LanCLs add glutathione to dehydroamino acids generated at phosphorylated sites in the proteome.

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.

Au-Pd separation enhances bimetallic catalysis of alcohol oxidation.

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 applications1-3. Supported gold nanoparticles are highly active for the dehydrogenation of the alcohol to an aldehyde4 but are less effective for oxygen reduction5,6. By contrast, supported palladium nanoparticles offer high efficacy for oxygen reduction5,6. This imbalance can be overcome by alloying gold with palladium, which gives enhanced activity to both reactions7,8,9; 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.

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.

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.

Heterogeneous Trimetallic Nanoparticles as Catalysts.

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.

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.

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.

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.

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.

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.

Methane Oxidation to Methanol in Water.

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 CO2. Indirect methods such as steam reforming produce CO and H2 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 N2O; 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 H2O2 as an oxidant (effectively O2 + 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, H2O2 is an expensive oxidant to use in the production of methanol.This observation of activity under mild conditions led to new approaches to utilize O2 as the oxidant. Supported precious metal nanoparticles have been shown to be active for a range of C-H activation reactions using O2 and H2O2, but the rapid decomposition of H2O2 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 H2O2 consumption was increased by 4 orders of magnitude, and crucially it was demonstrated for the first time that molecular O2 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.

Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts.

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, CO2 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.

Stable amorphous georgeite as a precursor to a high-activity catalyst.

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable--and hence little known and largely ignored--georgeite. The first three of these minerals are widely used as catalyst precursors for the industrially important methanol-synthesis and low-temperature water-gas shift (LTS) reactions, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite; with few exceptions it uses sodium carbonate as the carbonate source, but this also introduces sodium ions--a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts.

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.

Sulfur Promotion in Au/C Catalyzed Acetylene Hydrochlorination.

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.

A Perspective on Heterogeneous Catalysts for the Selective Oxidation of Alcohols.

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.

Spiers Memorial Lecture: Understanding reaction mechanisms in heterogeneously catalysed reactions.

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.

Identification of C2-C5 products from CO2 hydrogenation over PdZn/TiO2-ZSM-5 hybrid catalysts.

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.

A combined periodic DFT and QM/MM approach to understand the radical mechanism of the catalytic production of methanol from glycerol.

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 C3 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 C2 and C3 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.

The direct synthesis of hydrogen peroxide from H2 and O2 using Pd-Ni/TiO2 catalysts.

The direct synthesis of hydrogen peroxide (H2O2) from molecular H2 and O2 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/TiO2 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 H2O2 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 H2O2 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 H2O2 degradation reactions showing that this Pd-Ni catalyst has the potential to produce H2O2 selectively. This article is part of a discussion meeting issue 'Science to enable the circular economy'.