Highly efficient catalytic production of oximes from ketones using in situ-generated H2O2.

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.

Impact of the Experimental Parameters on Catalytic Activity When Preparing Polymer Protected Bimetallic Nanoparticle Catalysts on Activated Carbon.

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 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'.

Platinum Nanoparticle Inclusion into a Carbonized Polymer of Intrinsic Microporosity: Electrochemical Characteristics of a Catalyst for Electroless Hydrogen Peroxide Production.

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.

One pot microwave synthesis of highly stable AuPd@Pd supported core-shell nanoparticles.

A series of 1 wt% supported Au, Pd and AuPd nanoalloy catalysts were prepared via microwave assisted reduction of PdCl2 and HAuCl4 in a facile, one pot process. The resulting materials showed excellent activity for the direct synthesis of hydrogen peroxide from hydrogen and oxygen, with a synergistic effect observed on the addition of Au into a Pd catalyst. Detailed electron microscopy showed that the bimetallic particles exhibited a core-shell morphology, with an Au core surrounded by an Au-Pd shell, with a size between 10-20 nm. The presence of Au in the shell was confirmed by EDX studies, with corroborating data from XPS measurements showing a significant contribution of both Au and Pd in the spectra, with the Au signal increasing as the total Au content of the catalyst increased. No PdO was observed, suggesting a complete reduction of the metal chloride nanoparticles. Unlike similar catalysts prepared by sol-immobilisation methodology, the core-shell structures showed excellent stability during the hydrogen peroxide synthesis reaction, and no catalyst deactivation was observed over 4 reuse cycles. This is the first time the preparation of stable core-shell particles have been reported using microwave assisted reduction. The observation that these particles are core-shell, without the need of a complicated synthesis or high thermal treatment and form in just 15 minutes presents an exciting opportunity for this experimental technique.

Silver-palladium catalysts for the direct synthesis of hydrogen peroxide.

A series of bimetallic silver-palladium catalysts supported on titania were prepared by wet impregnation and assessed for the direct synthesis of hydrogen peroxide, and its subsequent side reactions. The addition of silver to a palladium catalyst was found to significantly decrease hydrogen peroxide productivity and hydrogenation, but crucially increase the rate of decomposition. The decomposition product, which is predominantly hydroxyl radicals, can be used to decrease bacterial colonies. The interaction between silver and palladium was characterized using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The results of the TPR and XPS indicated the formation of a silver-palladium alloy. The optimal 1% Ag-4% Pd/TiO2 bimetallic catalyst was able to produce approximately 200 ppm of H2O2 in 30 min. The findings demonstrate that AgPd/TiO2 catalysts are active for the synthesis of hydrogen peroxide and its subsequent decomposition to reactive oxygen species. The catalysts are promising for use in wastewater treatment as they combine the disinfectant properties of silver, hydrogen peroxide production and subsequent decomposition.This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation.

The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviours after heat treatment of Au/FeOx materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed to reveal the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. Correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeOx catalyst.

Direct synthesis of hydrogen peroxide in water at ambient temperature.

The direct synthesis of hydrogen peroxide (H2O2) from hydrogen and oxygen has been studied using an Au-Pd/TiO2 catalyst. The aim of this study is to understand the balance of synthesis and sequential degradation reactions using an aqueous, stabilizer-free solvent at ambient temperature. The effects of the reaction conditions on the productivity of H2O2 formation and the undesirable hydrogenation and decomposition reactions are investigated. Reaction temperature, solvent composition and reaction time have been studied and indicate that when using water as the solvent the H2O2 decomposition reaction is the predominant degradation pathway, which provides new challenges for catalyst design, which has previously focused on minimizing the subsequent hydrogenation reaction. This is of importance for the application of this catalytic approach for water purification.

Palladium-tin catalysts for the direct synthesis of H2O2 with high selectivity.

The direct synthesis of hydrogen peroxide (H2O2) from H2 and O2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H2O2. This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. We show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriate second metal oxide component, and we set out the design principles for producing high-selectivity Pd-based catalysts for direct H2O2 production that do not contain gold.

Gas phase stabiliser-free production of hydrogen peroxide using supported gold-palladium catalysts.

Hydrogen peroxide synthesis from hydrogen and oxygen in the gas phase is postulated to be a key reaction step in the gas phase epoxidation of propene using gold-titanium silicate catalysts. During this process H2O2 is consumed in a secondary step to oxidise an organic molecule so is typically not observed as a reaction product. We demonstrate that using AuPd nanoparticles, which are known to have high H2O2 synthesis rates in the liquid phase, it is possible to not only oxidise organic molecules in the gas phase but to detect H2O2 for the first time as a reaction product in both a fixed bed reactor and a pulsed Temporal Analysis of Products (TAP) reactor without stabilisers present in the gas feed. This observation opens up possibility of synthesising H2O2 directly using a gas phase reaction.

Oxidation of Aliphatic Alcohols by Using Precious Metals Supported on Hydrotalcite under Solvent- and Base-Free Conditions.

Precious metal nanoparticles supported on magnesium-aluminum hydrotalcite (HT), TiO2 , and MgO were prepared by sol immobilization and assessed for the catalytic oxidation of octanol, which is a relatively unreactive aliphatic alcohol, with molecular oxygen as the oxidant under solvent- and base-free conditions. Compared with the TiO2 - and MgO-supported catalysts, platinum HT gave the highest activity and selectivity towards the aldehyde. The turnover number achieved for the platinum HT catalyst was >3700 after 180 min under mild reaction conditions. Moreover, the results for the oxidation of different substrates indicate that a specific interaction of octanal with the platinum HT catalyst could lead to deactivation of the catalyst.

Base-free oxidation of glycerol using titania-supported trimetallic Au­Pd­Pt nanoparticles.

Base-free selective oxidation of glycerol has been investigated using trimetallic Au­Pd­Pt nanoparticles supported on titania and their corresponding bimetallic catalysts. Catalysts were prepared by the sol-immobilization method and characterized by means of TEM, UV/Vis spectroscopy, diffuse reflectance infrared fourier transform spectroscopy, X-ray photoelectron spectroscopy, and microwave plasma­atomic emission spectroscopy. It was found that of the bimetallic catalysts, Pd­Pt/TiO2 was the most active with high selectivity to C3 products. The addition of Au to this catalyst to form the trimetallic Au­Pd­Pt/TiO2, resulted in an increase in activity relative to Pd­Pt/TiO2. The turnover frequency increased from 210 h(−1) with the Pd­Pt/TiO2 catalyst to378 h(−1) for the trimetallic Au­Pd­Pt/TiO2 catalyst with retention of selectivity towards C3 products.

The direct synthesis of hydrogen peroxide using platinum-promoted gold-palladium catalysts.

The direct synthesis of hydrogen peroxide offers a potentially green route to the production of this important commodity chemical. Early studies showed that Pd is a suitable catalyst, but recent work indicated that the addition of Au enhances the activity and selectivity significantly. The addition of a third metal using impregnation as a facile preparation method was thus investigated. The addition of a small amount of Pt to a CeO2-supported AuPd (weight ratio of 1:1) catalyst significantly enhanced the activity in the direct synthesis of H2O2 and decreased the non-desired over-hydrogenation and decomposition reactions. The addition of Pt to the AuPd nanoparticles influenced the surface composition, thus leading to the marked effects that were observed on the catalytic formation of hydrogen peroxide. In addition, an experimental approach that can help to identify the optimal nominal ternary alloy compositions for this reaction is demonstrated.

Strategies for designing supported gold-palladium bimetallic catalysts for the direct synthesis of hydrogen peroxide.

Hydrogen peroxide is a widely used chemical but is not very efficient to make in smaller than industrial scale. It is an important commodity chemical used for bleaching, disinfection, and chemical manufacture. At present, manufacturers use an indirect process in which anthraquinones are sequentially hydrogenated and oxidized in a manner that hydrogen and oxygen are never mixed. However, this process is only economic at a very large scale producing a concentrated product. For many years, the identification of a direct process has been a research goal because it could operate at the point of need, producing hydrogen peroxide at the required concentration for its applications. Research on this topic has been ongoing for about 100 years. Until the last 10 years, catalyst design was solely directed at using supported palladium nanoparticles. These catalysts require the use of bromide and acid to arrest peroxide decomposition, since palladium is a very active catalyst for hydrogen peroxide hydrogenation. Recently, chemists have shown that supported gold nanoparticles are active when gold is alloyed with palladium because this leads to a significant synergistic enhancement in activity and importantly selectivity. Crucially, bimetallic gold-based catalysts do not require the addition of bromide and acids, but with carbon dioxide as a diluent its solubility in the reaction media acts as an in situ acid promoter, which represents a greener approach for peroxide synthesis. The gold catalysts can operate under intrinsically safe conditions using dilute hydrogen and oxygen, yet these catalysts are so active that they can generate peroxide at commercially significant rates. The major problem associated with the direct synthesis of hydrogen peroxide concerns the selectivity of hydrogen usage, since in the indirect process this factor has been finely tuned over decades of operation. In this Account, we discuss how the gold-palladium bimetallic catalysts have active sites for the synthesis and hydrogenation of hydrogen peroxide that are different, in contrast to monometallic palladium in which synthesis and hydrogenation operate at the same sites. Through treatment of the support with acids prior to the deposition of the gold-palladium bimetallic particles, we can obtain a catalyst that can make hydrogen peroxide at a very high rate without decomposing or hydrogenating the product. This innovation opens up the way to design improved catalysts for the direct synthesis process, and these possibilities are described in this Account.

Gold-nanoparticle-based catalysts for the oxidative esterification of 1,4-butanediol into dimethyl succinate.

The oxidation of 1,4-butanediol and butyrolactone have been investigated by using supported gold, palladium and gold-palladium nanoparticles. The products of such reactions are valuable chemical intermediates and, for example, can present a viable pathway for the sustainable production of polymers. If both gold and palladium were present, a significant synergistic effect on the selective formation of dimethyl succinate was observed. The support played a significant role in the reaction, with magnesium hydroxide leading to the highest yield of dimethyl succinate. Based on structural characterisation of the fresh and used catalysts, it was determined that small gold-palladium nanoalloys supported on a basic Mg(OH)2 support provided the best catalysts for this reaction.

Switching-off toluene formation in the solvent-free oxidation of benzyl alcohol using supported trimetallic Au-Pd-Pt nanoparticles.

Trimetallic Au-Pd-Pt nanoparticles have been supported on activated carbon by the sol-immobilisation method. They are found to be highly active and selective catalysts for the solvent-free aerobic oxidation of benzyl alcohol. The addition of Pt promotes the selectivity to the desired product benzaldehyde at the expense of toluene formation. Detailed aberration corrected STEM-XEDS analysis confirmed that the supported particles are indeed Au-Pd-Pt ternary alloys, but also identified composition fluctuations from particle-to-particle which vary systematically with nanoparticle size.

Au-Pd nanoalloys supported on Mg-Al mixed metal oxides as a multifunctional catalyst for solvent-free oxidation of benzyl alcohol.

Au-Pd nanoalloys supported on Mg-Al mixed metal oxides prepared using sol-immobilisation are found to be highly efficient and reusable catalysts for the solvent-free oxidation of benzyl alcohol using molecular oxygen under low pressure. When using this support alloying Pd with Au resulted in an increase in both activity and selectivity to benzaldehyde and moreover an improved resistance to catalyst deactivation compared with the monometallic Pd and Au catalysts. The turnover number for the Au/Pd 1:1 molar ratio catalyst achieved 13,000 after 240 min and the selectivity to benzaldehyde was maintained at 93%; this high catalytic activity can be retained in full after three successive uses. The ensemble and electronic effect of Au-Pd nanoalloys were studied by IR spectroscopy using CO chemisorption, XPS and HRTEM. Moreover, the bifunctional nature of the acid-base MgAl-MMO support was found to be important as the acid sites are considered to be responsible for the improvement of catalytic activity; while, the basic sites gave rise to high selectivity. A possible mechanism with Au-Pd nanoparticles as the active sites has been proposed, illustrating that the oxidation of benzyl alcohol can proceed through the cooperation between the Au-Pd nanoalloys and the base/acid sites on the surface of the support.

Synthesis of stable ligand-free gold-palladium nanoparticles using a simple excess anion method.

We report a convenient excess anion modification and post-reduction step to the impregnation method which permits the reproducible preparation of supported bimetallic AuPd nanoparticles having a tight particle size distribution comparable to that found for sol-immobilization materials but without the complication of ligands adsorbed on the particle surface. The advantageous features of the modified impregnation materials compared to those made by conventional impregnation include a smaller average particle size, an optimized random alloy composition, and improved compositional uniformity from particle-to-particle resulting in higher activity and stability compared to the catalysts prepared using both conventional impregnation and sol immobilization methods. Detailed STEM combined with EDX analyses of individual particles have revealed that an increase in anion concentration increases the gold content of individual particles in the resultant catalyst, thus providing a method to control/tune the composition of the nanoalloy particles. The improved activity and stability characteristics of these new catalysts are demonstrated using (i) the direct synthesis of hydrogen peroxide and (ii) the solvent-free aerobic oxidation of benzyl alcohol as case studies.

Preparation of ultra low loaded Au catalysts for oxidation reactions.

Cyanide leaching was used to obtain Au/SiO2 catalysts with very low gold loadings. A number of catalysts with a nominal 5 wt% target loading were prepared using impregnation and deposition precipitation techniques and these were found to be active catalysts for the solvent-free aerobic oxidation of benzyl alcohol. Exposure of these catalysts to a basic solution of NaCN for 10 min leached gold from the materials to give very pale pink catalysts which were found to contain just 0.06 wt% Au. The concentration of Au removed from the catalyst was constant regardless of the length of NaCN exposure. When the cyanide leached materials were employed for benzyl alcohol oxidation under the same conditions as the unleached parent catalysts, the conversions were identical. However, when the catalytic activity was normalised to the Au content (determined by ICP analysis) the TOFs were much higher for the NaCN treated catalysts (> 400,000 h(-1)). These results clearly demonstrate that NaCN leaching is an effective route to the development of catalysts containing very low gold content, whilst maintaining high activity. The leached materials were found to comprise metallic Au nanoparticles. The successful utilisation of ultra low loaded Au catalysts for selective oxidation, where the majority of the Au present is active and 98% of the spectator Au is removed, makes the industrial application of such materials more economically viable. Information obtained through the identification of these active structures using state of the art techniques may provide useful insights into how the reaction proceeds on the Au surface.