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[Display omitted] The difficulty of achieving both high conversion rate and high selectivity is a huge challenge in the catalytic aerobic oxidation of cyclohexane. In this paper, bismuth tungstate-bismuth oxychloride (Bi 2 WO 6 -BiOCl) nanoflower heterojunctions prepared via a one-step solvothermal process were applied in the photo-thermo synergetic catalytic oxidation of cyclohexane in the dried air. With the addition of little water at different reaction temperature, the ratio of bismuth to tungsten and the mass ratio of Bi 2 WO 6 to BiOCl can be precisely tailored in the nanoflower sphere composites with thin nanosheets. Their microscopic morphology, elemental composition, crystal structure, and photoelectrochemical characteristics were explored by different characterization methods. The Bi 2 WO 6 -BiOCl composites possessed poor photocatalytic and thermal performances with the low conversion rates of 1.43% and 2.68%, respectively. However, through the photo-thermo catalytic oxidation process, an exceptional conversion rate of 13.32% was achieved with excellent selectivity of 99.22% for cyclohexanone and cyclohexanol (KA oil) using the same Bi 2 WO 6 -BiOCl composites. This superior performance outstrips Bi 2 WO 6 flowers, BiOCl nanosheets and Bi 2 WO 6 -BiOCl composites with other compounding ratios. The creation of a high-low heterojunction in the Bi 2 WO 6 -BiOCl composite was confirmed by band energy analysis. The opto-electronic analysis, band energy analysis, sacrifice experiments, and active radical analysis were employed to elucidate the mechanism for the exceptional photo-thermo catalytic performance in detail. This work offers an exploratory solution to the challenges of high energy consumption and the difficulty in simultaneously achieving high selectivity and high conversion rates in cyclohexane oxidation, thus holding significant value. [ABSTRACT FROM AUTHOR]

Photo‐thermo catalysis utilizing light has been a promising strategy to improve the conventional thermal catalytic activity and attracts great attention nowadays. However, how heat works in synergy with light radiation is still unclear. This Concept article is trying to clarify the specific contents via summarizing the kinetic studies including 1) proposing elementary steps through pressure dependence studies, 2) estimating reaction barriers through measuring the apparent activation energies and 3) assigning the kinetically relevant step(s) with kinetic isotope effects (KIE) as well as 4) exploring the relationship of the reaction rate with the light excitation wavelength and light intensity. The challenges in kinetic studies such as describing the light‐induced carrier transfer process, the surface temperature under light illumination as well as reaction intermediates were discussed at the same time. Finally, an outlook about kinetic studies in clarifying the photo‐thermo catalysis reaction mechanism was proposed. [ABSTRACT FROM AUTHOR]

In this study, a transition metal-based perovskite oxide catalyst with high CH3OH yield was successfully developed. The A-site substitution by Pr3+ in La1-xPrxMn0.6Ni0.4O3-δ can effectively adjust the activity of the perovskite catalysts for the direct conversion of CO2 and H2O into hydrocarbon fuels, especially CH3OH. Based on the designed photo-thermo synergetic photosynthesis strategy, the first hour CH3OH yield of La1-xPrxMn0.6Ni0.4O3-δ reached 3.97 mmol g−1, while only 0.24 μmol g−1 under normal photocatalysis mode. The synergistic photo-thermo catalysis was demonstrated to be a promising strategy for the future artificial photosynthesis development.

• WO 3 -Co 3 O 4 composites were prepared by controlling the growth of Co 3 O 4 nanoparticles on WO 3 nanorods. • The Z-scheme WO 3 -Co 3 O 4 heterojunction leads to the boosted charge separation and the promoted catalytic performance. • The extended visible light absorption is acquired by WO 3 -Co 3 O 4 composites. • The high conversion of 11.46% with high selectivity of 99.12% is achieved by WO 3 -Co 3 O 4 composites. The selective catalytic oxidation of cyclohexane has important scientific research significance and application value in the field of heterogeneous catalysis. However, it is difficult for traditional catalytic systems to balance high conversion and high selectivity with convenient catalyst separation. In this study, Z-scheme WO 3 -Co 3 O 4 composites are conceived and synthesized through controlled growth of Co 3 O 4 square nanoparticles on WO 3 nanorods for the boosted photo-thermo catalytic performance in the cyclohexane oxidation. The morphology structure, interface chemical bonding and photoelectrochemical properties of WO 3 -Co 3 O 4 composites are investigated by various means of characterizations. The WO 3 - Co 3 O 4 composites present significantly increased catalytic performance than WO 3 nanorods and Co 3 O 4 nanoparticles in the photo-thermo synergistic catalytic oxidation of cyclohexane under dry air. The high conversion rate of 11.46% with a KA oil selectivity of 99.12% was achieved using WO 3 -Co 3 O 4 300 composite catalyst, which is 2.33 times that of WO 3 nanorods and 1.24 times that of Co 3 O 4 nanoparticles under the same catalytic conditions. The effect of reaction temperature and proportions of WO 3 -Co 3 O 4 on the catalytic performances have been comparatively surveyed. Furthermore, energy band structure analyses and sacrificial trap experiments elucidate the Z-scheme charge transfer mode in WO 3 -Co 3 O 4 composites to enhance the photo-thermo catalytic performance in cyclohexane oxidation. [Display omitted] [ABSTRACT FROM AUTHOR]

Kinetics, light contribution, photo-thermo catalysis, rate-determining step, reaction mechanism Keywords: kinetics; light contribution; photo-thermo catalysis; rate-determining step; reaction mechanism EN kinetics light contribution photo-thermo catalysis rate-determining step reaction mechanism 1 1 1 09/08/22 20220906 NES 220906 B Different kinetic studies b are summarized for helping to get deeper insight in the understanding of photo-thermo catalysis. Frontispiece: Determining the Reaction Mechanisms of Photo-Thermo Synergetic Processes by Kinetic Investigations. [Extracted from the article]

In this study, a transition metal-based perovskite oxide catalyst with high CH 3 OH yield was successfully developed. The A-site substitution by Pr3+ in La 1-x Pr x Mn 0.6 Ni 0.4 O 3-δ can effectively adjust the activity of the perovskite catalysts for the direct conversion of CO 2 and H 2 O into hydrocarbon fuels, especially CH 3 OH. Based on the designed photo-thermo synergetic photosynthesis strategy, the first hour CH 3 OH yield of La 1-x Pr x Mn 0.6 Ni 0.4 O 3-δ reached 3.97 mmol g−1, while only 0.24 μmol g−1 under normal photocatalysis mode. The synergistic photo-thermo catalysis was demonstrated to be a promising strategy for the future artificial photosynthesis development. [Display omitted] • In this study, a transition metal-based perovskite oxide catalyst with high CH 3 OH yield was developed. • The total carbon conversion rate can reach 6.73% with photo-thermo photosynthesis method. • The catalyst of La 1-x Pr x Mn 0.6 Ni 0.4 O 3-δ possesses abundant oxygen vacancies as active sites of CH 3 OH. [ABSTRACT FROM AUTHOR]