Selective production of methylindan and tetralin with xylose or hemicellulose.

Indan and tetralin are widely used as fuel additives and the intermediates in the manufacture of thermal-stable jet fuel, many chemicals, medicines, and shockproof agents for rubber industry. Herein, we disclose a two-step route to selectively produce 5-methyl-2,3-dihydro-1H-indene (abbreviated as methylindan) and tetralin with xylose or the hemicelluloses from agricultural or forestry waste. Firstly, cyclopentanone (CPO) was selectively formed with ~60% carbon yield by the direct hydrogenolysis of xylose or hemicelluloses on a non-noble bimetallic Cu-La/SBA-15 catalyst. Subsequently, methylindan and tetralin were selectively produced with CPO via a cascade self-aldol condensation/rearrangement/aromatization reaction catalyzed by a commercial H-ZSM-5 zeolite. When we used cyclohexanone (another lignocellulosic cycloketone) in the second step, the main product switched to dimethyltetralin. This work gives insights into the selective production of bicyclic aromatics with lignocellulose.

Converting Glycerol into Valuable Trioses by Cuδ+ -Single-Atom-Decorated WO3 under Visible Light.

Photocatalytic selective oxidation under visible light presents a promising approach for the sustainable transformation of biomass-derived wastes. However, achieving both high conversion and excellent selectivity poses a significant challenge. In this study, two valuable trioses, glyceraldehyde and dihydroxyacetone, are produced from glycerol over Cuδ+ -decorated WO3 photocatalyst in the presence of H2 O2 . The photocatalyst exhibits a remarkable five-fold increase in the conversion rate (3.81 mmol ⋅ g-1 ⋅ h-1 ) while maintaining a high selectivity towards two trioses (46.4 % to glyceraldehyde and 32.9 % to dihydroxyacetone). Through a comprehensive analysis involving X-ray photoelectron spectroscopy measurements with and without light irradiation, electron spin resonance spectroscopy, and isotopic analysis, the critical role of Cu+ species has been explored as efficient hole acceptors. These species facilitate charge transfer, promoting glycerol oxidation by photoholes, followed by coupling with OH- , which are subsequently dehydrated to yield the desired glyceraldehyde and dihydroxyacetone.

Synthesis of piperidines and pyridine from furfural over a surface single-atom alloy Ru1CoNP catalyst.

The sustainable production of value-added N-heterocycles from available biomass allows to reduce the reliance on fossil resources and creates possibilities for economically and ecologically improved synthesis of fine and bulk chemicals. Herein, we present a unique Ru1CoNP/HAP surface single-atom alloy (SSAA) catalyst, which enables a new type of transformation from the bio-based platform chemical furfural to give N-heterocyclic piperidine. In the presence of NH3 and H2, the desired product is formed under mild conditions with a yield up to 93%. Kinetic studies show that the formation of piperidine proceeds via a series of reaction steps. Initially, in this cascade process, furfural amination to furfurylamine takes place, followed by hydrogenation to tetrahydrofurfurylamine (THFAM) and then ring rearrangement to piperidine. DFT calculations suggest that the Ru1CoNP SSAA structure facilitates the direct ring opening of THFAM resulting in 5-amino-1-pentanol which is quickly converted to piperidine. The value of the presented catalytic strategy is highlighted by the synthesis of an actual drug, alkylated piperidines, and pyridine.

Hydrogenolysis-Isomerization of Waste Polyolefin Plastics to Multibranched Liquid Alkanes.

Upcycling of waste polyolefin plastics still meets with economic and technological challenges in practice. In this work, the catalytic hydrogenolysis-isomerization of nondegradable polyolefin plastic waste to high-value gasoline, diesel, and light lubricants with highly branched chain is achieved over a bifunctional Rh/Nb2 O5 catalyst under relatively mild conditions. Owing to the high efficiency of metallic Rh active sites, the dehydrogenation/hydrogenation of long carbon chains of polyolefins is enhanced. With the assistance of strong Brønsted acidity of Nb2 O5 , the cleavage of C-C bonds, skeletal rearrangements, as well as the ß-scission of alkylcarbenium ions occurs, which boosts the one-step solvent-free catalytic hydrogenolysis and isomerization of polyolefins. In addition, the preliminary economic analysis shows that this technology is economical, feasible, and has great potential in accelerating the transition to a circular plastics economy for sustainable development.

Overcoming Limitations in the Strong Interaction between Pt and Irreducible SiO2 Enables Efficient and Selective Hydrogenation of Anthracene.

Interactions between metals and oxide supports are crucial in determining catalytic activity, selectivity, and stability. For reducible oxide supported noble metals, a strong metal-support interaction (SMSI) has been widely recognized. Herein we report the intermediate selectivity and stability over an irreducible SiO2 supported Pt catalyst in the hydrogenation of anthracene that are significantly boosted due to the SMSI-induced formation of intermetallic Pt silicide and Pt-SiO2 interface. The limitation in the strong interaction between Pt nanoparticles and irreducible SiO2 has been breached by combining the strong electrostatic adsorption method and following the high temperature reduction strategy. Due to the isolated Pt active sites by Si atoms, the activated H species produced over the Pt2Si/SiO2 catalyst with an initial catalytic activity of 2.49 µmol/(m2/g)/h as well as TOF of 0.95 s-1 preferentially transfer to the outer ring of anthracene to 87% yield of symmetric octahydroanthracene (sym-OHA) by subsequent hydrogenation. In addition, the Pt2Si/SiO2 catalyst presents an excellent stability after five cycles, which can be attributed to the fact that intermetallic Pt2Si nanoparticles are anchored firmly onto the surface of the SiO2 support. The discovery contributes to broaden the horizons on the SMSI effect in the irreducible oxide supported metal particle catalysts and provides guidance to design the metal-SiO2 interface and tune the surface chemical properties in diverse application conditions.

Template-Preparation of Hollow PtNi Nanostrings as a Bifunctional Electrocatalyst for the Hydrogen Evolution and Oxygen Reduction Reactions.

Designing a highly active, stable and cost-effective electrocatalyst with multiple functionalities toward hydrogen evolution and oxygen reduction applications is crucial for the development of renewable energy sources. Here, the synthesis of hollow PtNi nanostrings via a facile two-step template method is reported. The PtNi nanostrings own Pt-rich rough surfaces, and hollow string-like structure with the structural disorder morphology. Impressively, the unique hollow PtNi nanostrings exhibit excellent electrocatalytic activity toward the hydrogen evolution and oxygen reduction reactions. The obtained overpotential is only 44.60 mV at current density of 10 mA cm-2 for hydrogen evolution reaction. Furthermore, the hollow PtNi nanostrings exhibit a high mass activity of 2.5 A mg-1Pt and a superior specific activity of 3.89 mA cm-2 at 0.90 V versus reversible hydrogen electrode in oxygen reduction reaction, respectively, which are 10 and 9 times higher than those of the commercial Pt/C. This work provides a promising approach for the synthesis of highly bifunctional electrocatalysts with a hollow sting-like structure to promote their application in the hydrogen evolution and oxygen reduction reactions.

A review on high catalytic efficiency of solid acid catalysts for lignin valorization.

It is imminent to develop renewable resources to replace fossil-derived energies as fossil resources are on the brink of exhaustion. Lignin is one of the major components of lignocellulosic biomass, which is a natural amorphous three-dimensional polymer with abundant C-O bonds and aromatic structure. Hence, valorization of lignin into high value-added liquid fuels and chemicals is regarded as a promising strategy to mitigate fossil resource shortages. Solid acid catalysts are extensively studied due to environmentally friendly in terms of the ease of separation, recovery and reduced amount of wastes. Hence, this review focuses on summarizing the recent progress of catalytic valorization of lignin over different kinds of solid acid catalysts including zeolites, heteropolyacids, metal oxides, amorphous SiO2-Al2O3, metal phosphates, and Lewis acid. Based on reviewing of current progress of lignin conversion, the challenges and future prospects are emphasized.

Tuning the Acidity of Pt/ CNTs Catalysts for Hydrodeoxygenation of Diphenyl Ether.

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid nanosheets, a series of Pt/xHMNO6/CNTs with different solid acid compositions (x = 5, 20 wt%; M = Nb, Ta; N = Mo, W) have been prepared by carbon nanotube pretreatment, protonic exchange, solid acid exfoliation, aggregation and finally Pt particles impregnation. The Pt/xHMNO6/CNTs are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and NH3-temperature programmed desorption. The study revealed that HNbWO6 nanosheets were attached on CNTs, with some edges of the nanosheets being bent in shape. The acid strength of the supported Pt catalysts increases in the following order: Pt/CNTs < Pt/5HNbWO6/CNTs < Pt/20HNbMoO6/CNTs < Pt/20HNbWO6/CNTs < Pt/20HTaWO6/CNTs. In addition, the catalytic hydroconversion of lignin-derived model compound: diphenyl ether using the synthesized Pt/20HNbWO6 catalyst has been investigated.

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area.

We demonstrate a method for the synthesis of NixNb1-xO catalysts with sponge-like and fold-like nanostructures. By varying the Nb:Ni ratio, a series of NixNb1-xO nanoparticles with different atomic compositions (x = 0.03, 0.08, 0.15, and 0.20) have been prepared by chemical precipitation. These NixNb1-xO catalysts are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The study revealed the sponge-like and fold-like appearance of Ni0.97Nb0.03O and Ni0.92Nb0.08O on the NiO surface, and the larger surface area of these NixNb1-xO catalysts, compared with the bulk NiO. Maximum surface area of 173 m2/g can be obtained for Ni0.92Nb0.08O catalysts. In addition, the catalytic hydroconversion of lignin-derived compounds using the synthesized Ni0.92Nb0.08O catalysts have been investigated.

A large randomised controlled intervention trial to prevent gastric cancer by eradication of Helicobacter pylori in Linqu County, China: baseline results and factors affecting the eradication.

OBJECTIVE: To clarify the full range of benefits and adverse consequences of Helicobacter pylori eradication as a strategy for gastric cancer prevention, the community-based intervention trial was launched in Linqu County, China. DESIGN: A total of 184,786 residents aged 25-54 years were enrolled in this trial and received (13)C-urea breath test. H. pylori positive participants were assigned into two groups, either receiving a 10-day quadruple anti-H. pylori treatment or lookalike placebos together with a single dosage of omeprazole and bismuth. RESULTS: The prevalence of H. pylori in trial participants was 57.6%. A total of 94,101 subjects completed the treatment. The overall H. pylori eradication rate was 72.9% in the active group. Gender, body mass index, history of stomach disease, baseline delta over baseline-value of (13)C-urea breath test, missed medication doses, smoking and drinking were independent predictors of eradication failure. The missed doses and high baseline delta over baseline-value were important contributors in men and women (all Ptrend<0.001). However, a dose-response relationship between failure rate and smoking or drinking index was found in men (all Ptrend<0.001), while high body mass index (Ptrend<0.001) and history of stomach disease were significant predictors in women. The treatment failure rate increased up to 48.8% (OR 2.87, 95% CI 2.24 to 3.68) in men and 39.4% (OR 2.67, 95% CI 1.61 to 4.42) in women with multiple factors combined. CONCLUSIONS: This large community-based intervention trial to eradicate H. pylori is feasible and acceptable. The findings of this trial lead to a distinct evaluation of factors influencing eradication that should be generally considered for future eradication therapies. TRIAL REGISTRATION NUMBER: ChiCTR-TRC-10000979 in accordance with WHO ICTRP requirements.