A Fully Conjugated Covalent Organic Framework with Oxidative and Reductive Sites for Photocatalytic Carbon Dioxide Reduction with Water.

Constructing a powerful photocatalytic system that can achieve the carbon dioxide (CO2 ) reduction half-reaction and the water (H2 O) oxidation half-reaction simultaneously is a very challenging but meaningful task. Herein, a porous material with a crystalline topological network, named viCOF-bpy-Re, was rationally synthesized by incorporating rhenium complexes as reductive sites and triazine ring structures as oxidative sites via robust -C=C- bond linkages. The charge-separation ability of viCOF-bpy-Re is promoted by low polarized π-bridges between rhenium complexes and triazine ring units, and the efficient charge-separation enables the photogenerated electron-hole pairs, followed by an intramolecular charge-transfer process, to form photogenerated electrons involved in CO2 reduction and photogenerated holes that participate in H2 O oxidation simultaneously. The viCOF-bpy-Re shows the highest catalytic photocatalytic carbon monoxide (CO) production rate (190.6 µmol g-1 h-1 with about 100 % selectivity) and oxygen (O2 ) evolution (90.2 µmol g-1 h-1 ) among all the porous catalysts in CO2 reduction with H2 O as sacrificial agents. Therefore, a powerful photocatalytic system was successfully achieved, and this catalytic system exhibited excellent stability in the catalysis process for 50 hours. The structure-function relationship was confirmed by femtosecond transient absorption spectroscopy and density functional theory calculations.

Construction of ß-Bi2O3/Bi2O2CO3 heterojunction photocatalyst for deep understanding the importance of separation efficiency and valence band position.

Constructing heterojunctions would result in the change of valence band position, which is an important factor determining the oxidative ability of photo-induced holes, has received scant attention. In this paper, ß-Bi2O3/Bi2O2CO3 composites with different ratios were obtained via ionic-liquid-assisted solvothermal and in-situ calcination processes. UV-vis DRS, Mott-Schottky test, and Kelvin probe measurement showed the change of band gaps of ß-Bi2O3 and Bi2O2CO3 before and after heterojunction formation. SPV, ESR, photocurrent, and scavenger experiments identified the separation efficiency of photo-generated electrons and holes, as well as the active species generated in the photocatalytic process. The photocatalytic mechanism was investigated by the degradation of Rhodamine B (RhB) upon visible-light and simulated sunlight, respectively. The results demonstrated that ß-Bi2O3/Bi2O2CO3 heterojunctions possessed enhanced separation efficiency and higher degradation ability than the individuals under visible-light irradiation due to effective electron transfer. However, lower performance under simulated sunlight was observed, although their separation efficiency remained high. The decisive reason for this was that the up-shift of valence band of Bi2O2CO3 induced by hybridization and the transition of holes from VB of Bi2O2CO3 to that of ß-Bi2O3 with more negative potential decreased the oxidative ability of holes, which surpassed the positive influence of enhanced separation efficiency.

Low-Temperature Methane Oxidation Triggered by Peroxide Radicals over Noble-Metal-Free MgO Catalyst.

Methane is a greenhouse gas that contributes to global warming. Hence, effectively removing the low concentration (<1000 ppm) of methane in the environment is an issue that deserves research in the field of catalysis. In this study, oxygen-magnesium bivacancies are simultaneously imbedded into MgO by designing an in situ reduction combustion atmosphere for oxygen release and substituting magnesium with carbon to induce the formation of magnesium vacancies. The DFT calculations reveal that the surface electron density of MgO is improved by the oxygen vacancy structure and the substitution of Mg by C in bulk; this accelerates migration of the charge from the material surface to the adsorbed oxygen species, which leads to abundant surface peroxide species that enable activation and oxidation of methane at a low temperature (below 200 °C). This work could provide a concept for developing non-noble or transition metal oxides for low-temperature activation and conversion of alkanes in the thermocatalytic field through reactive oxygen species.