Designing robust photocatalysts with broad light absorption, effective charge separation, and sufficient reactive sites is critical for achieving efficient solar energy conversion. However, realizing these aims simultaneously through a single material modulation approach poses a challenge. Here, a 2D ultrathin oxygen vacancy (Ov)-rich Bi2W0.2Mo0.8O6 solid solution photocatalyst is designed and fabricated to tackle the dilemma through component and structure optimization. Specifically, the construction of a solid solution with ultrathin structure initially facilitates the separation of photoinduced electron-hole pairs, while the introduction of Ov strengthens such separation. In the meantime, the presence of Ov extends light absorption to the NIR region, triggering a photothermal effect that further enhances the charge separation and accelerates the redox reaction. As such, photoinduced charge carriers in the Ov-Bi2W0.2Mo0.8O6 are separated step by step via the synergistic action of 2D solid solution, OV, and solar heating. Furthermore, the introduction of OV exposes surface metal sites that serve as reactive Lewis acid sites, promoting the adsorption and activation of toluene. Consequently, the designed Ov-Bi2W0.2Mo0.8O6 reveals an enhanced photothermal catalytic toluene oxidation rate of 2445 µmol g-1 h-1 under a wide spectrum without extra heat input. The performance is 9.0 and 3.9 times that of Bi2WO6 and Bi2MoO6 nanosheets, respectively.

In order to further reduce the energy consumption of the conventional thermal catalytic oxidation system and improve the degradation efficiency of pollutants, photothermal synergistic catalytic oxidation (PTSCO) system was constructed in this paper with propane as simulated pollutant representing VOCs, and then the modified α-MnO2 catalysts were prepared by using the acid activation method, which were used for the catalytic oxidation of propane in PTSCO. The α-MnO2 with appropriate acid concentration possessed excellent low-temperature reducibility, abundant active oxygen species, fast oxygen migration rate and a large number of acid sites. The optimal catalyst, H0.05-MnO2, had a T90 of 204 °C in the PTSCO system, which reduced by more than 30 °C relative to the α-MnO2 (T90 of 235 °C). Moreover, H0.05-MnO2 demonstrated excellent water resistance and long-term stability (T = 45 h). It was shown that the combination of photocatalysis and thermocatalysis can improve propane degradation by examining the kinetics of propane degradation in the PTSCO system and the conformational relationship of propane degradation by catalysts. Furthermore, a multi-pathway synergistic mechanism between photocatalysis and thermocatalysis in the PTSCO system was proposed. This work provided a theoretical basis for the preparation of high-performance catalysts and the catalytic degradation of propane.

Advancing the energy-intensive Haber-Bosch process faces significant challenges due to the intrinsic constraints of scaling relations in heterogeneous catalysis. Herein, we reported an approach of bending the \"seesaw effect\" to regulate the scaling relations over a tailored α-Fe metallic material (α-Fe-110s), realizing highly efficient light-driven thermal catalytic ammonia synthesis rate of 1260 μmol gcatalyst-1 h-1 without additional heating. Specifically, the thermal catalytic activity of α-Fe-110s was significantly enhanced by the novel stepped {110} surface, exhibiting a 3.8-fold increase compared to the commercial fused-iron catalyst with promoters at 350 °C. The photo-induced hot electron transfer further accelerates the dinitrogen dissociation and hydrogenation simultaneously, effectively overcoming the limitation of scaling relation over identical sites. Consequently, the ammonia production rate of α-Fe-110s was further enhanced by 30 times at the same temperature with irradiation. This work designs an efficient and sustainable system for ammonia synthesis and provides a novel approach for regulating the scaling relations in heterogeneous catalysis.

The exploitation of hierarchical carbon nanocages with superior light-to-heat conversion efficiency, together with their distinct structural, morphological, and electronic properties, in photothermal applications could provide effective solutions to long-standing challenges in diverse areas. Here, we demonstrate the discovery of pristine and nitrogen-doped hierarchical carbon nanocages as superior supports for highly loaded, small-sized Ru particles toward enhanced photothermal CO2 catalysis. A record CO production rate of 3.1 mol·gRu-1·h-1 with above 90% selectivity in flow reactors was reached for hierarchical nitrogen-doped carbon-nanocage-supported Ru clusters under 2.4 W·cm-2 illumination without external heating. Detailed studies reveal that the enhanced performance originates from the strong broadband sunlight absorption and efficient light-to-heat conversion of nanocage supports as well as the excellent intrinsic catalytic reactivity of sub-2 nm Ru particles. Our study reveals the great potential of hierarchical carbon nanocages in photothermal catalysis to reduce the fossil fuel consumption of various industrial chemical processes and stimulates interest in their exploitation for other demanding photothermal applications.

The rapid development of the battery industry has brought about a large amount of waste battery pollution. How to realize the high-value utilization of waste batteries is an urgent problem to be solved. Herein, cobalt and titanium compounds (LTCO) were firstly recovered from spent lithium-ion batteries (LIBs) using the carbon thermal reduction approach, and plasmonic attapulgite/Co(Ti)Ox (H-ATP/Co(Ti)Ox) nanocomposites were prepared by the microwave hydrothermal technique. H-ATP had a large specific surface area and enough active sites to capture CO2 molecules. The biochar not only reduced the spinel phase of waste LIBs into metal oxides including Co3O4 and TiO2 but also increased the separation and transmission of the carriers, thereby accelerating the adsorption and reduction of CO2. In addition, H-ATP/Co(Ti)Ox exhibited a localized surface plasmon resonance effect (LSPR) in the visible to near-infrared region and released high-energy hot electrons, enhancing the surface temperature of the catalyst and further improving the catalytic reduction of CO2 with a high CO yield of 14.7 μmol·g-1·h-1. The current work demonstrates the potential for CO2 reduction by taking advantage of natural mineral and spent batteries.

Nowadays, it is becoming increasingly urgent to lower the escalating carbon dioxide (CO2) to reduce greenhouse effect. Fortunately, it is an ideal strategy by using the inexhaustible solar energy as the driving force to manipulate the cycloaddition reaction, the atomic efficiency of which is 100 %. This work represents the first attempt on utilization of rare-earth metal Tb with atomic dispersion, and the structure of Tb coordinated with 4 N-atoms and 2B-atoms was constructed on interconnected carbon hollow spheres. The introduction of electron-deficient B reduces the electron density of Tb, thereby boosting Lewis acidity and promoting the occurrence of ring-opening reaction. The mechanism exploration enunciates that TbN4B2/C is a photothermal synergistic catalyst, the combined action of photogenerated electrons and strong Lewis acidic site of Tb reduces the free energy of the rate-determining step, and then improving the yield of cyclic carbonate up to 739 mmol g-1h-1.

The selective hydrodeoxygenation (HDO) of sustainable lignocellulosic biomass plays a pivotal role in the conversion of biomass into high-value fuels and chemicals. Nevertheless, HDO for biomass upgrading always demands high temperatures and high hydrogen (H2) pressure. Photothermal catalysis has been recognized as an effective approach for boosting chemical reactions under mild conditions while maintaining superior selectivity. Herein, we report the design of palladium-decorated defective tungsten oxide (Pd/WO3-x) catalysts with enhanced photothermal catalytic performances for the efficient HDO of vanillin. Pd/WO3-x nanoflowers have been synthesized through a solvothermal/in-situ reduction two-step strategy, and they exhibit notable photoabsorption in a wide range (200-1100 nm), high photothermal conversion and efficient charge separation efficiency. Under simulated sunlight irradiation (0.3 W cm-2), Pd/WO3-x exhibits a maximum vanillin conversion up to 86.8 % with a 2-methoxy-4-methylphenol (MMP) selectivity of 100 %, which is obviously higher than that (vanillin conversion = 33.1 %, MMP selectivity = 100 %) in the oil bath at the same temperature. Such higher conversion efficiency and selectivity under sunlight should result from the synergistic integration of hot electrons and photothermal heating, both of which are derived from localized surface plasmon resonance (LSPR) in WO3-x. Importantly, Pd/WO3-x catalyst demonstrates good stability and high selectivity to MMP even after 5 cycles. This work may offer a novel viewpoint on the advancement of photothermal catalysts and the realization of photothermal catalytic biomass conversion under mild conditions.

Low solar energy utilization efficiency and serious charge recombination remain major challenges for photocatalytic systems. Herein, a hollow core-shell Au/g-C3N4@Ag3PO4 photothermal nanoreactor is successfully prepared by a two-step deposition method. Benefit from efficient spectral utilization and fast charge separation induced by the unique hollow core-shell heterostructure, the H2 evolution rate of Au/g-C3N4@Ag3PO4 is 16.9 times that of the pristine g-C3N4, and the degradation efficiency of tetracycline is increased by 88.1%. The enhanced catalytic performance can be attributed to the ordered charge movement on the hollow core-shell structure and a local high-temperature environment, which effectively accelerates the carrier separation and chemical reaction kinetics. This work highlights the important role of the space confinement effect in photothermal catalysis and provides a promising strategy for the development of the next generation of highly efficient photothermal catalysts.

We report a solvothermal method for the synthesis of an oxygen vacancy-enriched ZrO2 photocatalyst with Co single atoms and Ni clusters immobilized on the surface. This catalyst presents superior performance for the reduction of CO2 in H2O vapor, with a CO yield reaching 663.84 μmol g-1 h-1 and a selectivity of 99.52%. The total solar-to-chemical energy conversion efficiency is up to 0.372‰, which is among the highest reported values. The success, on one hand, depends on the Co single atoms and Ni clusters for both extended spectrum absorption and serving as dual-active centers for CO2 reduction and H2O dissociation, respectively; on the other hand, this is attributed to the enhanced photoelectric and thermal effect induced by concentrated solar irradiation. We demonstrate that an intermediate impurity state is formed by the hybridization of the d-orbital of single-atom Co with the molecular orbital of H2O, enabling visible-light-driven excitation over the catalyst. In addition, Ni clusters play a crucial role in altering the adsorption configuration of CO2, with the localized surface plasmon resonance effect enhancing the activation and dissociation of CO2 induced by visible-near-infrared light. This study provides valuable insights into the synergistic effect of the dual cocatalyst toward both efficient photothermal coupling and surface redox reactions for solar CO2 reduction.

Carbon dioxide (CO2), a member of greenhouse gases, contributes significantly to maintaining a tolerable environment for all living species. However, with the development of modern society and the utilization of fossil fuels, the concentration of atmospheric CO2 has increased to 400 ppm, resulting in a serious greenhouse effect. Thus, converting CO2 into valuable chemicals is highly desired, especially with renewable solar energy, which shows great potential with the manner of photothermal catalysis. In this review, recent advancements in photothermal CO2 conversion are discussed, including the design of catalysts, analysis of mechanisms, engineering of reactors, and the corresponding techno-economic analysis. A guideline for future investigation and the anthropogenic carbon cycle are provided.