization of Disparate Catalytic Sites Drives Thermochemical Rate Enhancement.

Supported bimetallic catalysts commonly exhibit higher rates of reaction compared to their monometallic counterparts, but the origin of these enhancements is often poorly defined. The recent discovery that cooperative redox enhancement effects in Au-Pd systems promote bimetallic catalysis in thermochemical oxidation is an important development in this field. This effect aligns two important research fields, thermo- and electrocatalysis, but questions relating to the generality and origin of the effect remain. Here, we demonstrate that these effects can be observed in reactions over a range of bimetal combinations and reveal the origin using a combination of electrochemical and material characterization. We disclose that the observed activity enhancement in thermochemical systems is a result of the electrochemical polarization of two disparate catalytic sites. This forms an alternative operating potential for a given bimetallic system that increases the driving force of each of the composite half reactions in oxidative dehydrogenation. We therefore uncover the physicochemical descriptors that dictate whether these enhancement effects will be exhibited by a particular combination of supported metal catalysts and determine the magnitude of the effect.

Selective Oxidation of Methane to Methanol via In Situ H2O2 Synthesis.

The selective oxidation of methane to methanol, using H2O2 generated in situ from the elements, has been investigated using a series of ZSM-5-supported AuPd catalysts of varying elemental composition, prepared via a deposition precipitation protocol. The alloying of Pd with Au was found to offer significantly improved efficacy, compared to that observed over monometallic analogues. Complementary studies into catalytic performance toward the direct synthesis and subsequent degradation of H2O2, under idealized conditions, indicate that methane oxidation efficacy is not directly related to H2O2 production rates, and it is considered that the known ability of Au to promote the release of reactive oxygen species is the underlying cause for the improved performance of the bimetallic catalysts.

Recognizing the best catalyst for a reaction.

Heterogeneous catalysis is immensely important, providing access to materials essential for the well-being of society, and improved catalysts are continuously required. New catalysts are frequently tested under different conditions making it difficult to determine the best catalyst. Here we describe a general approach to identify the best catalyst using a data set based on all reactions under kinetic control to calculate a set of key performance indicators (KPIs). These KPIs are normalized to take into account the variation in reaction conditions. Plots of the normalized KPIs are then used to demonstrate the best catalyst using two case studies: (i) acetylene hydrochlorination, a reaction of current interest for vinyl chloride manufacture, and (ii) the selective oxidation of methane to methanol using O2 in water, a reaction that has attracted very recent attention in the academic literature.

Lithium-Directed Transformation of Amorphous Iridium (Oxy)hydroxides To Produce Active Water Oxidation Catalysts.

The oxygen evolution reaction (OER) is crucial to future energy systems based on water electrolysis. Iridium oxides are promising catalysts due to their resistance to corrosion under acidic and oxidizing conditions. Highly active iridium (oxy)hydroxides prepared using alkali metal bases transform into low activity rutile IrO2 at elevated temperatures (>350 °C) during catalyst/electrode preparation. Depending on the residual amount of alkali metals, we now show that this transformation can result in either rutile IrO2 or nano-crystalline Li-intercalated IrOx. While the transition to rutile results in poor activity, the Li-intercalated IrOx has comparative activity and improved stability when compared to the highly active amorphous material despite being treated at 500 °C. This highly active nanocrystalline form of lithium iridate could be more resistant to industrial procedures to produce PEM membranes and provide a route to stabilize the high populations of redox active sites of amorphous iridium (oxy)hydroxides.

Insights into the Effect of Metal Ratio on Cooperative Redox Enhancement Effects over Au- and Pd-Mediated Alcohol Oxidation.

The aerobic oxidation of alcohols and aldehydes over supported heterogeneous catalysts can be considered as comprising two complementary and linked processes: dehydrogenation and oxygen reduction. Significant rate enhancements can be observed when these processes are catalyzed by independent active sites, coupled by electron transport between the two catalysts. This effect, termed cooperative redox enhancement (CORE), could significantly influence how researchers approach catalyst design, but a greater understanding of the factors which influence it is required. Herein, we demonstrate that the Au/Pd ratio used in physical mixtures of monometallic catalysts and phase-separated Au and Pd bimetallic catalysts dramatically influences the degree to which CORE effects can promote alcohol oxidation. Perhaps more interestingly, the roles of Au and Pd in this coupled system are determined to be interchangeable. Preliminarily, we hypothesize that this is attributed to the relative rates of the coupled reactions and demonstrate how physical properties can influence this. This deeper understanding of the factors which influence CORE is an important development in bimetallic catalysis.

Approaching Theoretical Performances of Electrocatalytic Hydrogen Peroxide Generation by Cobalt-Nitrogen Moieties.

Electrocatalytic oxygen reduction reaction (ORR) has been intensively studied for environmentally benign applications. However, insufficient understanding of ORR 2 e- -pathway mechanism at the atomic level inhibits rational design of catalysts with both high activity and selectivity, causing concerns including catalyst degradation due to Fenton reaction or poor efficiency of H2 O2 electrosynthesis. Herein we show that the generally accepted ORR electrocatalyst design based on a Sabatier volcano plot argument optimises activity but is unable to account for the 2 e- -pathway selectivity. Through electrochemical and operando spectroscopic studies on a series of CoNx /carbon nanotube hybrids, a construction-driven approach based on an extended "dynamic active site saturation" model that aims to create the maximum number of 2 e- ORR sites by directing the secondary ORR electron transfer towards the 2 e- intermediate is proven to be attainable by manipulating O2 hydrogenation kinetics.

The effect of dissolved chlorides on the photocatalytic degradation properties of titania in wastewater treatment.

We investigate the effect of chlorides on the photocatalytic degradation of phenol by titania polymorphs (anatase and rutile). We demonstrate how solubilised chlorides can affect the hydroxyl radical formation on both polymorphs with an overall effect on their photodegradative activity. Initially, the photocatalytic activity of anatase and rutile for phenol degradation is investigated in both standard water and brines. With anatase, a significant reduction of the phenol conversion rate is observed (from a pseudo-first-order rate constant k = 5.3 × 10-3 min-1 to k = 3.5 × 10-3 min-1). In contrast, the presence of solubilised chlorides results in enhancement of rutile activity under the same reaction conditions (from 2.3 × 10-3 min-1 to 4.8 × 10-3 min-1). Periodic DFT methods are extensively employed and we show that after the generation of charge separation in the modelled titania systems, adsorbed chlorides are the preferential site for partial hole localisation, although small energy differences are computed between partially localised hole densities over adsorbed chloride or hydroxyl. Moreover, chlorides can reduce or inhibit the ability of r-TiO2 (110) and a-TiO2 (101) systems to localise polarons in the slab structure. These results indicate that both mechanisms - hole scavenging and the inhibition of hole localisation - can be the origin of the effect of chlorides on photocatalytic activity of both titania polymorphs. These results provide fundamental insight into the photocatalytic properties of titania polymorphs and elucidate the effect of adsorbed anions over radical formation and oxidative decomposition of organic pollutants.

Uncovering Structure-Activity Relationships in Pt/CeO2 Catalysts for Hydrogen-Borrowing Amination.

The hydrogen-borrowing amination of alcohols is a promising route to produce amines. In this study, experimental parameters involved in the preparation of Pt/CeO2 catalysts were varied to assess how physicochemical properties influence their performance in such reactions. An amination reaction between cyclopentanol and cyclopentylamine was used as the model reaction for this study. The Pt precursor used in the catalyst synthesis and the properties of the CeO2 support were both found to strongly influence catalytic performance. Aberration corrected scanning transmission electron microscopy revealed that the most active catalyst comprised linearly structured Pt species. The formation of these features, a function result of epitaxial Pt deposition along the CeO2 [100] plane, appeared to be dependent on the properties of the CeO2 support and the Pt precursor used. Density functional theory calculations subsequently confirmed that these sites were more effective for cyclopentanol dehydrogenation-considered to be the rate-determining step of the process-than Pt clusters and nanoparticles. This study provides insights into the desirable catalytic properties required for hydrogen-borrowing amination but has relevance to other related fields. We consider that this study will provide a foundation for further study in this atom-efficient area of chemistry.

Methane Oxidation to Methanol.

The direct transformation of methane to methanol remains a significant challenge for operation at a larger scale. Central to this challenge is the low reactivity of methane at conditions that can facilitate product recovery. This review discusses the issue through examination of several promising routes to methanol and an evaluation of performance targets that are required to develop the process at scale. We explore the methods currently used, the emergence of active heterogeneous catalysts and their design and reaction mechanisms and provide a critical perspective on future operation. Initial experiments are discussed where identification of gas phase radical chemistry limited further development by this approach. Subsequently, a new class of catalytic materials based on natural systems such as iron or copper containing zeolites were explored at milder conditions. The key issues of these technologies are low methane conversion and often significant overoxidation of products. Despite this, interest remains high in this reaction and the wider appeal of an effective route to key products from C-H activation, particularly with the need to transition to net carbon zero with new routes from renewable methane sources is exciting.

Methanol synthesis from CO2 and H2 using supported Pd alloy catalysts.

A number of Pd based materials have been synthesised and evaluated as catalysts for the conversion of carbon dioxide and hydrogen to methanol, a useful platform chemical and hydrogen storage molecule. Monometallic Pd catalysts show poor methanol selectivity, but this is improved through the formation of Pd alloys, with both PdZn and PdGa alloys showing greatly enhanced methanol productivity compared with monometallic Pd/Al2O3 and Pd/TiO2 catalysts. Catalyst characterisation shows that the 1 : 1 ß-PdZn alloy is present in all Zn containing post-reaction samples, including PdZn/Ga2O3, with the Pd2Ga alloy formed for the Pd/Ga2O3 sample. The heat of mixing was calculated for a variety of alloy compositions with high values determined for both PdZn and Pd2Ga alloys, at ca. -0.6 eV per atom and ca. -0.8 eV per atom, respectively. However, ZnO is more readily reduced than Ga2O3, providing a possible explanation for the preferential formation of the PdZn alloy, rather than PdGa, when in the presence of Ga2O3.

Advancing Critical Chemical Processes for a Sustainable Future: Challenges for Industry and the Max Planck-Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT).

Catalysis is involved in around 85 % of manufacturing industry and contributes an estimated 25 % to the global domestic product, with the majority of the processes relying on heterogeneous catalysis. Despite the importance in different global segments, the fundamental understanding of heterogeneously catalysed processes lags substantially behind that achieved in other fields. The newly established Max Planck-Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT) targets innovative concepts that could contribute to the scientific developments needed in the research field to achieve net zero greenhouse gas emissions in the chemical industries. This Viewpoint Article presents some of our research activities and visions on the current and future challenges of heterogeneous catalysis regarding green industry and the circular economy by focusing explicitly on critical processes. Namely, hydrogen production, ammonia synthesis, and carbon dioxide reduction, along with new aspects of acetylene chemistry.

Reversible Growth of Gold Nanoparticles in the Low-Temperature Water-Gas Shift Reaction.

Supported gold nanoparticles are widely studied catalysts and are among the most active known for the low-temperature water-gas shift reaction, which is essential in fuel and energy applications, but their practical application has been limited by their poor thermal stability. The catalysts deactivate on-stream via the growth of small Au nanoparticles. Using operando X-ray absorption and in situ scanning transmission electron microscopy, we report direct evidence that this process can be reversed by carrying out a facile oxidative treatment, which redisperses the gold nanoparticles and restores catalytic activity. The use of in situ methods reveals the complex dynamics of supported gold nanoparticles under reaction conditions and demonstrates that gold catalysts can be easily regenerated, expanding their scope for practical application.

N-Heterocyclic Carbene Modified Palladium Catalysts for the Direct Synthesis of Hydrogen Peroxide.

Heterogeneous palladium catalysts modified by N-heterocyclic carbenes (NHCs) are shown to be highly effective toward the direct synthesis of hydrogen peroxide (H2O2), in the absence of the promoters which are typically required to enhance both activity and selectivity. Catalytic evaluation in a batch regime demonstrated that through careful selection of the N-substituent of the NHC it is possible to greatly enhance catalytic performance when compared to the unmodified analogue and reach concentrations of H2O2 rivaling that obtained by state-of-the-art catalysts. The enhanced performance of the modified catalyst, which is retained upon reuse, is attributed to the ability of the NHC to electronically modify Pd speciation.

The Critical Role of ßPdZn Alloy in Pd/ZnO Catalysts for the Hydrogenation of Carbon Dioxide to Methanol.

The rise in atmospheric CO2 concentration and the concomitant rise in global surface temperature have prompted massive research effort in designing catalytic routes to utilize CO2 as a feedstock. Prime among these is the hydrogenation of CO2 to make methanol, which is a key commodity chemical intermediate, a hydrogen storage molecule, and a possible future fuel for transport sectors that cannot be electrified. Pd/ZnO has been identified as an effective candidate as a catalyst for this reaction, yet there has been no attempt to gain a fundamental understanding of how this catalyst works and more importantly to establish specific design criteria for CO2 hydrogenation catalysts. Here, we show that Pd/ZnO catalysts have the same metal particle composition, irrespective of the different synthesis procedures and types of ZnO used here. We demonstrate that all of these Pd/ZnO catalysts exhibit the same activity trend. In all cases, the ß-PdZn 1:1 alloy is produced and dictates the catalysis. This conclusion is further supported by the relationship between conversion and selectivity and their small variation with ZnO surface area in the range 6-80 m2g-1. Without alloying with Zn, Pd is a reverse water-gas shift catalyst and when supported on alumina and silica is much less active for CO2 conversion to methanol than on ZnO. Our approach is applicable to the discovery and design of improved catalysts for CO2 hydrogenation and will aid future catalyst discovery.