Gold nanoparticle doped graphitic carbon nitride (Au/g-C3N4) photocatalysts were synthesized via different preparation methods and evaluated for the visible-light-driven degradation of methyl orange at room temperature. All Au-modified samples exhibited superior photocatalytic activity compared to unmodified g-C3N4, which was attributed to the positive role of gold in enhancing charge separation. Notably, catalysts containing well-dispersed Au bimodal size distribution (<0.5 nm intercalated between the layers and 2 nm on the surface) displayed the highest efficiency, achieving complete methyl orange degradation within 180 min. The superior activity of the simple impregnation-derived sample was attributed to its small Au particle size and strong interaction with the g-C3N4 matrix, which facilitated electron trapping and reactive oxygen species generation as shown by photoluminescence, photocurrent response and electrochemical impedance spectroscopy Nyquist plots. The degradation mechanism was determined based on radical scavenger experiments and the dominant reactive species observed were superoxide radicals (O2(center dot-)), hydroxyl radicals ((OH)-O-center dot), and photogenerated holes (h(+)). The solution pH was found to significantly influence the initial adsorption of methyl orange onto the catalyst surface, thereby affecting the overall degradation process. Among the tested strategies, incipient wetness and impregnation routes emerged as promising, facile approaches for the preparation of efficient photocatalysts. This work highlights how synthesis methodology critically governs the physicochemical properties and photocatalytic performance of Au/g-C3N4, offering valuable insights for the design of photocatalysts as sustainable materials for water purification.

In this article, we report the modification and photocatalytic evaluation of commercial TiO 2 -P25 under visible light for methyl orange (MO) dye degradation under visible light. The activity of materials doped with N, Pd, Pt and Au on to the TiO 2 -P25 was evaluated, with optimal photocatalytic performance achieved using Au nanoparticles doped on an N-functionalized titania surface. X-ray diffraction (XRD), physical nitrogen adsorption/desorption isotherm curves, transmission electron microscopy (TEM), diffuse reflectance spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) were used to study the structural and textural properties of the samples. The chemical species present in the bulk and surface of the catalysts were identified using X-ray photoelectron spectroscopy (XPS) and microwave plasma-atomic emission spectroscopy. The results show that Au/N-TiO 2 photocatalyst presents a remarkable enhanced activity for MO dye degradation, under visible light illumination, reaching 100% after 4 h. The enhanced photocatalytic activity using this composite is attributable to the well-dispersed and small size of Au nanoparticles, large surface area, reduction of band-gap energy and the interaction between nitrogen and Au which promoted a synergistic effect. This article is part of the discussion meeting issue ‘Green carbon for the chemical industry of the future’.

The ammoximation of ketones to the corresponding oxime via the in situ production of H2O2 offers a viable alternative to the current means of industrial-scale production, in particular for the synthesis of cyclohexanone oxime, a key precursor to Nylon-6. Herein, we demonstrate that using a bifunctional catalyst, consisting of Pd-based bimetallic nanoparticles immobilized onto a TS-1 carrier, it is possible to bridge the considerable condition gap that exists between the two key distinct reaction pathways that constitute an in-situ approach (i.e., the direct synthesis of H2O2 and ketone ammoximation). The formation of PdAu nanoalloys is found to be crucial in achieving high reactivity and in promoting catalytic stability, with the optimal materials and the monometallic Pd analogue.

Supported PdSn catalysts are highly effective for the direct synthesis of hydrogen peroxide showing significantly higher selectivity to comparable PdAu catalysts.

Sol immobilization is used to produce bimetallic catalysts with higher activity to monometallic counterparts for a wide range of environmental and commercial catalytic transformations. Analysis of complementary surface characterization (XPS, Boehm's titration, and zeta potential measurements) was used to elucidate alterations in the surface functionality of two activated carbon supports during acid exposure. When considered in parallel to the experimentally determined electrostatic and conformational changes of the polymer surrounding the nanoparticles, an electrostatic model is proposed describing polymer protected nanoparticle deposition with several polymer-carbon support examples described. Consideration of the electrostatic interactions ensures full deposition of the polymer protected nanoparticles and at the same time influences the structure of the bimetallic nanoparticle immobilized on the support. The normalized activity of AuPd catalysts prepared with 133 ppm H2SO4 has a much higher activity for the direct synthesis of hydrogen peroxide compared to catalysts prepared in the absence of acid. Detailed characterization by XPS indicates that the surface becomes enriched in Au in the Au-Pd samples prepared with acid, suggesting an improved dispersion of smaller bimetallic nanoparticles, rich in Au, that are known to be highly active for the direct synthesis reaction. Subsequent microscopy measurements confirmed this hypothesis, with the acid addition catalysts having a mean particle size ∼2 nm smaller than the zero acid counterparts. The addition of acid did not result in a morphology change, and random alloyed bimetallic AuPd nanoparticles were observed in catalysts prepared by sol immobilization in the presence and absence of acid. This work shows that the deposition of polymer protected AuPd nanoparticles onto activated carbon is heavily influenced by the acid addition step in the sol immobilization process. The physicochemical properties of both the polymer and the activated carbon support should be considered when designing a bimetallic nanoparticle catalyst by sol immobilization to ensure the optimum performance of the final catalyst.

The in situ synthesis of H2O2 offers an attractive alternative to the current industrial route to cyclohexanone oxime, a major precursor to Nylon-6.

The ammoximation of cyclohexanone using preformed hydrogen peroxide (H2O2) 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, H2O2 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 H2O2, 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 H2O2 and TS-1, while allowing for considerable process intensification.

In this paper we aim to highlight the need to consider the possible role of autocatalysis in oxidation reactions when using molecular oxygen as the terminal oxidant. Oxygen in its ground state is a diradical, and depending on the reaction conditions, it can initiate oxidation through radical pathways through mechanisms which do not require the presence of a catalyst. Consequently, we contrast the oxidation of benzyl alcohol with oxidation of α-pinene. For benzyl alcohol oxidation the initial reaction is the oxidative dehydrogenation to form benzaldehyde, a non-radical process; but the subsequent over-oxidation to benzoic acid is a radical process. In this case the role of the autocatalysed reaction can be minimised. With α-pinene, the oxidation reaction is via radical pathways and now the autocatalysed reaction can be dominant and, indeed, can be the preferred pathway for the formation of high yields of the desired verbenone product.

This Account is to commemorate the 70th birthday of Graham Hutchings and his diverse and distinguished career in catalysis, working in industry and academia. The scope of his work is wide ranging, and he has contributed to many areas of catalysis and has been a pioneer in several of them. Notable contributions to the discipline include novel methods of catalyst preparation for both metal oxides and supported nanoparticles, selective oxidation, acetylene hydrochlorination, and direct hydrogen peroxide synthesis, and he has played a central role in the discovery, application, and understanding of gold-based catalysts. The aim of this article is to provide an outline of his career and highlight some of the contributions he has made to the field of catalysis. Successfully supervising over 190 Ph.D. students, working directly with more than 90 postdoctoral researchers, and collaborating widely nationally and internationally, his work has influenced many in the discipline of heterogeneous catalysis.

Simon Kondrat opened discussion of the paper by Valerii Bukhtiyarov: The influence on butene selectivity by using metal acetate precursors is very interesting. Your work and findings remind me of previous work by myself and others on the influence of heat treatment atmosphere on the final metal

Low temperature oxidation of alcohols over heterogeneous catalysts is exceptionally challenging, particularly under neutral conditions. Herein, we report on an efficient, base-free method to oxidise glycerol over a 0.5%Pd-0.5%Fe/SiO 2 catalyst at ambient temperature in the presence of gaseous H 2 and O 2 . The exceptional catalytic performance was attributed to the in situ formation of highly reactive surface-bound oxygenated species, which promote the dehydrogenation on the alcohol. The PdFe bimetallic catalyst was determined to be significantly more active than corresponding monometallic analogues, highlighting the important role both metals have in this oxidative transformation. Fe leaching was confirmed to occur over the course of the reaction but sequestering experiments, involving the addition of bare carbon to the reactions, confirmed that the reaction was predominantly heterogeneous in nature. Investigations with electron paramagnetic resonance spectroscopy suggested that the reactivity in the early stages was mediated by surface-bound reactive oxygen species; no homogeneous radical species were observed in solution. This theory was further evidenced by a direct H 2 O 2 synthesis study, which confirmed that the presence of Fe in the bimetallic catalyst neither improved the synthesis of H 2 O 2 nor promoted its decomposition over the PdFe/SiO 2 catalyst.

The oxidation of cyclohexane via the in-situ production of H2O2 from molecular H2 and O2 offers an attractive route to the current industrial means of producing cyclohexanone and cyclohexanol (KA oil), key materials in the production of Nylon. The in-situ route has the potential to overcome the significant economic and environmental concerns associated with the use of commercial H2O2, while also allowing for the use of far lower reaction temperatures than those typical of the purely aerobic route to KA oil. Herein we demonstrate the efficacy of a series of bi-functional Pd-based catalysts, which offer appreciable concentrations of KA oil, under conditions where limited activity is observed using O2 alone. In particular the introduction of V into a supported Pd catalyst is seen to improve KA oil concentration by an order of magnitude, compared to the Pd-only analogue. In particular we ascribe this improvement in catalytic performance to the development of Pd domains of mixed oxidation state upon V incorporation as evidenced through X-ray photoelectron spectroscopy.

Bimetallic Pd-Fe catalysts supported on TiO2 are shown to be highly effective toward the selective oxidation of benzyl alcohol to benzaldehyde via the in situ production of H2O2 from molecular H2 and O2, under conditions where no reaction is observed with molecular O2 alone. The rate of benzyl alcohol oxidation observed over supported Pd-Fe nanoparticles is significantly higher than those of either Pd-Au or Pd-only analogues. This enhanced activity can be attributed to the bifunctionality of the Pd-Fe catalyst to both synthesize H2O2 and catalyze the production of oxygen-based radical specie,s as indicated by an electron paramagnetic resonance analysis. Further studies also reveal the noninnocent nature of the solvent, resulting in the propagation of radical generation pathways.

Globally, water disinfection is reliant on chlorination, but requires a route that avoids the formation of chemical residues. Hydrogen peroxide, a broad-spectrum biocide, can offer such an alternative, but is typically less effective than traditional approaches to water remediation. Here, we show that the reactive oxygen species—which include hydroxyl, hydroperoxyl and superoxide radicals—formed over a AuPd catalyst during the synthesis of hydrogen peroxide from hydrogen and air are over 107 times more potent than an equivalent amount of preformed hydrogen peroxide and over 108 times more effective than chlorination under equivalent conditions. The key to bactericidal and virucidal efficacy is the radical flux that forms when hydrogen and oxygen are activated on the catalyst. This approach could form the basis of an alternative method for water disinfection, particularly in communities not currently served by traditional means of water remediation or where access to potable water is scarce. Despite its biocidal properties, the use of hydrogen peroxide is still limited in the context of water disinfection. Here an approach is disclosed based on the generation of H2O2 in situ by means of an AuPd catalyst, which can compete with chlorination methods by generating a highly reactive radical flux.

The use of a hydrophobic solvent in combination with water leads to significant suppression of H2O2 degradation pathways over a AuPd/C catalyst.

The oxidation of cyclohexane via the in-situ production of H2O2 from molecular H2 and O2 offers an attractive route to the current industrial means of producing cyclohexanone and cyclohexanol (KA oil), both key materials in the production of Nylon. Herein we demonstrate that through the in-situ production of H2O2 supported AuPd nanoparticles catalyse the formation of KA oil under conditions where activity is limited when using molecular O2, with no loss in catalytic activity observed upon re-use. The effect of key reaction parameters, including reaction temperature, catalyst mass and H2:O2 ratio are evaluated.

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 direct synthesis of hydrogen peroxide (H2O2) 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/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'.

Catalysts consisting of Au, Pd and their alloys have been shown to be active oxidation catalysts. These materials can use dioxygen or hydrogen peroxide as the oxidant with CO and activated organic molecules using O2(g) while more challenging cases, such as methane to partial oxygenates, relying on H2O2. Although H2O2 is a green oxidant, the incorporation of dioxygen greatly reduces overall cost and so there is an incentive to find new ways to reduce the reliance on H2O2. In this study we use DFT calculations to discuss the direct synthesis of H2O2 from H2(g) and O2(g) and use this understanding to identify the important surface species derived from dioxygen. We cover the adsorption of oxygen, hydrogen and water to model Au and Pd nanoclusters and the oxidation of the metals, since reduction of any oxides formed will consume H2. We then turn to the production of a surface hydroperoxy species; the first step in the synthesis of H2O2. This can occur via hydrogenation of O2(ads) with H2(ads) or via protonation of O2(ads) by solvent water. Both routes are found to be energetically reasonable, but the latter is likely to be favoured under experimental conditions.

Catalytic hydrogenation of levulinic acid to form gamma-valerolactone was studied over Cu-ZrO2 catalysts doped with metal oxides from the first-row transition metals. The Cu-ZrO2 material was prepared by oxalate gel coprecipitation, and dopants were added by an incipient wetness approach. The addition of 1% Mn into Cu ZrO2 significantly increases the yield of y-valerolactone, and the catalytic activity of Mn/Cu-ZrO2 was found to be 1.6 times higher than that of the undoped Cu ZrO2 catalyst. Catalyst characterization suggests that the Mn dopant improves the dispersion of Cu on the surface of ZrO2. Kinetic studies show that the reaction order with respect to the substrate concentration is approximately zero. However, the order of reaction with respect to the partial pressure of H-2 is different for the Mn/Cu-ZrO2 and Cu-ZrO2 catalysts. Comparison of reaction products from reactions carried out in H2O and D2O solvents using H-1 NMR and C-13 NMR show that there is a pre equilibrium keto enol isomerization step under our reaction conditions. DFT calculations show that the enol isomers have a higher affinity for the Cu surface, which may improve the substrate in the hydrogenation step of the reaction.