Engineering Lewis-Acid Defects on ZnO Quantum Dots by Trace Transition-Metal Single Atoms for High Glycerol-to-Glycerol Carbonate Conversion.

Efficient conversion of biomass wastes into valuable chemicals has been regarded as a sustainable approach for green and circular economy. Herein, a highly efficient catalytic conversion of glycerol (Gly) into glycerol carbonate (GlyC) by carbonylation with the commercially available urea is presented using low-cost transition metal single atoms supported on zinc oxide quantum dots (M1-ZnO QDs) as a catalyst without using any solvent. A facile one-step wet chemical synthesis allows various types of metal single atoms to simultaneously dope and introduce Lewis-acid defects in the ZnO QD structure. It is found that doping with a trace amount of isolated metal atoms greatly boosts the catalytic activity with Gly conversion of 90.7%, GlyC selectivity of 100.0%, and GlyC yield of 90.6%. Congruential results from both Density Functional Theory (DFT) and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) studies reveal that the superior catalytic performance can be attributed to the enriched Lewis acid sites that endow optimal adsorption, formation of the intermediate for coupling between urea and Gly, and desorption of GlyC. Moreover, the tiny size of ZnO QDs efficiently promotes the accessibility of these active sites to the reactants.

Extraction of silica from sugarcane bagasse ash and its utilization in zeolite 4A synthesis for CO2 adsorption.

Sugarcane bagasse ash (SCBA) is a solid waste containing a high amount of silica (SiO2) and is suitable to utilize as a silica source for synthesizing zeolite NaA. SCBA is typically calcined at high temperatures before silica extraction. The method is not environmentally friendly because it consumes energy and produces CO2. This work demonstrates an alternative extraction method of SiO2 from SCBA by treating it with hydrochloric (HCl) and sodium hydroxide (NaOH) solution. The obtained mixture was separated by paper filter No. 1 (P) and a combination of paper filter and syringe filter (PS). The solution was neutralized by HCl solution, producing silica (SiO2-P and SiO2-PS) with a purity of 98 wt%. Both SiO2 samples and SCBA were utilized to synthesize zeolite NaA for CO2 adsorption. The CO2 adsorption capacities of NaA-P and NaA-PS were 4.30 and 4.10 mmol gadsorbent -1, in the same range as commercial NaA. The capacity is influenced by the total basicity of zeolite. The CO2 adsorption behavior of all samples correlates well with the Toth model. The CO2 adsorption kinetics agrees well with the pseudo-second-order kinetic model. Overall, this work shows the successful extraction of silica via using a direct NaOH solution, yielding high-purity silica sufficient for synthesizing zeolite NaA, a promising adsorbent of CO2.

General Pyrolysis for High-Loading Transition Metal Single Atoms on 2D-Nitro-Oxygeneous Carbon as Efficient ORR Electrocatalysts.

Single-atom catalysts (SACs) possess the potential to involve the merits of both homogeneous and heterogeneous catalysts altogether and thus have gained considerable attention. However, the large-scale synthesis of SACs with rich isolate-metal sites by simple and low-cost strategies has remained challenging. In this work, we report a facile one-step pyrolysis that automatically produces SACs with high metal loading (5.2-15.9 wt %) supported on two-dimensional nitro-oxygenated carbon (M1-2D-NOC) without using any solvents and sacrificial templates. The method is also generic to various transition metals and can be scaled up to several grams based on the capacity of the containers and furnaces. The high density of active sites with N/O coordination geometry endows them with impressive catalytic activities and stability, as demonstrated in the oxygen reduction reaction (ORR). For example, Fe1-2D-NOC exhibits an onset potential of 0.985 V vs RHE, a half-wave potential of 0.826 V, and a Tafel slope of -40.860 mV/dec. Combining the theoretical and experimental studies, the high ORR activity could be attributed its unique FeO-N3O structure, which facilitates effective charge transfer between the surface and the intermediates along the reaction, and uniform dispersion of this active site on thin 2D nanocarbon supports that maximize the exposure to the reactants.

Unraveling the Adsorption Behavior of Thymol on Carbon and Silica Nanospheres for Prolonged Antibacterial Activity: Experimental and DFT Studies.

Functionalization of thymol (Thy) on nanocarriers is a key step in achieving prolonged antimicrobial activity. This requires nanomaterials with uniform particle diameters and suitable thymol sorption. Herein, hollow carbon (HC) and SiO2-carbon core-shell (SiO2@C) were investigated due to their diverse morphologies and ease of surface modification. HC (14 ± 1 nm size) and SiO2@C (10 ± 1.5 nm size) were synthesized by the Stöber method before thymol was loaded by incipient wetness impregnation. Nanoparticle physicochemical properties were characterized by advanced techniques, including X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). Adsorption energies of thymol on the carbon and SiO2 surfaces were elucidated by density functional theory (DFT) simulations. Moreover, the in vitro thymol release profiles and antibacterial activity were evaluated. The experimental results indicated that the oxy-carbon surface species of HC led to longer thymol release profiles than the -OH group of SiO2@C. The DFT calculations revealed that the weaker physical interaction of thymol on HC was better for drug release than that on SiO2@C. Thus, a longer thymol release profile of HC with hollow structures showed better antibacterial performance against Gram-positive bacteria Staphylococcus aureus than that of SiO2@C with core-shell structures. This work confirms the important role of carbon morphology and specific functional groups in thymol release profiles for the further development of inhibition products.

Structural Evolution of Iron-Loaded Metal-Organic Framework Catalysts for Continuous Gas-Phase Oxidation of Methane to Methanol.

Catalytic partial oxidation of methane presents a promising route to convert the abundant but environmentally undesired methane gas to liquid methanol with applications as an energy carrier and a platform chemical. However, an outstanding challenge for this process remains in developing a catalyst that can oxidize methane selectively to methanol with good activity under continuous flow conditions in the gas phase using O2 as an oxidant. Here, we report a Fe catalyst supported by a metal-organic framework (MOF), Fe/UiO-66, for the selective and on-stream partial oxidation of methane to methanol. Kinetic studies indicate the continuous production of methanol at a superior reaction rate of 5.9 × 10-2 µmolMeOH gFe-1 s-1 at 180 °C and high selectivity toward methanol, with the catalytic turnover verified by transient methane isotopic measurements. Through an array of spectroscopic characterizations, electron-deficient Fe species rendered by the MOF support is identified as the probable active site for the reaction.

Insight into the photocatalytic reduction of hexavalent chromium using photodeposited metal nanoparticle-TiO2 photocatalysis.

Hexavalent chromium (Cr(VI)) is carcinogenic to organisms. It is widely used in several industries. In this work, we investigated the Cr(VI) photocatalytic reaction with a scavenger on Pt and Cu-TiO2 photocatalysts. Metal-deposited TiO2 was successfully synthesized by a photodeposition method. TEM-EDX, XRD, and UV-DR were analyzed to study the changes in morphology, crystallinity, and the electronic properties of photocatalysts. The rate of charge recombination during reduction and photoluminescence (PL) spectroscopy was used to examine the catalysts in depth. Cu-TiO2 demonstrates the highest photocatalytic activity for 63.74% of Cr(VI) removal. To understand the photoreduction of Cr(VI), the fate transformation of Cr species during the adsorption and reaction was investigated using in situ XANES. The results demonstrated that the Cr(III) was noticeably main component adsorbed over the catalyst, particularly in Cu-TiO2. The presence of humic acid can boost the Cr(VI) removal efficiency and enhanced the Cr(VI) reduction to Cr(III). We believe that the extensive research on Cr(VI) photoreduction on metal-TiO2 heterojunction will provide a comprehensive understanding of catalytic behaviors, paving the way for rationally designed novel Cr reduction catalysts.

Platinum/carbon dots nanocomposites from palm bunch hydrothermal synthesis as highly efficient peroxidase mimics for ultra-low H2O2 sensing platform through dual mode of colorimetric and fluorescent detection.

Detection of hydrogen peroxide and glucose in nanomolar level is crucial for point-of-care medical diagnosis. It has been reported that human's central nervous system diseases such as Alzheimer's disease, Parkinson's disease, and even amyotrophic lateral sclerosis, are presumably caused H2O2 or reactive radical species (ROS). Sensing of H2O2 released from human biofluids, tissues, organ from metabolism disorder at ultra-low concentration assists for early identification of severe diabetis mellitus related to glucose, and heart attack, as well as stroke related to cholesterol. In this work, carbon dots (CDs) having an average diameter at 6.99 nm with highly photoluminescence performance were successfully synthesized from palm empty fruit bunch (EFB) using green and environmentally friendly process via hydrothermal condition. CDs acted well on peroxidase-like activity for H2O2 detection at room temperature, however their sensitivity on ultra-low H2O2 concentration needed to be improved. To enhance their reactivity on H2O2 nanozyme activity at room temperature, synthesis of hybrid metal nanoparticles (AgNPs and PtNPs) on CDs surface was established. The findings exhibited that CDs/PtNPs was the most suitable nanozyme achieving highly efficient peroxidase mimic for dual mode of colorimetric and fluorescent H2O2 sensing platform at very low limit of detection of 0.01 mM (10 nM) H2O2.

The Role of N and S Doping on Photoluminescent Characteristics of Carbon Dots from Palm Bunches for Fluorimetric Sensing of Fe3+ Ion.

This work aims to enhance the value of palm empty fruit bunches (EFBs), an abundant residue from the palm oil industry, as a precursor for the synthesis of luminescent carbon dots (CDs). The mechanism of fIuorimetric sensing using carbon dots for either enhancing or quenching photoluminescence properties when binding with analytes is useful for the detection of ultra-low amounts of analytes. This study revealed that EFB-derived CDs via hydrothermal synthesis exceptionally exhibited luminescence properties. In addition, surface modification for specific binding to a target molecule substantially augmented their PL characteristics. Among the different nitrogen and sulfur (N and S) doping agents used, including urea (U), sulfate (S), p-phenylenediamine (P), and sodium thiosulfate (TS), the results showed that PTS-CDs from the co-doping of p-phenylenediamine and sodium thiosulfate exhibited the highest PL properties. From this study on the fluorimetric sensing of several metal ions, PTS-CDs could effectively detect Fe3+ with the highest selectivity by fluorescence quenching to 79.1% at a limit of detection (LOD) of 0.1 µmol L-1. The PL quenching of PTS-CDs was linearly correlated with the wide range of Fe3+ concentration, ranging from 5 to 400 µmol L-1 (R2 = 0.9933).