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.

Glucaric acid is being used increasingly as a food additive, corrosion inhibitor, in deicing, and in detergents, and is also a potential starting material for the production of adipic acid, the key monomer for nylon-66. This work describes a techno-economic analysis of a potential bio-based process for the production of pure glucaric acid from corn stover (biomass). Two alternative routes for oxidation of glucose to glucaric acid are considered: via heterogeneous catalytic oxidation with air, and by homogeneous glucose oxidation using nitric acid. Techno-economic and lifecycle assessments (TEA, LCA) are made for both oxidation routes and cover the entire process from biomass to pure crystalline glucaric acid that can be used as a starting material for the production of valuable chemicals. This is the first TEA of pure glucaric acid production incorporating ion exchange and azeotropic evaporation below 50°C to avoid lactone formation. The developed process models were simulated in Aspen Plus V9. The techno-economic assessment shows that both production routes are economically viable leading to minimum selling prices of glucaric acid of ∼$2.53/kg and ∼$2.91/kg for the heterogeneous catalytic route and the homogeneous glucose oxidation route respectively. It is shown that the heterogeneous catalytic oxidation route is capable of achieving a 22% lower environmental impact than the homogeneous glucose oxidation route. Opportunities for further improvement in sustainable glucaric acid production at industrial scale are identified and discussed.

Quantitative correlative 1H–13C NMR has long been discussed as a potential method for quantifying the components of complex reaction mixtures. Here, we show that quantitative HMBC NMR can be applied to understand the complexity of the catalytic oxidation of glucose to glucaric acid, which is a promising bio-derived precursor to adipic acid, under aqueous aerobic conditions. It is shown through 2D NMR analysis that the product streams of this increasingly studied reaction contain lactone and dilactone derivatives of acid products, including glucaric acid, which are not observable/quantifiable using traditional chromatographic techniques. At 98% glucose conversion, total C6 lactone yield reaches 44%. Furthermore, a study of catalyst stability shows that all Pt catalysts undergo product-mediated chemical leaching. Through catalyst development studies, it is shown that sequestration of leached Pt can be achieved through use of carbon supports.

Catalytic upgrading of CO2 to value-added chemicals is an important challenge within the chemical sciences. Of particular interest are catalysts which are both active and selective for the hydrogenation of CO2 to methanol. PdZn alloy nanoparticles supported on TiO2 via a solvent-free chemical vapour impregnation method are shown to be effective for this reaction. This synthesis technique is shown to minimise surface contaminants, which are detrimental to catalyst activity. The effect of reductive heat treatments on both structural properties of PdZn/TiO2 catalysts and rates of catalytic CO2 hydrogenation are investigated. PdZn nanoparticles formed upon reduction showed high stability towards particle sintering at high reduction temperature with average diameter of 3-6 nm to give 1710 mmol kg(-1) h of methanol. Reductive treatment at high temperature results in the formation of ZnTiO3 as well as PdZn, and gives the highest methanol yield.

Eschewing the common trend toward use of catalysts composed of Cu, it is reported that PdZn alloys are active for CO2 hydrogenation to oxygenates. It is shown that enhanced CO2 conversion is achievable through the introduction of Bronsted acid sites, which promote dehydration of methanol to dimethyl ether. We report that deposition of PdZn alloy nanoparticles onto the solid acid ZSM-5, via chemical vapor impregnation affords catalysts for the direct hydrogenation of CO2 to DME. This catalyst shows dual functionality; catalyzing both CO2 hydrogenation to methanol and its dehydration to dimethyl in a single catalyst bed, at temperatures of >270 degrees C. A physically mixed bed comprising 5% Pd 15% Zn/TiO2 and H-ZSM-5 shows a comparably high performance, affording a dimethyl ether synthesis rate of 546 mmol kg(cat)(-1) h(-1) at a reaction temperature of 270 degrees C.

Adamik, RK, Hernández-Ibáñez, N, Iniesta, J, Edwards, JK, Howe, AGR, Armstrong, RD, Taylor, SH, Roldan, A, Rong, Y, Malpass-Evans, R, Carta, M, McKeown, NB, He, D & Marken, F 2018, 'Platinum nanoparticle inclusion into a carbonized polymer of intrinsic microporosity: Electrochemical characteristics of a catalyst for electroless hydrogen peroxide production', Nanomaterials, vol. 8, no. 7, 542. https://doi.org/10.3390/nano8070542

The one-step vacuum carbonization synthesis of a platinum nano-catalyst embedded in a microporous heterocarbon (Pt@cPIM) is demonstrated. A nitrogen-rich polymer of an intrinsic microporosity (PIM) precursor is impregnated with PtCl62− to give (after vacuum carbonization at 700 °C) a nitrogen-containing heterocarbon with embedded Pt nanoparticles of typically 1–4 nm diameter (with some particles up to 20 nm diameter). The Brunauer-Emmett-Teller (BET) surface area of this hybrid material is 518 m2 g−1 (with a cumulative pore volume of 1.1 cm3 g−1) consistent with the surface area of the corresponding platinum-free heterocarbon. In electrochemical experiments, the heterocarbon-embedded nano-platinum is observed as reactive towards hydrogen oxidation, but essentially non-reactive towards bigger molecules during methanol oxidation or during oxygen reduction. Therefore, oxygen reduction under electrochemical conditions is suggested to occur mainly via a 2-electron pathway on the outer carbon shell to give H2O2. Kinetic selectivity is confirmed in exploratory catalysis experiments in the presence of H2 gas (which is oxidized on Pt) and O2 gas (which is reduced on the heterocarbon surface) to result in the direct formation of H2O2.

The article Solvent Free Synthesis of PdZn/TiO 2 Catalysts for the Hydrogenation of CO 2 to Methanol by Hasliza Bahruji, Jonathan Ruiz Esquius, Michael Bowker, Graham Hutchings, Robert D. Armstrong, Wilm Jones was originally published Online First without open access. After publication in volume 61, issue 3–4, pages 144–153, the author decided to opt for Open Choice and to make the article an open access publication. Therefore, the copyright of the article has been changed to ©The Author(s) 2018 and the article is forthwith distributed under the terms of the Creative Commons Attribution 4.0 International License ( http://creativecommons.org/licenses/by/4.0/ ), which permits use, duplication, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.

Partial oxidative upgrading of C1 -C3 alkanes over Cu/ZSM-5 catalysts prepared by chemical vapour impregnation (CVI) has been studied. The undoped ZSM-5 support is itself able to catalyse selective oxidations, for example, methane to methanol, using mild reaction conditions and the green oxidant H2 O2 . Addition of Cu suppresses secondary oxidation reactions, affording methanol selectivities of up to 97 %. Characterisation studies attribute this ability to population of specific Cu sites below the level of total exchange (Cu/Al<0.5). These species also show activity for radical-based methane oxidation, with productivities exceeding those of the parent zeolite supports. When tested for ethane and propane oxidation reactions, comparable trends are observed.

Liquid-phase catalytic oxidation of glycerol in aqueous solutions using porous solid catalysts represents a viable strategy for the sustainable production of fine chemicals from renewable resources. Various aspects of these novel types of reactions are still under investigation. Catalyst deactivation is one of those issues that need to be understood and addressed in order to make these processes commercially viable. In a previous study, it has been reported that the catalytic activity of Au/TiO2 catalysts for the oxidation of glycerol with O-2 under basic conditions can be severely inhibited by some reaction intermediates or products. It was suggested that the presence of certain species blocks the active sites of the catalyst, preventing the adsorption of glycerol, which in turn results in a decrease of reaction rate. In this work, we used NMR relaxation time measurements in order to assess surface interactions of glycerol in a Au/TiO2 catalyst pretreated with aqueous solutions of various oxygenates, including intermediates and products of glycerol oxidation, under basic conditions, in particular, evaluating changes in glycerol adsorption properties. The NMR T-1/T-2 ratio of glycerol, which is indicative of the strength of interaction of glycerol with the catalyst surface, traces out well the trend in catalytic activity in the presence of different additives, suggesting that adsorption of glycerol onto the catalyst surface plays a crucial role in the reaction, which supports the hypothesis previously made in the literature. This experimental approach and the related results represent a significant advance in the understanding of liquid-phase catalytic reactions occurring over solid surfaces, which can be used to understand and optimize catalytic processes and the effect of intermediate and product inhibition.

Glucaric acid has potential applications in food, pharmaceutical and polymer industries yet no methodology exists within the public domain for isolation of this key bio-derived platform molecule as a pure, crystalline solid. Here we demonstrate the difficulties, which arise in doing so and report development of a process for derivation of free-glucaric acid from its Ca2+/K+ glucarate salts, which are both commercially available. Employing Amberlyst-15 (H+) exchange resin and azeotrope drying, powdered glucaric acid is prepared at > 99.96 % purity in 98.7 % dry yield.

The 11th NGCS meeting took place between 5th and 9th of June 2016, and was hosted in Tromso/Norway. The latest developments from academic and industrial perspectives were discussed and presented in (1) Production of Synthesis Gas, (2) Synthesis Gas to Fuels and Chemicals, (3) Direct Conversion of Methane, (4) Conversion of Light Paraffins, (5) Natural Gas in Energy Conversion, and (6) Techno-Economic Aspects. Along with the social events and the post-symposium excursions, this NGCS meeting was a memorable symposium for all participants. (C) 2017 Elsevier B.V. All rights reserved.

Catalytic methane oxidation using N2 O was investigated at 300 °C over Fe-ZSM-5. This reaction rapidly produces coke (retained organic species), and causes catalyst fouling. The introduction of water into the feed-stream resulted in a significant decrease in the coke selectivity and an increase in the selectivity to the desired product, methanol, from ca. 1 % up to 16 %. A detailed investigation was carried out to determine the fundamental effect of water on the reaction pathway and catalyst stability. The delplot technique was utilised to identify primary and secondary reaction products. This kinetic study suggests that observed gas phase products (CO, CO2 , CH3 OH, C2 H4 and C2 H6 ) form as primary products whilst coke is a secondary product. Dimethyl ether was not detected, however we consider that the formation of C2 products are likely to be due to an initial condensation of methanol within the pores of the zeolite and hence considered pseudo-primary products. According to a second order delplot analysis, coke is considered a secondary product and its formation correlates with CH3 OH formation. Control experiments in the absence of methane revealed that the rate of N2 O decomposition is similar to that of the full reaction mixture, indicating that the loss of active alpha-oxygen sites is the likely cause of the decrease in activity observed and water does not inhibit this process.

A nitrogen-containing polymer of intrinsic microporosity (PIM-EA-TB-H-2; nitrogen adsorption surface area 846 m(2) g(-1)) is vacuum carbonized at 700 degrees C and thereby directly without post-treatment converted into a microporous heterocarbon (cPIM; N-2 adsorption surface area 425 m(2) g(-1)). Nitrogen functionalities in the polymer backbone are retained in the heterocarbon and appear responsible for unusual time-, electrolyte-, and pH-dependent properties. Electrochemical characterization suggests a high specific capacitance (typically 50 F g(-1)) but only after prolonged immersion in aqueous HClO4. The time dependent increase in capacitance during immersion is assigned to slow hydration and ingress of HClO4 into hydrophobic micropores (H2SO4 or H3PO4 are more hydrophilic and much less effective). Once hydrated, the microporous heterocarbon exhibits pH-dependent capacitance "switching" over a wide pH range and analytical applications as "capacitive" pH sensor are proposed. (C) 2017 Elsevier Ltd. All rights reserved.

The selective partial oxidation of short chain alkanes is a key challenge within catalysis research. Direct ethane oxidation to oxygenates is a difficult aim, but potentially rewarding, and it could lead to a paradigm shift in the supply chain of several bulk chemicals. Unfortunately, low C–H bond reactivity and kinetically labile products are just some reasons affecting the development and commercialisation of such processes. Research into direct ethane oxidation is therefore disparate, with approaches ranging from oxidation in the gas phase at high temperatures to enzyme catalysed hydroxylation under ambient conditions. Furthermore, in overcoming the barrier posed by the chemically inert C–H bond a range of oxidants have been utilised. Despite years of research, this remains an intriguing topic from both academic and commercial perspectives. Herein we describe some recent developments within the field of catalytic ethane oxidation focusing on the formation of oxygenated products, whilst addressing the key challenges which are still to be overcome.

We report the oxidation of propane under mild aqueous conditions using H2O2 as the oxidant.