Efficient Degradation of Sulfamethoxazole by Diatomite-Supported Hydroxyl-Modified UIO-66 Photocatalyst after Calcination.

Sulfamethoxazole (SMX) is a widely used antibiotic to treat bacterial infections prevalent among humans and animals. SMX undergoes several transformation pathways in living organisms and external environments. Therefore, the development of efficient remediation methods for treating SMX and its metabolites is needed. We fabricated a photo-Fenton catalyst using an UIO-66 (Zr) metal-organic framework (MOF) dispersed in diatomite by a single-step solvothermal method for hydroxylation (HO-UIO-66). The HO-UIO-66-0/DE-assisted Fenton-like process degraded SMX with 94.7% efficiency; however, HO-UIO-66 (Zr) is not stable. We improved the stability of the catalyst by introducing a calcination step. The calcination temperature is critical to improving the catalytic efficiency of the composite (for example, designated as HO-UIO-66/DE-300 to denote hydroxylated UIO-66 dispersed in diatomite calcined at 300 °C). The degradation of SMX by HO-UIO-66/DE-300 was 93.8% in 120 min with 4 mmol/L H2O2 at pH 3 under visible light radiation. The O1s XPS signatures signify the stability of the catalyst after repeated use for SMX degradation. The electron spin resonance spectral data suggest the role of h+, •OH, •O2-, and 1O2 in SMX degradation routes. The HO-UIO-66/DE-300-assisted Fenton-like process shows potential in degrading pharmaceutical products present in water and wastewater.

Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon.

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g.

Monocyclic aromatic hydrocarbons production from catalytic cracking of pine wood-derived pyrolytic vapors over Ce-Mo2N/HZSM-5 catalyst.

A series of Mo2N/HZSM-5 and transition metal modified Mo2N/HZSM-5 catalysts were prepared for the catalytic upgrading of pine wood-derived pyrolytic vapors for the selective production of monocyclic aromatic hydrocarbons (MAHs), while restraining the formation of polycyclic aromatic hydrocarbons (PAHs). Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were performed to determine the effects of several factors on selective MAHs production, including Mo2N loading on HZSM-5, transition metal (Fe, Ce, La, Cu, Cr) modification of Mo2N/HZSM-5, pyrolysis temperature, and catalyst-to-biomass ratio. In addition, quantitative experiments were conducted to determine the actual yields of major aromatic hydrocarbons and the source of aromatic hydrocarbons from basic biomass components. Results indicated that among the various catalysts, the Ce-10%Mo2N/HZSM-5 exhibited the best performance on promoting the formation of MAHs and restraining the generation of PAHs. Under the optimal conditions, the actual yields of MAHs and PAHs from Ce-10%Mo2N/HZSM-5 catalytic process were 99.8mg/g and 7.5mg/g, while those from HZSM catalyst were only 77.2mg/g and 23.7mg/g respectively. Furthermore, the possible catalytic mechanism of the Ce-Mo2N/HZSM-5 catalyst was proposed based on the catalyst characterization.

Selective Conversion of 5-Hydroxymethylfuraldehyde Using Cp*Ir Catalysts in Aqueous Formate Buffer Solution.

The highly selective hydrogenation/hydrolytic ring-opening reaction of 5-hydroxymethylfuraldehyde (5-HMF) was catalyzed by homogeneous Cp*Ir(III) half-sandwich complexes to produce 1-hydroxy-2,5-hexanedione (HHD). Adjustment of pH was found to regulate the distribution of products and reaction selectivity, and full conversion of 5-HMF to HHD with 99 % selectivity was achieved at pH 2.5. A mechanistic study revealed that the hydrolysis/ring-opening reaction of 2,5-bis-(hydroxymethyl)furan is the important intermediate reaction step. In addition, an isolated yield of 85 % for HHD was obtained in a 10 g-scale experiment, and the reaction with fructose as the starting material also led to a 98 % GC yield (71.9 % to fructose) of HHD owing to the excellent tolerance of the catalyst under acidic conditions.

Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers.

Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated.

Aerobic oxidation of hydroxymethylfurfural and furfural by using heterogeneous Cox Oy -N@C catalysts.

2,5-Furandicarboxylic acid (FDCA) is considered to be a promising replacement for terephthalic acid since they share similar structures and properties. In contrast to FDCA, 2,5-furandicarboxylic acid methyl (FDCAM) has properties that allow it to be easily purified. In this work, we reported an oxidative esterification of 5-hydroxymethylfurfural (HMF) and furfural to prepare corresponding esters over Cox Oy -N@C catalysts using O2 as benign oxidant. High yield and selectivity of FDCAM and methyl 2-furoate were obtained under optimized conditions. Factors which influenced the product distribution were examined thoroughly. The Cox Oy -N@C catalysts were recycled five times and no significant loss of activity was detected. Characterization of the catalysts could explain such phenomena. Using XPS and TGA, we made a thorough investigation of the effects of ligand and pyrolysis temperature on catalyst activity.