Kaixin Li

One-pot transformation of cellobiose to formic acid and levulinic acid over ionic-liquid-based polyoxometalate hybrids.

Currently, levulinic acid (LA) and formic acid (FA) are considered as important carbohydrates for the production of value-added chemicals. Their direct production from biomass will open up a new opportunity for the transformation of biomass resource to valuable chemicals. In this study, one-pot transformation of cellobiose into LA and FA was demonstrated, using a series of multiple-functional ionic liquid-based polyoxometalate (IL-POM) hybrids as catalytic materials. These IL-POMs not only markedly promoted the production of valuable chemicals including LA, FA and monosaccharides with high selectivities, but also provided great convenience of the recovery and the reuse of the catalytic materials in an environmentally friendly manner. Cellobiose conversion of 100%, LA selectivity of 46.3%, and FA selectivity of 26.1% were obtained at 423 K and 3 MPa for 3 h in presence of oxygen. A detailed catalytic mechanism for the one-pot transformation of cellobiose was also presented.

Titania-Supported gold nanoparticles as efficient catalysts for the oxidation of cellobiose to organic acids in aqueous medium

Titania‐supported gold nanoparticles were prepared by using the deposition–precipitation method, followed by reduction under a hydrogen flow. The catalytic activity of these as‐prepared catalysts was explored in the oxidation of cellobiose to gluconic acid with molecular oxygen, and the properties of these catalysts were examined by using XRD, TEM, temperature‐programmed desorption of NH3, energy‐dispersive X‐ray spectroscopy, UV/Vis, and X‐ray photoemission spectroscopy (XPS). The catalyst sample reduced at high temperature demonstrated an excellent catalytic activity in the oxidation of cellobiose. The characterization results revealed the strong metal–support interaction between the gold nanoparticles and titania support. Hydrogen reduction at higher temperatures (usually >600 °C) plays a vital role in affording a unique interface between gold nanoparticles and titania support surfaces, which thus improves the catalytic activity of gold/titania by fine‐tuning both the electronic and structural properties of the gold nanoparticles and titania support.

Mechanistic and kinetic studies on biodiesel production catalyzed by an efficient pyridinium based ionic liquid

Biodiesels produced from renewable sources exhibit superior fuel properties and renewability and they are more environmentally friendly than petroleum-based fuels. In this paper, a three-step transesterification, catalyzed by a pyridinium-based Bronsted acidic ionic liquid (BAIL), for biodiesel production was investigated using density functional theory (DFT) calculations at the B3LYP/6-311++G(d) level. The DFT results elucidate the detailed catalytic cycle, which involves the formation of a covalent reactant–BAIL–(methanol)n (n = 1/3) intermediate and two transition states. Hydrogen bond interactions were found to exist throughout the process of the catalytic cycle, which are of special importance for stabilizing the intermediate and transition states. Thus, a mechanism involving cooperative hydrogen bonding for BAIL-catalyzed biodiesel production was established. The Gibbs free energy profile based on the above mechanism was validated by the subsequent kinetic study. The trend of activation energy from kinetic mathematical models was reasonably consistent with that obtained from the DFT calculations.

Heterojunction-Assisted Co3S4@Co3O4 Core–Shell Octahedrons for Supercapacitors and Both Oxygen and Carbon Dioxide Reduction Reactions

Expedition of electron transfer efficiency and optimization of surface reactant adsorption products desorption processes are two main challenges for developing non-noble catalysts in the oxygen reduction reaction (ORR) and CO2 reduction reaction (CRR). A heterojunction prototype on Co3 S4 @Co3 O4 core-shell octahedron structure is established via hydrothermal lattice anion exchange protocol to implement the electroreduction of oxygen and carbon dioxide with high performance. The synergistic bifunctional catalyst consists of p-type Co3 O4 core and n-type Co3 S4 shell, which afford high surface electron density along with high capacitance without sacrificing mechanical robustness. A four electron ORR process, identical to the Pt catalyzed ORR, is validated using the core-shell octahedron catalyst. The synergistic interaction between cobalt sulfide and cobalt oxide bicatalyst reduces the activation energy to convert CO2 into adsorbed intermediates and hereby enables CRR to run at a low overpotential, with formate as the highly selective main product at a high faraday efficiency of 85.3%. The remarkable performance can be ascribed to the synergistic coupling effect of the structured co-catalysts; heterojunction structure expedites the electron transfer efficiency and optimizes surface reactant adsorption product desorption processes, which also provide theoretical and pragmatic guideline for catalyst development and mechanism explorations.

Hydrothermally driven three-dimensional evolution of mesoporous hierarchical europium oxide hydrangea microspheres for non-enzymatic sensors of hydrogen peroxide detection

Hydrothermal synthesis of mesoporous europium oxide hierarchical hydrangea microspheres for electrochemical detection of hydrogen peroxide (H2O2) has been successfully achieved. The as-prepared stable enzyme-free sensor is capable of performing H2O2 detection in a broad linear range, with high sensitivity, a remarkably low detection limit and rapid response.

Understanding the role of hydrogen bonding in Brønsted acidic ionic liquid-catalyzed transesterification: a combined theoretical and experimental investigation

Brønsted acidic ionic liquids (BAILs) can play a dual role, as a solvent and as a catalyst, in many reactions. However, molecular details of the catalytic mechanism are poorly understood. We present here a density functional theory (DFT) study for the catalytic mechanism of the transesterification of methyl ester (ME) with trimethylolpropane (TMP), in the presence of three representative BAILs, namely, N-methylimidazole-IL, pyridinium-IL, and triethylamine-IL. The deprotonation of the BAIL cation and the transesterification step are investigated. Key inter- and intra-molecular hydrogen bonds (HBs) that govern the catalytic performance of BAILs were identified and analyzed using natural bond orbital (NBO) and atoms in molecule (AIM) methods. For the deprotonation of BAILs, it was found that the intermolecular O-HO HB between the hydroxyl group of TMP and the oxygen of the sulfonic group of BAIL was indispensable for proton transfer. DFT computed free energy barriers for the transesterification step are in excellent agreement with the experimental results only after taking into account the BAIL cation-anion interaction in terms of HBs in which the O-HO between the hydroxyl group of the anion and the oxygen of the sulfonic group of the cation was the strongest HB, suggesting the role of the anion in governing the catalytic activity of BAILs. The existence of the HBs suggested by DFT calculations was further validated using in situ FTIR experiments/ATR-FTIR.