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Formaldehyde is an important intermediate that affects the catalyst performance in the methanol-to-hydrocarbons (MTH) conversion. In this study, photoelectron photoion coincidence spectroscopy was applied to elucidate the formation of this species in empty quartz and stainless steel reactors as well as over zeolite catalysts (ZSM-5 and BETA) and commonly used bed diluents (silicon carbide and quartz). The yields of formaldehyde in an empty stainless steel reactor and over the crude silicon carbide particles were found to be higher or comparable to those over the zeolite catalysts under similar reaction conditions. In the former two systems, formaldehyde is formed via methanol dehydrogenation, which is catalyzed by transition metals and yields hydrogen and carbon monoxide as the main byproducts. Thus produced formaldehyde is readily consumed in the MTH reaction, wherein its conversion is higher for the more acidic zeolites. The formaldehyde generated by the transition metal sites causes a decrease of the catalyst stability as well as a reduction of the propeneto-ethene ratio, as corroborated by catalytic tests exploring different contacting patterns between the ZSM-5 catalyst and stainless steel chips or silicon carbide particles. These results uncover an important role of methanol dehydrogenation in the MTH conversion, which is relevant for the laboratory testing of the zeolite catalysts and the industrial implementation of this technology., ACS Catalysis, 12 (21), ISSN:2155-5435

This article investigates the activity of TiO2-rutile and TiO2-anatase polymorphs in the catalytic HBr oxidation, which is an enabling process to close the halogen loop in bromine-mediated transformation of natural gas to high-value chemicals and liquid fuels. The evaluation of rutile-, anatase-, and rutile-anatase TiO2 catalysts, exhibiting the variable specific surface areas, revealed that anatase phase is also active in this reaction. Nonetheless, in contrast to photocatalytic processes in which anatase is typically more active than rutile, rutile exhibits ca. 2–5 times higher intrinsic rates of HBr oxidation than anatase. Thereby, the apparent activation energies and reaction orders with respect to HBr, O2, and H2O display similar values for the two polymorphs. The activity differences were rationalized by density functional theory analysis, which showed that HBr oxidation follows a similar defect-driven mechanism over the most stable rutile (110) and anatase (101) surfaces. Herein, HBr activates the catalyst through a self-doping mechanism that involves the substitution of surface oxygen by bromine with the concomitant reduction of Ti4+ to Ti3+ centers. This forms a defect level that is placed in the band gap and allows for the O2 activation on the catalyst surface. While the HBr adsorption and H2O desorption display a similar energy profiles on both polymorphs, the O2 activation and Br2 evolution are more facile over rutile compared to anatase surface due to shorter distances between the coordinatively unsaturated Ticus sites and easier reduction of Ti4+ centers upon product desorption, respectively.

Halogen chemistry constitutes an essential part in the industrial production of polymers and gains increasing attention as an attractive strategy to activate light alkanes that constitute natural gas. CeO2-based catalysts offer an exciting potential for advances in hydrogen halide recovery that enables a high efficiency of halogen-based processes for activation of small molecules. This review provides an overview of recently developed ceria-based catalysts in the context of polymer industry (polyvinyl chloride, polyurethanes, and polycarbonates) and activation of light hydrocarbons for natural gas upgrading. In addition, mechanistic insight and the challenges of ceria catalysts are provided, aiding the design of future catalytic materials and applications.

The catalyzed semi hydrogenation of dibromomethane (CH2Br2) to methyl bromide (CH3Br) is a key step in the bromine mediated upgrading of methane. This study presents a cutting edge strategy combini...

A dual system comprising two catalytic reactors connected in series was developed for the direct conversion of ethene to vinyl chloride monomer (VCM). The first reactor uses ZrO2-supported ceria (CeO2/ZrO2) to perform ethene oxychlorination to 1,2-dichloroethene (EDC) that is dehydrochlorinated to VCM in the second reactor over calcium-promoted γ-Al2O3. The choice of carrier for ceria is of critical importance to maximize the EDC production by reducing combustion products. While MgO, SiO2, SiC, TiO2, ZSM-5, and γ-Al2O3 carriers induced higher overoxidation compared to bulk ceria, ZrO2 was the only carrier that suppressed COx formation. Moreover, the latter carrier led to the highest oxychlorination activity. The unique performance of the CeO2/ZrO2 catalyst was rationalized by its ability to promote chlorine evolution and to suppress the combustion of chlorinated products, as inferred from the activity evaluation in HCl and VCM oxidation, respectively. The outstanding redox properties, enabling operation at low temperature and thus high selectivity, are associated with the formation of defective CeO2 nanoparticles, contrasting the low activity over Ce–Zr mixed oxide. In order to subsequently form VCM, an efficient EDC dehydrochlorination catalyst was designed by moderating the acidity of γ-Al2O3via calcium doping and used in a reactor after CeO2/ZrO2. This dual catalyst system displayed 100% selectivity to VCM at 25% ethene conversion, surpassing the space time yield of the best ethene-to-VCM catalyst EuOCl by a factor of four, where the first step is operated at an elevated temperature of about 100–150 K with respect to cupric chloride benchmarks. In addition, the catalytic dehydrochlorination, operated at a lower temperature of 100 K than the current non-catalytic process, showed minimized coke formation. This developed system rendered stable after slight initial deactivation, offering promising potential to intensify VCM production.

Radical-mediated gas-phase reactions play an important role in the conversion of methane under non-oxidative conditions into olefins and aromatics over iron-modified silica catalysts. Herein, we used operando photoelectron photoion coincidence spectroscopy to disentangle the elusive C2+ radical intermediates participating in the complex reaction network. Our experiments pinpointed different C2-C5 radical species that allow for a stepwise growth of the hydrocarbon chains. Herein, propargyl radicals (H2C-C≡C-H) are identified as essential precursors for the formation of aromatics, which contribute with the formation of heavier hydrocarbon products via hydrogen abstraction - acetylene addition routes (HACA mechanism). These results provide comprehensive mechanistic insights that are relevant for development of methane valorization processes., Angewandte Chemie. International Edition, 60 (45), ISSN:1433-7851, ISSN:1521-3773, ISSN:0570-0833

The impact of halogens (Cl2 and Br2) and hydrogen halides (HCl and HBr) on the structural stability of zeolite catalysts constitutes an important yet poorly understood aspect of their performance i...

Dichloromethane (CH2Cl2) hydrodechlorination to chloromethane (CH3Cl) is a pivotal step toward the successful implementation of chlorine-mediated methane-to-liquid technologies. This study investig...

The product distribution in direct alkane functionalization by oxyhalogenation strongly depends on the halogen of choice. We demonstrate that the superior selectivity to olefins over an iron phosphate catalyst in oxychlorination is the consequence of a surface‐confined reaction. By contrast, in oxybromination alkane activation follows a gas‐phase radical‐chain mechanism and yields a mixture of alkyl bromide, cracking, and combustion products. Surface‐coverage analysis of the catalyst and identification of gas‐phase radicals in operando mode are correlated to the catalytic performance by a multi‐technique approach, which combines kinetic studies with advanced characterization techniques such as prompt‐gamma activation analysis and photoelectron photoion coincidence spectroscopy. Rationalization of gas‐phase and surface contributions by density functional theory reveals that the molecular level effects of chlorine are pivotal in determining the stark selectivity differences. These results provide strategies for unraveling detailed mechanisms within complex reaction networks.

This article investigates SiO2-supported Ru-, Pt-, Ir-, Rh-, and Pd-based catalysts (1 wt % metal loading) as new catalytic systems for the oxychlorination and oxybromination of methane, both pivotal steps in the halogen-mediated production of commodities from natural gas. Furthermore, this article provides insights into the structure–performance relationships and mechanism of these reactions as a function of the metal and the hydrogen halide. In-depth characterization of the equilibrated catalysts by X-ray diffraction, electron microscopy, Raman, and X-ray photoelectron spectroscopies demonstrate a fast restructuring of the starting oxide nanoparticles into metallic, metal silicide, or metal halide phases. The oxychlorination activity, which decreases in the order: Ru/SiO2 > Pt/SiO2 > Ir/SiO2 > Rh/SiO2 ≈ Pd/SiO2, is enhanced in the presence of metal oxides, while the activity order in oxybromination: Ru/SiO2 ≈ Ir/SiO2 ≈ Pd/SiO2 > Pt/SiO2 > Rh/SiO2 is less dependent on the phase composition. The highest s...

Development of catalysts that could surpass the activity and selectivity constraints of the non-catalytic radical-mediated halogenation of methane constitutes a long-standing challenge, which exhibits great potential to valorise this readily available resource for the production of commodities. This study presents comprehensive performance maps of a large library of materials, comprising carriers (quartz, SiO2, SiC, α-Al2O3, γ-Al2O3 and carbon), noble metals (Pt, Pd and Ru), metal oxides (Fe2O3 and CeO2), chlorides (PdCl2 and CuCl2) and oxyfluorides (TaOF3) supported on SiO2, γ-Al2O3, carbon or H-ZSM-5 carriers, sulfated systems (S-ZrO2, S-ZrO2-SBA-15, S-TiO2, S-Nb2O5, S-Ta2O5 and Nafion) and zeolites (3A, H-USY, H-MOR, H-SAPO-34, H-BETA and H-ZSM-5), in the chlorination and bromination of methane under practically relevant conditions and gains insights into the nature of the catalytic effects as a function of the catalyst and halogen of choice. The chlorination activity of different catalyst beds at low temperatures (473–523 K) was 2–5.5 times higher compared to that of the empty reactor of identical volume, while the bromination rate was almost unaffected by the solids in the whole temperature range (643–723 K). Except for zeolites and Pt/carbon, which promoted polyhalogenation, selectivities to halomethanes over most of the catalysts were similar to those in the non-catalytic reactions and were higher in bromination (SCH3Br = 80–95% versus SCH3Cl = 52–90% at XCH4 = 5–18%). The formation of carbon oxides (SCOx = 2–28%) over several materials in chlorination and virtually all systems in bromination implied the decomposition of halomethanes, which at higher temperatures led to coking, particularly in the latter reaction. The kinetic fingerprints along with the marginal impact of the Si : Al ratio, counter ions and extraframework aluminium species on the performance of the most active H-ZSM-5 catalyst indicated that methane chlorination over various materials is governed by the radical-chain mechanism, which limits the scope for breaking the selectivity–conversion relationships by tailoring the catalyst acidity. Nonetheless, the enhancement of chlorination activity over zeolites that followed a volcano-like dependence on their micropore size coupled with a more significant impact of the intracrystalline mesoporosity and crystallite size on the product distribution revealed the important role of confinement effects in this reaction, which may pave the way for advancements in the production of chloromethanes., Catalysis Science & Technology, 9 (17), ISSN:2044-4753, ISSN:2044-4761

Catalysed alkane oxyhalogenation has recently been demonstrated as an attractive route for the selective functionalisation of natural gas into commodity chemicals such as alkyl halides or olefins. Herein, we assess the role of the hydrogen halide on the product distribution in ethane and propane oxyhalogenation over europium oxychloride and europium oxybromide catalysts. While olefins are the main reaction products in oxychlorination (selectivity ≥95%), the formation of alkyl bromides (selectivity ≤95%) is favoured in oxybromination, particularly at low conversion levels. At high conversion levels, olefins are also observed, although the selectivity is generally limited (≤60%) due to the formation of cracking and combustion products. A comprehensive kinetic analysis of the oxyhalogenation, halogenation, and oxidative dehydrogenation of the alkanes as well as of the dehydrohalogenation of the alkyl halides provide insights on the complex reaction network, which proceeds through alkyl halide formation followed by its conversion to olefins and/or halocarbons. The observed selectivity differences primarily originate from (i) the halide-dependent alkane activation path, which is surface-driven in oxychlorination, while it mostly occurs via gas-phase halogenation in oxybromination, along with (ii) the preferred tendency of alkyl chlorides towards catalytic dehydrochlorination pathways opposing alkyl bromides that undergo further bromination routes in the gas phase. Finally, detailed characterisation corroborated the above findings and revealed the higher structural stability of europium oxychloride compared to the analogous oxybromide phase under oxyhalogenation conditions. These results deepen the understanding of the alkane oxyhalogenation chemistry on catalyst surfaces for the manufacture of valuable commodities.

Angewandte Chemie. International Edition, 56 (44), ISSN:1433-7851, ISSN:1521-3773, ISSN:0570-0833

Unravelling the pathways of catalytic methane functionalization sets the foundations for the efficient production of valuable chemicals and fuels from this abundant feedstock. The catalytic oxybromination of methane into platform compounds bromomethane and dibromomethane constitutes a prominent example, although it displays a puzzling reaction network that has been speculated to involve free-radical intermediates. Here, photoelectron photoion coincidence spectroscopy with synchrotron radiation was used to provide evidence of the evolution of gaseous methyl and bromine radicals over (VO)2P2O7 and EuOBr catalysts and the strong correlation between the formation of methyl radicals and the production of bromomethanes. Complemented by kinetic data on methane oxybromination and non-catalytic methane bromination, these results imply the surface-catalysed generation of bromine radicals and molecular bromine followed by the gas-phase methane bromination, which is rationalized by density functional theory calculations. The findings emphasize the role of both surface and gas-phase steps in halogen-mediated C–H bond activation over heterogeneous catalysts. Catalytic oxybromination is an important strategy for the upgrade of methane. Here, Perez-Ramirez and co-workers employ operando photoelectron photoion coincidence spectroscopy as well as kinetic analyses and molecular simulations to unravel the complex reaction mechanism.

ChemCatChem, 10 (6), ISSN:1867-3880, ISSN:1867-3899

ACS Catalysis, 8 (1), ISSN:2155-5435

Angewandte Chemie. International Edition, 56 (33), ISSN:1433-7851, ISSN:1521-3773, ISSN:0570-0833

ACS Catalysis, 7 (3), ISSN:2155-5435

Development of catalytic technologies enabling the direct functionalization of light alkanes, main components of abundant natural gas, into value-added chemicals and liquid fuels is quite possibly the key strategy to transit from the oil to the renewables era. A cornerstone to meet this great challenge comprises the in-depth understanding of complex reaction mechanisms over dynamic surfaces, allowing to elucidate catalyst design criteria for selective alkane functionalization processes. Prominent examples are the oxybromination of methane into bromomethanes (CH3Br+CH2Br2) and the oxychlorination of ethane into ethylene, which are the two highly selective routes (selectivity ≤98.5%) that have been proposed to involve gas-phase pathways or purely surface-driven reactions, respectively. Herein, we review our recent efforts to uncover these complex reaction schemes that combine kinetic analysis with advanced operando characterization techniques, including prompt-gamma activation analysis and photoelectron photoion coincidence spectroscopy, ultimately rationalized by density functional theory calculations. In particular, alkane activation to methyl bromide in oxybromination was found to occur in the gas-phase with evolved bromine and bromine radical species, thus enabling to decouple the formation of highly reactive methane-derived intermediates from the catalyst surface that are prone towards combustion. In contrast, the selectivity control in ethane oxychlorination is achieved via a purely surface-driven functionalization of ethane into ethyl chloride, which is further dehydrochlorinated to ethylene over chlorine modified active centers., Chimia, 73 (4), ISSN:0009-4293

Nature Chemistry, 8 (8), ISSN:1755-4349, ISSN:1755-4330

Catalytic HBr oxidation is an integral step in the bromine-mediated functionalisation of alkanes to valuable chemicals. This study establishes the relationships between the mechanism of HBr oxidation over rutile-type oxides (RuO2, IrO2, TiO2) and their apparent catalytic performance. Comparison with the well-studied HCl oxidation revealed distinct differences in surface chemistry between HBr and HCl oxidation that impact the stability and activity of the catalysts. The kinetic fingerprints of both oxidation reactions over the three rutile-type oxides investigated are compared using temporal analysis of products, which substantiates the energy profiles derived from density functional theory. The quantitative determination of the halogen uptake under operando conditions using prompt gamma activation analysis demonstrates that RuO2 suffers from extensive subsurface bromination upon contact with hydrogen bromide, particularly at low temperature and low O2 : HBr ratios, which negatively affects the stability of the catalyst. TiO2 exhibits intrinsically low halogen coverage (30–50%) under all the conditions investigated, due to its unique defect-driven mechanism that renders it active and stable for Br2 production. On the contrary, for HCl oxidation TiO2 is inactive, and the chlorination of the highly active RuO2 is limited to the surface. Differences in the extent of surface halogenation of the materials were also confirmed by high-resolution transmission electron microscopy and explained by the DFT calculations. These insights into the molecular-level processes taking place under working conditions pave the way for the design of the next generation catalysts for bromine production.

Angewandte Chemie. International Edition, 55 (50), ISSN:1433-7851, ISSN:1521-3773, ISSN:0570-0833

Angewandte Chemie. International Edition, 55 (9), ISSN:1433-7851, ISSN:1521-3773, ISSN:0570-0833

The paper analyzes some issues on the comorbidity between schizophrenia and cancer. Epidemiological studies have reported contradictory results, but it is certain that patients with schizophrenia are more likely to suffer from risk factors for cancer development, such as increased alcohol abuse, obesity, nicotine dependence and decreased physical activity. The paper gives guidelines for the treatment of cancer in patients with schizophrenia, and discusses possible interactions between chemotherapy and psychotropic drugs. Particular attention is paid to the use of antipsychotics which increase the level of prolactin, in view of the possible risk of breast and endometrial cancer in patients with schizophrenia.