Surface and Bulk Chemistry of Mechanochemically Synthesized Tohdite Nanoparticles.

Aluminum oxides, oxyhydroxides, and hydroxides are important in different fields of application due to their many attractive properties. However, among these materials, tohdite (5AlO·HO) is probably the least known because of the harsh conditions required for its synthesis. Herein, we report a straightforward methodology to synthesize tohdite nanopowders (particle diameter ∼13 nm, specific surface area ∼102 m g) via the mechanochemically induced dehydration of boehmite (γ-AlOOH).

In situ synchrotron x-ray diffraction studies monitoring mechanochemical reactions of hard materials: Challenges and limitations.

In situ monitoring of mechanochemical reactions of soft matter is feasible by synchrotron diffraction experiments. However, so far, reactions of hard materials in existing polymer milling vessels failed due to insufficient energy input. In this study, we present the development of a suitable setup for in situ diffraction experiments at a synchrotron facility.

Mechanochemical Synthesis of Catalytic Materials.

The mechanochemical synthesis of nanomaterials for catalytic applications is a growing research field due to its simplicity, scalability, and eco-friendliness. Besides, it provides materials with distinct features, such as nanocrystallinity, high defect concentration, and close interaction of the components in a system, which are, in most cases, unattainable by conventional routes. Consequently, this research field has recently become highly popular, particularly for the preparation of catalytic materials for various applications, ranging from chemical production over energy conversion catalysis to environmental protection.

Response to Comment on "High-surface-area corundum by mechanochemically induced phase transformation of boehmite".

Li commented that our report claims that methods reported thus far cannot enable the production of high-purity corundum with surface areas greater than 100 m g, and that our obtained material could be porous aggregates rather than nanoparticles. We disagree with both of these suggestions.

High-surface-area corundum by mechanochemically induced phase transformation of boehmite.

In its nanoparticulate form, corundum (α-AlO) could lead to several applications. However, its production into nanoparticles (NPs) is greatly hampered by the high activation energy barrier for its formation from cubic close-packed oxides and the sporadic nature of its nucleation. We report a simple synthesis of nanometer-sized α-AlO (particle diameter ~13 nm, surface areas ~140 m g) by the mechanochemical dehydration of boehmite (γ-AlOOH) at room temperature.

Olefins from Natural Gas by Oxychlorination.

Ethylene and propylene are the key building blocks of the chemical industry, but current processes are unable to close the growing gap between demand and manufacture. Reported herein is an exceptional europium oxychloride (EuOCl) catalyst for the selective (≥95 %) production of light olefins from ethane and propane by oxychlorination chemistry, thus achieving yields of ethylene (90 %) and propylene (40 %) unparalleled by any existing olefin production technology. Moreover, EuOCl is able to process mixtures of methane, ethane, and propane to produce the olefins, thereby reducing separation costs of the alkanes in natural gas.

Europium Oxybromide Catalysts for Efficient Bromine Looping in Natural Gas Valorization.

The industrialization of bromine-mediated natural gas upgrading is contingent on the ability to fully recycle hydrogen bromide (HBr), which is the end form of the halogen after the activation and coupling of the alkanes. Europium oxybromide (EuOBr) is introduced as a unique catalytic material to close the bromine loop via HBr oxidation, permitting low-temperature operation and long lifetimes with a stoichiometric feed (O :HBr=0.25)-conditions at which any catalyst reported to date severely deactivates because of excessive bromination.

Halogen-Mediated Conversion of Hydrocarbons to Commodities.

Halogen chemistry plays a central role in the industrial manufacture of various important chemicals, pharmaceuticals, and polymers. It involves the reaction of halogens or halides with hydrocarbons, leading to intermediate compounds which are readily converted to valuable commodities. These transformations, predominantly mediated by heterogeneous catalysts, have long been successfully applied in the production of polymers.

Selective Production of Carbon Monoxide via Methane Oxychlorination over Vanadyl Pyrophosphate.

A catalytic process is demonstrated for the selective conversion of methane into carbon monoxide via oxychlorination chemistry. The process involves addition of HCl to a CH -O feed to facilitate C-H bond activation under mild conditions, leading to the formation of chloromethanes, CH Cl and CH Cl . The latter are oxidized in situ over the same catalyst, yielding CO and recycling HCl.

Catalyst design for natural-gas upgrading through oxybromination chemistry.

Natural gas contains large volumes of light alkanes, and its abundant reserves make it an appealing feedstock for value-added chemicals and fuels. However, selectively activating the C-H bonds in these useful hydrocarbons is one of the greatest challenges in catalysis. Here we report an attractive oxybromination method for the one-step functionalization of methane under mild conditions that integrates gas-phase alkane bromination with heterogeneously catalysed HBr oxidation, a step that is usually executed separately.

Oxychlorination-Dehydrochlorination Chemistry on Bifunctional Ceria Catalysts for Intensified Vinyl Chloride Production.

Ceria catalyzes the one-step production of the vinyl chloride monomer (VCM) from ethylene with a high yield because of its bifunctional character: redox centers oxychlorinate ethylene to ethylene dichloride (EDC), which is subsequently dehydrochlorinated to VCM over strong acid sites generated in situ. Nanocrystalline CeO2 and CeO2-ZrO2 lead to a VCM yield of 25 % in a single pass, outperforming the best reported systems and reaching industrially attractive levels. The use of CeO2 intensifies the current two-step process within PVC production encompassing CuCl2 -catalyzed oxychlorination and thermal cracking.

Understanding CeO2 as a Deacon catalyst by probe molecule adsorption and in situ infrared characterisations.

CeO(2) has been identified as an efficient catalyst for HCl oxidation in the temperature range of 623-723 K provided that the oxygen content in the feed mixture was sufficiently high to avoid bulk chlorination and thus deactivation. Here we characterise ceria in its fresh and post-reaction states by adsorption of CO(2), NH(3) and CO. Micro-calorimetry, FTIR and TPD experiments are complemented by DFT calculations, which assess adsorption energies and vibrational frequencies.

Development of industrial catalysts for sustainable chlorine production.

The heterogeneously catalyzed gas-phase oxidation of HCl to Cl(2) offers an energy-efficient and eco- friendly route to recover chlorine from HCl-containing byproduct streams in the chemical industry. This process has attracted renewed interest in the last decade due to an increased chlorine demand and the growing excess of byproduct HCl from chlorination processes. Since its introduction (by Deacon in 1868) and till recent times, the industrialization of this reaction has been hindered by the lack of sufficiently active and durable materials.

A delafossite-based copper catalyst for sustainable Cl2 production by HCl oxidation.

A copper catalyst based on a delafossite precursor (CuAlO(2)) displays high activity and extraordinary lifetime in the gas-phase oxidation of HCl to Cl(2), representing a cost-effective alternative to RuO(2)-based catalysts for chlorine recycling.