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Propane dehydrogenation (PDH), an important process for propylene synthesis, relies on expensive noble metals or highly toxic oxides as catalysts. In a recent publication in Science, Gong and coworkers report a breakthrough discovery for PDH by introducing a sustainable catalyst composed of titanium oxide overlayers encapsulating nickel nanoparticles, termed Ni@TiOx. This innovative catalyst showcases exceptional performance in PDH, exhibiting high propylene selectivity and stability under industrially relevant conditions. The study elucidates the role of defective TiOx overlayers and the electronic promotional effect of subsurface Ni in enhancing catalytic activity, translating a traditional model catalyst system into a sustainable industrial catalyst for low-carbon energy and the chemical industry., (© 2024 Wiley‐VCH GmbH.)

Alkoxycarbonylation reactions are common in the chemical industry, yet process sustainability is limited by the inefficient utilization of CO. In this study, we address this issue and demonstrate that significant improvements can be achieved by adopting a heterogeneously catalyzed process, using a Ru/NbO x catalyst. The Ru/NbO x catalyst enables the direct synthesis of methyl propionate, a key industrial commodity, with over 98% selectivity from CO, ethylene and methanol, without any ligands or acid/base promoters. Under ambient CO pressure, a high CO utilization efficiency (336 mmol ester mol CO -1 h -1 ) is achieved. Mechanistic investigations reveal that CO undergoes a methoxycarbonyl (COOCH 3 ) intermediate pathway, attacking the terminal carbon atom of alkene and yielding linear esters. The origins of prevailing linear regioselectivity in esters are revealed. The infrared spectroscopic feature of the key COOCH 3 species is observed at 1750 cm -1 (C=O vibration) both experimentally and computationally. The broad substrate applicability of Ru/NbO x catalyst for ester production is demonstrated. This process offers a sustainable and efficient approach with high CO utilization and atom economy for the synthesis of esters., (© 2024. The Author(s).)

Taste and odor are crucial factors in evaluating the quality of drinking water for consumers. Geosmin is an example of a pollutant commonly found in potable water responsible for earthy and musty taste, and odor even at low concentrations. We have investigated the use of a hybrid two-step adsorption-mineralization process for low-level volatile organic compounds removal from potable water using dielectric barrier discharge over common metal oxides (MO). The system proposed is a proof of principle with tert -butanol (TBA) used as a model compound for geosmin removal/degradation during wastewater treatment when combined with an appropriate metal oxide adsorbent. Initial assessments of the adsorption properties of titania by density functional theory (DFT) calculations and experimental tests indicated that the adsorption of geosmin and TBA with water present results in only weak interactions between the sorbate and the metal oxide. In contrast, the DFT results show that alumina could be a suitable adsorbent for these tertiary alcohols and were reinforced by experimental studies. We find that while there is a competitive effect between the water and TBA adsorption from gaseous/liquid feed, the VOC can be removed, and the alumina will be regenerated by the reactive oxygen species (ROS) produced by a dielectric barrier discharge (DBD). The use of alumina in conjunction with NTP leads to efficient degradation of the adsorbate and the formation of oxygenated intermediates (formates, carbonates, and carboxylate-type species), which could then be mineralized for the regeneration of the adsorbent. A reaction mechanism has been proposed based on the in-situ infrared measurements and DFT calculations, while the removal of TBA with conventional heating is indicative of a gradual desorption process as a function of temperature rather than the destruction of the adsorbate. Furthermore, steady performance was observed after several adsorption-regeneration cycles, indicating no alteration of the adsorption properties of alumina during the NTP treatment and demonstrating the potential of the approach to be applied in the treatment of high throughput of water, without the challenges faced by the biocatalysts or formation of toxic byproducts., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

ConspectusHydrogen peroxide (H 2 O 2 ) 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 H 2 O 2 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 H 2 O 2 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 H 2 O 2 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 H 2 O 2 that offer high synthesis rates and >99% H 2 utilization, we have recently turned our attention to a range of oxidative transformations where H 2 O 2 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 H 2 O 2 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 H 2 O 2 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 H 2 O 2 (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 H 2 O 2 synthesis and it inspires broader interest from the scientific community.

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., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

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 H 2 O 2 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 CoN x /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 O 2 hydrogenation kinetics., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

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.

The selective oxidation of methane to methanol, using H 2 O 2 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 H 2 O 2 , under idealized conditions, indicate that methane oxidation efficacy is not directly related to H 2 O 2 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., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

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 O 2 in water, a reaction that has attracted very recent attention in the academic literature., (© 2023. Springer Nature Limited.)

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 IrO 2 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 IrO 2 or nano-crystalline Li-intercalated IrO x . While the transition to rutile results in poor activity, the Li-intercalated IrO x 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.

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., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

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-TiO 2 (110) and a-TiO 2 (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.

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/Al 2 O 3 and Pd/TiO 2 catalysts. Catalyst characterisation shows that the 1 : 1 β-PdZn alloy is present in all Zn containing post-reaction samples, including PdZn/Ga 2 O 3 , with the Pd 2 Ga alloy formed for the Pd/Ga 2 O 3 sample. The heat of mixing was calculated for a variety of alloy compositions with high values determined for both PdZn and Pd 2 Ga alloys, at ca. -0.6 eV per atom and ca. -0.8 eV per atom, respectively. However, ZnO is more readily reduced than Ga 2 O 3 , providing a possible explanation for the preferential formation of the PdZn alloy, rather than PdGa, when in the presence of Ga 2 O 3 .

The hydrogen-borrowing amination of alcohols is a promising route to produce amines. In this study, experimental parameters involved in the preparation of Pt/CeO 2 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 CeO 2 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 CeO 2 [100] plane, appeared to be dependent on the properties of the CeO 2 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., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

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., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

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.

Heterogeneous palladium catalysts modified by N-heterocyclic carbenes (NHCs) are shown to be highly effective toward the direct synthesis of hydrogen peroxide (H 2 O 2 ), 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 H 2 O 2 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 rise in atmospheric CO 2 concentration and the concomitant rise in global surface temperature have prompted massive research effort in designing catalytic routes to utilize CO 2 as a feedstock. Prime among these is the hydrogenation of CO 2 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 CO 2 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 β-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 m 2 g -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 CO 2 conversion to methanol than on ZnO. Our approach is applicable to the discovery and design of improved catalysts for CO 2 hydrogenation and will aid future catalyst discovery., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The ammoximation of cyclohexanone using preformed hydrogen peroxide (H 2 O 2 ) is currently applied commercially to produce cyclohexanone oxime, an important feedstock in nylon-6 production. We demonstrate that by using supported gold-palladium (AuPd) alloyed nanoparticles in conjunction with a titanium silicate-1 (TS-1) catalyst, H 2 O 2 can be generated in situ as needed, producing cyclohexanone oxime with >95% selectivity, comparable to the current industrial route. The ammoximation of several additional simple ketones is also demonstrated. Our approach eliminates the need to transport and store highly concentrated, stabilized H 2 O 2 , potentially achieving substantial environmental and economic savings. This approach could form the basis of an alternative route to numerous chemical transformations that are currently dependent on a combination of preformed H 2 O 2 and TS-1, while allowing for considerable process intensification.

The development and application of trimetallic nanoparticles continues to accelerate rapidly as a result of advances in materials design, synthetic control, and reaction characterization. Following the technological successes of multicomponent materials in automotive exhausts and photovoltaics, synergistic effects are now accessible through the careful preparation of multielement particles, presenting exciting opportunities in the field of catalysis. In this review, we explore the methods currently used in the design, synthesis, analysis, and application of trimetallic nanoparticles across both the experimental and computational realms and provide a critical perspective on the emergent field of trimetallic nanocatalysts. Trimetallic nanoparticles are typically supported on high-surface-area metal oxides for catalytic applications, synthesized via preparative conditions that are comparable to those applied for mono- and bimetallic nanoparticles. However, controlled elemental segregation and subsequent characterization remain challenging because of the heterogeneous nature of the systems. The multielement composition exhibits beneficial synergy for important oxidation, dehydrogenation, and hydrogenation reactions; in some cases, this is realized through higher selectivity, while activity improvements are also observed. However, challenges related to identifying and harnessing influential characteristics for maximum productivity remain. Computation provides support for the experimental endeavors, for example in electrocatalysis, and a clear need is identified for the marriage of simulation, with respect to both combinatorial element screening and optimal reaction design, to experiment in order to maximize productivity from this nascent field. Clear challenges remain with respect to identifying, making, and applying trimetallic catalysts efficiently, but the foundations are now visible, and the outlook is strong for this exciting chemical field.

In oxidation reactions catalysed by supported metal nanoparticles with oxygen as the terminal oxidant, the rate of the oxygen reduction can be a limiting factor. This is exemplified by the oxidative dehydrogenation of alcohols, an important class of reactions with modern commercial applications 1-3 . Supported gold nanoparticles are highly active for the dehydrogenation of the alcohol to an aldehyde 4 but are less effective for oxygen reduction 5,6 . By contrast, supported palladium nanoparticles offer high efficacy for oxygen reduction 5,6 . This imbalance can be overcome by alloying gold with palladium, which gives enhanced activity to both reactions 7,8,9 ; however, the electrochemical potential of the alloy is a compromise between that of the two metals, meaning that although the oxygen reduction can be improved in the alloy, the dehydrogenation activity is often limited. Here we show that by separating the gold and palladium components in bimetallic carbon-supported catalysts, we can almost double the reaction rate compared with that achieved with the corresponding alloy catalyst. We demonstrate this using physical mixtures of carbon-supported monometallic gold and palladium catalysts and a bimetallic catalyst comprising separated gold and palladium regions. Furthermore, we demonstrate electrochemically that this enhancement is attributable to the coupling of separate redox processes occurring at isolated gold and palladium sites. The discovery of this catalytic effect-a cooperative redox enhancement-offers an approach to the design of multicomponent heterogeneous catalysts., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Selective oxidation of higher alcohols using heterogeneous catalysts is an important reaction in the synthesis of fine chemicals with added value. Though the process for primary alcohol oxidation is industrially established, there is still a lack of fundamental understanding considering the complexity of the catalysts and their dynamics under reaction conditions, especially when higher alcohols and liquid-phase reaction media are involved. Additionally, new materials should be developed offering higher activity, selectivity, and stability. This can be achieved by unraveling the structure-performance correlations of these catalysts under reaction conditions. In this regard, researchers are encouraged to develop more advanced characterization techniques to address the complex interplay between the solid surface, the dissolved reactants, and the solvent. In this mini-review, we report some of the most important approaches taken in the field and give a perspective on how to tackle the complex challenges for different approaches in alcohol oxidation while providing insight into the remaining challenges., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The combination of a methanol synthesis catalyst and a solid acid catalyst opens the possibility to obtain olefins or paraffins directly from CO2 and H2 in one step. In this work several PdZn/TiO2-ZSM-5 hybrid catalysts were employed under CO2 hydrogenation conditions (240-360 °C, 20 bar, CO2/N2/H2 = 1 : 1 : 3) for the synthesis of CH3OH, consecutive dehydration to dimethyl ether and further oxygenate conversion to hydrocarbons. No significant changes after 36 h reaction on the methanol synthesis catalyst (PdZn/TiO2) were observed by XRD, XAS or XPS. No olefins were observed, indicating that light olefins undergo further hydrogenation under the reaction conditions, yielding the corresponding alkanes. Increasing the aluminium sites in the zeolites (Si : Al ratio 80 : 1, 50 : 1 and 23 : 1) led to a higher concentration of mild Brønsted acid sites, promoting hydrocarbon chain growth.

Methane represents one of the most abundant carbon sources for fuel or chemical production. However, remote geographical locations and high transportation costs result in a substantial proportion being flared at the source. The selective oxidation of methane to methanol remains a grand challenge for catalytic chemistry due to the large energy barrier for the initial C-H activation and prevention of overoxidation to CO 2 . Indirect methods such as steam reforming produce CO and H 2 chemical building blocks, but they consume large amounts of energy over multistage processes. This makes the development of the low-temperature selective oxidation of methane to methanol highly desirable and explains why it has remained an active area of research over the last 50 years.The thermodynamically favorable oxidation of methane to methanol would ideally use only molecular oxygen. Nature effects this transformation with the enzyme methane monooxygenase (MMO) in aqueous solution at ambient temperature with the addition of 2 equiv of a reducing cofactor. MMO active sites are Fe and Cu oxoclusters, and the incorporation of these metals into zeolitic frameworks can result in biomimetic activity. Most approaches to methane oxidation using metal-doped zeolites use high temperature with oxygen or N 2 O; however, demonstrations of catalytic cycles without catalyst regeneration cycles are limited. Over the last 10 years, we have developed Fe-Cu-ZSM-5 materials for the selective oxidation of methane to methanol under aqueous conditions at 50 °C using H 2 O 2 as an oxidant (effectively O 2 + 2 reducing equiv), which compete with MMO in terms of activity. To date, these materials are among the most active and selective catalysts for methane oxidation under this mild condition, but industrially, H 2 O 2 is an expensive oxidant to use in the production of methanol.This observation of activity under mild conditions led to new approaches to utilize O 2 as the oxidant. Supported precious metal nanoparticles have been shown to be active for a range of C-H activation reactions using O 2 and H 2 O 2 , but the rapid decomposition of H 2 O 2 over metal surfaces limits efficiency. We identified that this decomposition could be minimized by removing the support material and carrying out the reaction with colloidal AuPd nanoparticles. The efficiency of methanol production with H 2 O 2 consumption was increased by 4 orders of magnitude, and crucially it was demonstrated for the first time that molecular O 2 could be incorporated into the methanol produced with 91% selectivity. The understanding gained from these two approaches provides valuable insight into possible new routes to selective methane oxidation which will be presented here in the context of our own research in this area.

Heterogeneous catalysis lies at the heart of the chemical and fuel manufacturing industries and hence is a cornerstone of many economies. Many of the commercially operated heterogeneous catalysts have remained basically unchanged for decades, undergoing small but important optimisation of their formulations. Yet we all acknowledge that there is a continuous drive towards improved catalysts or designing new ones. At the heart of these studies has been the need to gain an improved understanding of the reaction mechanism for these important reactions since this can unlock new ways to improve catalyst design and, of course, the ultimate aim is to design catalysts based on the detailed understanding of the reaction mechanism. These advanced studies have been aided in the last decade by two key factors, namely: (a) access to advanced characterisation techniques based on synchrotron methods and aberration-corrected microscopy that can probe the nature of the active site, and (b) the application of high-level computational methods to understand how the reactants and products interact at the active site. In this paper this theme will be explored using two examples to bring out the complexity in gaining an understanding of a reaction mechanism. Using the zeolite H-ZSM-5 as an example of a single site catalyst, the mechanism of the conversion of methanol to the first hydrocarbon carbon-carbon bond will be discussed. In this section the use of model reactants and reaction probes will be used to try to differentiate between different mechanistic proposals. The second example explores the use of gold catalysts for CO oxidation and acetylene hydrochlorination. In both these examples the importance of advanced characterisation and theory will be highlighted.

Enzyme-mediated damage repair or mitigation, while common for nucleic acids, is rare for proteins. Examples of protein damage are elimination of phosphorylated Ser/Thr to dehydroalanine/dehydrobutyrine (Dha/Dhb) in pathogenesis and aging. Bacterial LanC enzymes use Dha/Dhb to form carbon-sulfur linkages in antimicrobial peptides, but the functions of eukaryotic LanC-like (LanCL) counterparts are unknown. We show that LanCLs catalyze the addition of glutathione to Dha/Dhb in proteins, driving irreversible C-glutathionylation. Chemo-enzymatic methods were developed to site-selectively incorporate Dha/Dhb at phospho-regulated sites in kinases. In human MAPK-MEK1, such "elimination damage" generated aberrantly activated kinases, which were deactivated by LanCL-mediated C-glutathionylation. Surveys of endogenous proteins bearing damage from elimination (the eliminylome) also suggest it is a source of electrophilic reactivity. LanCLs thus remove these reactive electrophiles and their potentially dysregulatory effects from the proteome. As knockout of LanCL in mice can result in premature death, repair of this kind of protein damage appears important physiologically., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The production of methanol from glycerol over a basic oxide, such as MgO, using high reaction temperatures (320 °C) is a promising new approach to improving atom efficiency in the production of biofuels. The mechanism of this reaction involves the homolytic cleavage of the C 3 feedstock, or its dehydration product hydroxyacetone, to produce a hydroxymethyl radical species which can then abstract an H atom from other species. Obtaining a detailed reaction mechanism for this type of chemistry is difficult due to the large number of products present when the system is operated at high conversions. In this contribution we show how DFT based modelling studies can provide new insights into likely reaction pathways, in particular the source of H atoms for the final step of converting hydroxymethyl radicals to methanol. We show that water is unlikely to be important in this stage of the process, C-H bonds of C 2 and C 3 species can give an energetically favourable pathway and that the disproportionation of hydroxymethyl radicals to methanol and formaldehyde produces a very favourable route. Experimental analysis of reaction products confirms the presence of formaldehyde. The calculations presented in this work also provide new insight into the role of the catalyst surface in the reaction showing that the base sites of the MgO(100) are able to deprotonate hydroxymethyl radicals but not methanol itself. In carrying out the calculations we also show how periodic DFT and QM/MM approaches can be used together to obtain a rounded picture of molecular adsorption to surfaces and homolytic bond cleavage which are both central to the reactions studied.

Glycerol solutions were vaporized and reacted over ceria catalysts with different morphologies to investigate the relationship of product distribution to the surface facets exposed, particularly, the yield of bio-renewable methanol. Ceria was prepared with cubic, rodlike, and polyhedral morphologies via hydrothermal synthesis by altering the concentration of the precipitating agent or synthesis temperature. Glycerol conversion was found to be low over the ceria with a cubic morphology, and this was ascribed to both a low surface area and relatively high acidity. Density functional theory calculations also showed that the (100) surface is likely to be hydroxylated under reaction conditions which could limit the availability of basic sites. Methanol space-time-yields over the polyhedral ceria samples were more than four times that for the cubic material at 400 °C, where 201 g of methanol was produced per hour per kilogram of the catalyst. Under comparable glycerol conversions, we show that the rodlike and polyhedral catalysts produce a major intermediate to methanol, hydroxyacetone (HA), with a selectivity of ca. 45%, but that over the cubic sample, this was found to be 15%. This equates to a 13-fold increase in the space-time-yield of HA over the polyhedral samples compared to the cubes at 320 °C. The implications of this difference are discussed with respect to the reaction mechanism, suggesting that a different mechanism dominates over the cubic catalysts to that for rodlike and polyhedral catalysts. The strong association between exposed surface facets of ceria to high methanol yields is an important consideration for future catalyst design in this area., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The formation of highly active and stable acetylene hydrochlorination catalysts is of great industrial importance. The successful replacement of the highly toxic mercuric chloride catalyst with gold has led to a flurry of research in this area. One key aspect, which led to the commercialization of the gold catalyst is the use of thiosulphate as a stabilizing ligand. This study investigates the use of a range of sulfur containing compounds as promoters for production of highly active Au/C catalysts. Promotion is observed across a range of metal sulfates, non-metal sulfates, and sulfuric acid treatments. This observed enhancement can be optimized by careful consideration of either pre- or post-treatments, concentration of dopants used, and modification of washing steps. Pre-treatment of the carbon support with sulfuric acid (0.76 m) resulted in the most active Au/C in this series with an acetylene conversion of ≈70% at 200 °C., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

A series of ceria-based solid solution metal oxides were prepared by co-precipitation and evaluated as catalysts for glycerol cleavage, principally to methanol. The catalyst activity and selectivity to methanol were investigated with respect to the reducibility of the catalysts. Oxides comprising Ce-Pr and Ce-Zr were prepared, calcined and compared to CeO 2 , Pr 6 O 11 and ZrO 2 . The oxygen storage capacity of the catalysts was examined with analysis of Raman spectroscopic measurements and a temperature programmed reduction, oxidation and reduction cycle. The incorporation of Pr resulted in significant defects, as evidenced by Raman spectroscopy. The materials were evaluated as catalysts for the glycerol to methanol reaction, and it was found that an increased defect density or reducibility was beneficial. The space-time yield of methanol normalized to surface area over CeO 2 was found to be 0.052 mmol MeOH  m -2  h -1 , and over CeZrO 2 and CePrO 2 , this was to 0.029 and 0.076 mmol MeOH  m -2  h -1 , respectively. The inclusion of Pr reduced the surface area; however, the carbon mole selectivity to methanol and ethylene glycol remained relatively high, suggesting a shift in the reaction pathway compared to that over ceria. This article is part of a discussion meeting issue 'Science to enable the circular economy'.

The direct synthesis of hydrogen peroxide (H 2 O 2 ) from molecular H 2 and O 2 offers an attractive, decentralized alternative to production compared to the current means of production, the anthraquinone process. Herein we evaluate the performance of a 0.5%Pd-4.5%Ni/TiO 2 catalyst in batch and flow reactor systems using water as a solvent at ambient temperature. These reaction conditions are considered challenging for the synthesis of high H 2 O 2 concentrations, with the use of sub-ambient temperatures and alcohol co-solvents typical. Catalytic activity was observed to be stable to prolonged use in multiple batch experiments or in a flow system, with selectivities towards H 2 O 2 of 97% and 85%, respectively. This study was carried out in the absence of halide or acid additives that are typically used to inhibit sequential H 2 O 2 degradation reactions showing that this Pd-Ni catalyst has the potential to produce H 2 O 2 selectively. This article is part of a discussion meeting issue 'Science to enable the circular economy'.

The replacement of HgCl 2 /C with Au/C as a catalyst for acetylene hydrochlorination represents a significant reduction in the environmental impact of this industrial process. Under reaction conditions atomically dispersed cationic Au species are the catalytic active site, representing a large-scale application of heterogeneous single-site catalysts. While the metal nuclearity and oxidation state under operating conditions has been investigated in catalysts prepared from aqua regia and thiosulphate, limited studies have focused on the ligand environment surrounding the metal centre. We now report K-edge soft X-ray absorption spectroscopy of the Cl and S ligand species used to stabilise these isolated cationic Au centres in the harsh reaction conditions. We demonstrate the presence of three distinct Cl species in the materials; inorganic Cl - , Au-Cl, and C-Cl and how these species evolve during reaction. Direct evidence of Au-S interactions is confirmed in catalysts prepared using thiosulfate precursors which show high stability towards reduction to inactive metal nanoparticles. This stability was clear during gas switching experiments, where exposure to C 2 H 2 alone did not dramatically alter the Au electronic structure and consequently did not deactivate the thiosulfate catalyst., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Single-site catalysts can demonstrate high activity and selectivity in many catalytic reactions. The synthesis of these materials by impregnation from strongly oxidizing aqueous solutions or pH-controlled deposition often leads to low metal loadings or a range of metal species. Here, we demonstrate that simple impregnation of the metal precursors onto activated carbon from a low-boiling-point, low-polarity solvent, such as acetone, results in catalysts with an atomic dispersion of cationic metal species. We show the generality of this method by producing single-site Au, Pd, Ru and Pt catalysts supported on carbon in a facile manner. Single-site Au/C catalysts have previously been validated commercially to produce vinyl chloride, and here we show that this facile synthesis method can produce effective catalysts for acetylene hydrochlorination in the absence of the highly oxidizing acidic solvents previously used.

In this review, we discuss selected examples from recent literature on the role of the support on directing the nanostructures of Au-based monometallic and bimetallic nanoparticles. The role of support is then discussed in relation to the catalytic properties of Au-based monometallic and bimetallic nanoparticles using different gas phase and liquid phase reactions. The reactions discussed include CO oxidation, aerobic oxidation of monohydric and polyhydric alcohols, selective hydrogenation of alkynes, hydrogenation of nitroaromatics, CO 2 hydrogenation, C-C coupling, and methane oxidation. Only studies where the role of support has been explicitly studied in detail have been selected for discussion. However, the role of support is also examined using examples of reactions involving unsupported metal nanoparticles (i.e., colloidal nanoparticles). It is clear that the support functionality can play a crucial role in tuning the catalytic activity that is observed and that advanced theory and characterization add greatly to our understanding of these fascinating catalysts.

The oxidation of glycerol under alkaline conditions in the presence of a heterogeneous catalyst can be tailored to the formation of lactic acid, an important commodity chemical. Despite recent advances in this area, the mechanism for its formation is still a subject of contention. In this study, we use a model 1 wt. % AuPt/TiO 2 catalyst to probe this mechanism by conducting a series of isotopic labeling experiments with 1,3- 13 C glycerol. Optimization of the reaction conditions was first conducted to ensure high selectivity to lactic acid in the isotopic labeling experiments. Selectivity to lactic acid increased with temperature and concentration of NaOH, but increasing the O 2 pressure appeared to influence only the rate of reaction. Using 1,3- 13 C glycerol, we demonstrate that conversion of pyruvaldehyde to lactic acid proceeds via a base-promoted 1,2-hydride shift. There was no evidence to suggest that this occurs via a 2,1-methide shift under the conditions used in this study.

The development of efficient technologies to prevent the emission of hazardous chlorinated organics from industrial sources without forming harmful byproducts, such as dioxins, is a major challenge in environmental chemistry. Herein, we report a new hydrolytic destruction route for efficient chlorinated organics elimination and demonstrate that phosphoric acid-modified CeO 2 (HP-CeO 2 ) can decompose chlorobenzene (CB) without forming polychlorinated congeners under the industry-relevant reaction conditions. The active site and reaction pathway were investigated, and it was found that surface phosphate groups initially react with CB and water to form phenol and HCl, followed by deep oxidation. The high on-stream stability of the catalyst was due to the efficient generation of HCl, which removes Cl from the catalyst surface and ensures O 2 activation and therefore deep oxidation of the hydrocarbons. Subsequent density functional theory calculations revealed a distinctly decreased formation energy of an oxygen vacancy at nearest (V O-1 ) and next-nearest (V O-2 ) surface sites to the bonded phosphate groups, which likely contributes to the high rate of oxidation observed over the catalyst. Significantly, no dioxins, which are frequently formed in the conventional oxidation route, were observed. This work not only reports an efficient route and corresponding phosphate active site for chlorinated organics elimination but also illustrates that the rational design of the reaction route can solve some of the most important challenges in environmental catalysis.

Continuous low-level supply or in situ generation of hydrogen peroxide (H 2 O 2 ) is essential for the stability of unspecific peroxygenases, which are deemed ideal biocatalysts for the selective activation of C-H bonds. To envisage potential large scale applications of combined catalytic systems the reactions need to be simple, efficient and produce minimal by-products. We show that gold-palladium nanoparticles supported on TiO 2 or carbon have sufficient activity at ambient temperature and pressure to generate H 2 O 2 from H 2 and O 2 and supply the oxidant to the engineered unspecific heme-thiolate peroxygenase PaDa-I. This tandem catalyst combination facilitates efficient oxidation of a range of C-H bonds to hydroxylated products in one reaction vessel with only water as a by-product under conditions that could be easily scaled.