Aerobic Oxidative Cleavage of C(OH)-C Bonds to Produce Aromatic Aldehydes Catalyzed by Cu -1,10-phenanthroline Complex.

Effective cleavage and functionalization of C(OH)-C bonds is of great importance for the production of value-added chemicals from renewable biomass resources such as carbohydrates, lignin and their derivatives. The efficiency and selectivity of oxidative cleavage of C(OH)-C bonds are hindered by their inert nature and various side reactions associated with the hydroxyl group. The oxidative conversion of secondary alcohols to produce aldehydes is particularly challenging because the generated aldehydes tend to be over-oxidized to acids or the other side products.

Deep eutectic solvent-assisted fabrication of zirconium phytate thin nanosheets for important biomass transformations.

Utilization of naturally occurring resources to construct functional catalytic materials is significantly important, and facile and environmental-benign strategies are highly desired to afford the materials having a specific structure and good catalytic activity. Herein, we reported an innovative deep eutectic solvent (DES)-assisted strategy to synthesize zirconium phytate with a thin nanosheet structure (denoted as Zr-Phy-) using plant-originated phytic acid (PhyA) as the renewable building block. This strategy was eco-friendly and adjustable owing to the designability of DESs.

Nanoparticles and single atoms of cobalt synergistically enabled low-temperature reductive amination of carbonyl compounds.

Low-temperature and selective reductive amination of carbonyl compounds is a highly promising approach to access primary amines. However, it remains a great challenge to conduct this attractive route efficiently over earth-abundant metal-based catalysts. Herein, we designed several Co-based catalysts (denoted as Co@C-N(), where represents the pyrolysis temperature) by the pyrolysis of the metal-organic framework ZIF-67 at different temperatures.

Highly efficient C(CO)-C(alkyl) bond cleavage in ketones to access esters over ultrathin N-doped carbon nanosheets.

Selective oxidative cleavage of the C(CO)-C bond in ketones to access esters is a highly attractive strategy for upgrading ketones. However, it remains a great challenge to realize this important transformation over heterogeneous metal-free catalysts. Herein, we designed a series of porous and ultrathin N-doped carbon nanosheets (denoted as CN-, where represents the pyrolysis temperature) as heterogeneous metal-free catalysts.

Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets.

Oxidative cyanation of aldehydes provides a promising strategy for the cyanide-free synthesis of organic nitriles. Design of robust and cost-effective catalysts is the key for this route. Herein, we designed a series of Se,S,N-tri-doped carbon nanosheets with a hierarchical porous structure (denoted as Se,S,N-CNs-x, x represents the pyrolysis temperature).

Robust selenium-doped carbon nitride nanotubes for selective electrocatalytic oxidation of furan compounds to maleic acid.

Selective oxidation of biomass-derived furan compounds to maleic acid (MA), an important bulk chemical, is a very attractive strategy for biomass transformation. However, achieving a high MA selectivity remains a great challenge. Herein, we for the first time successfully designed and fabricated Se-doped graphitic carbon nitride nanotubes with a chemical formula of CN-Se.

Fabrication of Superamphiphilic Carbon Using Lignosulfonate for Enhancing Selective Hydrogenation Reactions in Pickering Emulsions.

Superamphiphilic materials have great potential to enhance the mass transfer between phases in liquid-liquid catalysis due to their special affinities. Constructing superamphiphilic surfaces that possess superhydrophilic and superhydrophobic properties simultaneously has been a tough assignment. So, exploration of simple methods to prepare such materials using renewable and abundant feedstocks is highly desired.

Synthesis of thioethers, arenes and arylated benzoxazoles by transformation of the C(aryl)-C bond of aryl alcohols.

Transformation of aryl alcohols into high-value functionalized aromatic compounds by selective cleavage and functionalization of the C(aryl)-C(OH) bond is of crucial importance, but very challenging by far. Herein, for the first time, we report a novel and versatile strategy for activation and functionalization of C(aryl)-C(OH) bonds by the cooperation of oxygenation and decarboxylative functionalization. A diverse range of aryl alcohol substrates were employed as arylation reagents the cleavage of C(aryl)-C(OH) bonds and effectively converted into corresponding thioether, arene, and arylated benzoxazole products in excellent yields, in a Cu based catalytic system using O as the oxidant.

Ordered-Mesoporous-Carbon-Confined Pb/PbO Composites: Superior Electrocatalysts for CO Reduction.

CO electroreduction has gained significant interest. However, fabricating cost-effective nonprecious-metal electrocatalysts that can selectively convert CO to a specific product remains highly challenging. Herein, Pb-based materials consisting of Pb and PbO confined in ordered mesoporous carbon (OMC) (Pb/PbO@OMC) were constructed for CO electroreduction to CO.

Selective catalytic transformation of lignin with guaiacol as the only liquid product.

Guaiacol is an important feedstock for producing various high-value chemicals. However, the current production route of guaiacol relies heavily on fossil resources. Using lignin as a cheap and renewable feedstock to selectively produce guaiacol has great potential, but it is a challenge because of its heterogeneity and inert reactivity.

Self-supported hydrogenolysis of aromatic ethers to arenes.

Arenes are widely used chemicals and essential components in liquid fuels, which are currently produced from fossil feedstocks. Here, we proposed the self-supported hydrogenolysis (SSH) of aromatic ethers to produce arenes using the hydrogen source within the reactants, and it was found that RuW alloy nanoparticles were very efficient catalyst for the reactions. This route is very attractive and distinguished from the reported studies on the cleavage of the C─O bonds.

Nitrogen Dioxide Catalyzed Aerobic Oxidative Cleavage of C(OH)-C Bonds of Secondary Alcohols to Produce Acids.

Stable organic nitroxyl radicals are an important class of catalysts for oxidation reactions, but their wide applications are hindered by their steric hinderance, high cost, complex operation, and separation procedures. Herein, NO in DMSO is shown to effectively catalyze the aerobic oxidative cleavage of C(OH)-C bonds to form a carboxylic group, and NO was generated in situ by decomposition of nitrates. A diverse range of secondary alcohols were selectively converted into acids in excellent yields in this transition-metal-free system without any additives.

An electrocatalytic route for transformation of biomass-derived furfural into 5-hydroxy-2(5)-furanone.

Development of efficient strategies for biomass valorization is a highly attractive topic. Herein, we conducted the first work on electrocatalytic oxidation of renewable furfural to produce the key bioactive intermediate 5-hydroxy-2(5)-furanone (HFO). It was demonstrated that using HO as the oxygen source and metal chalcogenides (CuS, ZnS, PbS, ) as electrocatalysts, the reaction could proceed efficiently, and the CuS nanosheets prepared in this work showed the best performance and provided high HFO selectivity (83.

Surface engineering in PbS partial oxidation: towards an advanced electrocatalyst for reduction of levulinic acid to γ-valerolactone.

Development of mild and efficient strategies for biomass conversion is of great significance, and design of advanced catalysts is crucial for biomass valorization. Herein, we designed PbS-based electrocatalysts through a surface engineering strategy partial oxidation, and the degree of surface oxidation of PbS to PbSO could be easily tuned by calcination temperature. It was discovered that the prepared electrocatalysts could efficiently catalyze reduction of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) using water as the hydrogen source.

Ambient Reductive Amination of Levulinic Acid to Pyrrolidones over Pt Nanocatalysts on Porous TiO Nanosheets.

Construction of N-substituted pyrrolidones from biomass-derived levulinic acid (LA) via reductive amination is a highly attractive route for biomass valorization. However, realizing this transformation using H as the hydrogen source under mild conditions is still very challenging. Herein, we designed porous TiO nanosheets-supported Pt nanoparticles (Pt/P-TiO) as the heterogeneous catalyst.

Dataset on the mechanical property of graphite after molten FLiNaK salt infiltration.

Presented in this article are mechanical property and microstructural data for fluoride molten salt infiltrated graphite at high temperature. Four infiltration pressures (0 kPa, 450 kPa, 600 kPa, and 1000 kPa) and two kinds of graphite (IG-110 and NG-CT-10) were used during molten salt infiltration. After fluoride molten salt infiltration, compression testing and tension testing were performed at 700 °C to determine compressive strength, tensile strength, softening coefficient, stress-strain curve, and absorbed energy.

Supercritical diethylamine facilitated loading of ultrafine Ru particles on few-layer graphene for solvent-free hydrogenation of levulinic acid to γ-valerolactone.

We demonstrate a facile and versatile method to grow Ru particles uniformly on pristine few-layer graphene (FLG) in supercritical diethylamine. In particular, a large number of Ru subnanometer clusters less than 1.0 nm were observed.

Ionic liquid accelerates the crystallization of Zr-based metal-organic frameworks.

The Zr-based metal-organic frameworks are generally prepared by solvothermal procedure. To overcome the slow kinetics of nucleation and crystallization of Zr-based metal-organic frameworks is of great interest and challenging. Here, we find that an ionic liquid as solvent can significantly accelerate the formation of Zr-based metal-organic frameworks at room temperature.

Catalytic Transformation of Lignocellulose into Chemicals and Fuel Products in Ionic Liquids.

Innovative valorization of naturally abundant and renewable lignocellulosic biomass is of great importance in the pursuit of a sustainable future and biobased economy. Ionic liquids (ILs) as an important kind of green solvents and functional fluids have attracted significant attention for the catalytic transformation of lignocellulosic feedstocks into a diverse range of products. Taking advantage of some unique properties of ILs with different functions, the catalytic transformation processes can be carried out more efficiently and potentially with lower environmental impacts.

Efficient Generation of Lactic Acid from Glycerol over a Ru-Zn-Cu /Hydroxyapatite Catalyst.

The biodiesel production process generates a significant amount of glycerol as a byproduct. A drive to add value has attracted worldwide attention, with the aim of improving the overall effectiveness and profitability of biodiesel production. Herein, we report hydroxyapatite (HAP)-supported Ru-Zn-Cu (Ru-Zn-Cu /HAP) as effective catalysts for the transformation of glycerol to lactic acid (LA).

Synthesis of ketones from biomass-derived feedstock.

Cyclohexanone and its derivatives are very important chemicals, which are currently produced mainly by oxidation of cyclohexane or alkylcyclohexane, hydrogenation of phenols, and alkylation of cyclohexanone. Here we report that bromide salt-modified Pd/C in HO/CHCl can efficiently catalyse the transformation of aromatic ethers, which can be derived from biomass, to cyclohexanone and its derivatives via hydrogenation and hydrolysis processes. The yield of cyclohexanone from anisole can reach 96%, and the yields of cyclohexanone derivatives produced from the aromatic ethers, which can be extracted from plants or derived from lignin, are also satisfactory.

Preparation of Ru/Graphene using Glucose as Carbon Source and Hydrogenation of Levulinic Acid to γ-Valerolactone.

The preparation of functional materials and value-added chemicals using biomass-derived feedstocks is an interesting topic. Herein, we propose a method to prepare Ru/graphene catalyst using glucose as the carbon source. The catalyst was characterized by scanning and transmission electron microscopies, Raman and X-ray photoelectron spectroscopies, and X-ray diffraction.

Using the hydrogen and oxygen in water directly for hydrogenation reactions and glucose oxidation by photocatalysis.

Direct utilization of the abundant hydrogen and oxygen in water for organic reactions is very attractive and challenging in chemistry. Herein, we report the first work on the utilization of the hydrogen in water for the hydrogenation of various organic compounds to form valuable chemicals and the oxygen for the oxidation of glucose, simultaneously by photocatalysis. It was discovered that various unsaturated compounds could be efficiently hydrogenated with high conversion and selectivity by the hydrogen from water splitting and glucose reforming over Pd/TiO under UV irradiation (350 nm).