Metal Organic Frameworks as Polysulfide Reaction Modulators for Lithium Sulfur Batteries: Advances and Perspectives.

Currently, lithium sulfur (Li-S) battery with high theoretical energy density has attracted great research interest. However, the diffusion and loss process of intermediate lithium polysulfide during charge-discharge hindered the application of the Li-S battery in modern life. To overcome this issue, metal organic frameworks (MOFs) and their composites have been regarded as effective additions to restrain the LiPS diffusion process for Li-S battery. Benefiting from the unique structure with rich active sites to adsorb LiPS and accelerate the LiPS redox, the Li-S batteries with MOFs modified exhibit superior electrochemical performance. Considering the rapid development of MOFs in Li-S battery, this review summarizes the recent studies of MOFs and their composites as the sulfur host materials, functional interlayer, separator coating layer, and separator/solid electrolyte for Li-S batteries in detail. In addition, the promising design strategies of functional MOF materials are proposed to improve the electrochemical performance of Li-S battery.

Catalytic Oxidation of Toluene over Pt/CeO2 Catalysts: A Double-Edged Sword Effect of Strong Metal-Support Interaction.

Strong metal-support interaction (SMSI), which has drawn widespread attention in heterogeneous catalysis, is thought to significantly affect the catalytic performance for volatile organic chemical (VOC) abatement. In the present study, strong interactions between platinum and ceria are constructed by modulating the oxygen vacancy concentration of CeO2 through a NaBH4 reduction method. For a catalyst with higher content of oxygen vacancy, more electrons would transfer from ceria to Pt, which is attributed to the stronger effect of SMSI. The obtained electron-richer Pt sites exhibit higher ability for toluene activation, contributing to better performance for toluene oxidation. On the other hand, the stronger metal-support interaction would facilitate CeOx species migrating to the Pt nanoparticle surface and forming an encapsulated structure. Smaller Pt dispersion leads to fewer sites for toluene adsorption and activation, which is to the disadvantage of the reaction. Therefore, taking the negative and positive effects together, the Pt/CeO2-0.5 catalyst has the highest catalytic performance for toluene abatement. Our study provides new insights into strong metal-support interaction on toluene oxidation and contributes to designing noble metal catalysts for VOC abatement.

Non-Interacting Ni and Fe Dual-Atom Pair Sites in N-Doped Carbon Catalysts for Efficient Concentrating Solar-Driven Photothermal CO2 Reduction.

Solar-to-chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO2 reduction. Herein, a new concentrated solar-driven photothermal system coupling a dual-metal single-atom catalyst (DSAC) with adjacent Ni-N4 and Fe-N4 pair sites is designed for boosting gas-solid CO2 reduction with H2 O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)-N-C DSAC exhibits a superior photothermal catalytic performance for CO2 reduction to CO (86.16 µmol g-1 h-1 ), CH4 (135.35 µmol g-1 h-1 ) and CH3 OH (59.81 µmol g-1 h-1 ), which are equivalent to 1.70-fold, 1.27-fold and 1.23-fold higher than those of the Fe-N-C catalyst, respectively. Based on theoretical simulations, the Fermi level and d-band center of Fe atom is efficiently regulated in non-interacting Ni and Fe dual-atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)-N-C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni-N-N-Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO3 pathways) for solar-driven photothermal CO2 reduction to initial CO production.

The lanthanide doping effect on toluene catalytic oxidation over Pt/CeO2 catalyst.

The present work was undertaken to know the lanthanide doping effect on the physicochemical properties of Pt/CeO2 catalysts and their catalytic activity for toluene oxidation. A series of lanthanide ions (La, Pr, Nd, Sm and Gd) were incorporated into ceria lattice by hydrothermal method, and the Pt nanoparticles with equal quality were successfully loaded on various ceria-based supports. Their catalytic performance toward toluene oxidation shows a remarkable lanthanide-doping effect, and the activity is much dependent on the ion radius and valence state of dopants. Owing to smaller ion radius and low valence state, the dopant of Gd would form more Gd-Ce complex and less GdO8-type complex, generating more oxygen vacancies and then promoting oxygen replenishment. Furthermore, the high concentration of oxygen vacancy would drive electrons to transfer from support to metal, and thus electron-rich and under-coordinated Pt particles that are favorable for toluene adsorption and dissociation are obtained. Attributing to above positive factors, the doping of Gd would effectively enhance the catalytic oxidation of toluene over Pt/CeO2 catalyst. In addition, the Pt/CeGdO2 sample exhibits an excellent reaction stability and resistance of concentration impact.

A MnOx@Eu-CeOx nanorod catalyst with multiple protective effects: Strong SO2-tolerance for low temperature DeNOx processes.

A novel MnOx@Eu-CeOx catalyst with multiple protective attributes was designed and fabricated using a chemical precipitation method and tested for its low temperature SCR activity. The subject MnOx@Eu-CeOx nanorod catalyst exhibited superior SCR performance and strong SO2-tolerance. The formation of the composite-shell structure enhanced the catalysts' surface acidity and redox performance, which resulted in excellent SCR performance. Moreover, the TG results suggested that the protective effect of the EuOx-CeOx composite-shell effectively reduced the deposition of the surface sulphates. The XPS, XRD analysis results of the subject catalyst together with theoretical calculations provided strong evidence that there was a strong interaction between Mn and Ce in the MnOx@Eu-CeOx. This significant interaction could provide maximum protection to the core from the effect of SO2, which also contributed to the high SO2 resistance of the catalyst. In situ FT-IR results also indicated that the chemisorbed species on MnOx@Eu-CeOx were much more stable in the presence of SO2 compared to Eu-CeOx/MnOx, which resulted in the deposition of significantly less sulphates. This low temperature SCR catalyst with multiple protective attributes, including composite shell, strong interaction and core-shell structure, is the key to long-term resistance to SO2.