Efficient Photothermal Catalytic Oxidation Enabled by Three-Dimensional Nanochannel Substrates.

Photothermal catalysis exhibits promising prospects to overcome the shortcomings of high-energy consumption of traditional thermal catalysis and the low efficiency of photocatalysis. However, there is still a challenge to develop catalysts with outstanding light absorption capability and photothermal conversion efficiency for the degradation of atmospheric pollutants. Herein, we introduced the Co3O4 layer and Pt nanoclusters into the three-dimensional (3D) porous membrane through the atomic layer deposition (ALD) technique, leading to a Pt/Co3O4/AAO monolithic catalyst. The 3D ordered nanochannel structure can significantly enhance the solar absorption capacity through the light-trapping effect. Therefore, the embedded Pt/Co3O4 catalyst can be rapidly heated and the O2 adsorbed on the Pt clusters can be activated to generate sufficient O2- species, exhibiting outstanding activity for the diverse VOCs (toluene, acetone, and formaldehyde) degradation. Optical characterization and simulation calculation confirmed that Pt/Co3O4/AAO exhibited state-of-the-art light absorption and a notable localized surface plasmon resonance (LSPR) effect. In situ diffuse reflectance infrared Fourier transform spectrometry (in situ DRIFTS) studies demonstrated that light irradiation can accelerate the conversion of intermediates during toluene and acetone oxidation, thereby inhibiting byproduct accumulation. Our finding extends the application of AAO's optical properties in photothermal catalytic degradation of air pollutants.

Strain-Engineering of Mesoporous Cs3 Bi2 Br9 /BiVO4 S-Scheme Heterojunction for Efficient CO2 Photoreduction.

Slow charge kinetics and unfavorable CO2 adsorption/activation strongly inhibit CO2 photoreduction. In this study, a strain-engineered Cs3 Bi2 Br9 /hierarchically porous BiVO4 (s-CBB/HP-BVO) heterojunction with improved charge separation and tailored CO2 adsorption/activation capability is developed. Density functional theory calculations suggest that the presence of tensile strain in Cs3 Bi2 Br9 can significantly downshift the p-band center of the active Bi atoms, which enhances the adsorption/activation of inert CO2 . Meanwhile, in situ irradiation X-ray photoelectron spectroscopy and electron spin resonance confirm that efficient charge transfer occurs in s-CBB/HP-BVO following an S-scheme with built-in electric field acceleration. Therefore, the well-designed s-CBB/HP-BVO heterojunction exhibits a boosted photocatalytic activity, with a total electron consumption rate of 70.63 µmol g-1 h-1 , and 79.66% selectivity of CO production. Additionally, in situ diffuse reflectance infrared Fourier transform spectroscopy reveals that CO2 photoreduction undergoes a formaldehyde-mediated reaction process. This work provides insight into strain engineering to improve the photocatalytic performance of halide perovskite.

Constructing Highly Active Metal Oxides for Toluene Degradation by Fenton Iron Mud Modulation.

Fenton iron mud (IM) is a hazardous solid waste produced by Fenton oxidation technology after treating industrial wastewater. Thus, it is necessary and challenging to develop a recycling technology to back-convert dangerous materials into useful products. Herein, we develop a sustainable approach to prepare highly active metal oxides via a solid-state grinding method. IM, as an amorphous material, can disperse and interact well with these supported metal oxides, boosting toluene degradation significantly. Among these IM-based catalysts, the catalyst 8% MnOx/IM-0.2VC exhibits the best performance (T100 = 290 °C), originating from the oxide-support interaction and optimal balance between low-temperature reducibility and oxygen vacancy concentration. In addition, in situ diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) results expound that ring breakage is prone to occur on MnOx, and oxygen vacancies are beneficial to adsorb oxygen and activate oxygen species to boost toluene oxidation following the Mars-van Krevelen mechanism. This work advances a complete industrial hazardous waste recycling route to develop extremely active catalysts.

Quenching-Induced Defect-Rich Platinum/Metal Oxide Catalysts Promote Catalytic Oxidation.

Enhancing oxygen activation through defect engineering is an effective strategy for boosting catalytic oxidation performance. Herein, we demonstrate that quenching is an effective strategy for preparing defect-rich Pt/metal oxide catalysts with superior catalytic oxidation activity. As a proof of concept, quenching of α-Fe2O3 in aqueous Pt(NO3)2 solution yielded a catalyst containing Pt single atoms and clusters over defect-rich α-Fe2O3 (Pt/Fe2O3-Q), which possessed state-of-the-art activity for toluene oxidation. Structural and spectroscopic analyses established that the quenching process created abundant lattice defects and lattice dislocations in the α-Fe2O3 support, and stronger electronic interactions between Pt species and Fe2O3 promote the generation of higher oxidation Pt species to modulate the adsorption/desorption behavior of reactants. In situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) characterization studies and density functional theory (DFT) calculations determined that molecular oxygen and Fe2O3 lattice oxygen were both activated on the Pt/Fe2O3-Q catalyst. Pt/CoMn2O4, Pt/MnO2, and Pt/LaFeO3 catalysts synthesized by the quenching method also offered superior catalytic activity for toluene oxidation. Results encourage the wider use of quenching for the preparation of highly active oxidation catalysts.

Quenching-induced surface modulation of perovskite oxides to boost catalytic oxidation activity.

Quenching is a powerful method for modulating surface structures of metal oxide nanocatalysts to achieve high catalytic oxidation activities, but it is still challenging. Herein, a catalyst of ultrafine Co3O4 nanoparticles decorated on Co-doped LaMnO3 (Co3O4/LaCoxMn1-xO3) is synthesized via one-step quenching perovskite-type LaMnO3 nanocatalyst into an aqueous solution of cobalt nitrate, which exhibits significantly improved catalytic performance with toluene (1000 ppm) conversion of 90% at 269 °C under the gas hourly space velocity of 72000 mL g-1 h-1. The high catalytic activity correlates with large surface area, abundant oxygen vacancies and good reducibility. Furthermore, density functional theory calculations disclose that Co doping and interfacial effect of Co3O4/LaCoxMn1-xO3 can achieve lower C-H bond activation energy. These findings provide a unique and effective route towards surface modification of nanocatalysts.