Photothermal Catalysis Research Articles

Efficient UV-Vis-NIR Responsive CO2 Reduction Photocatalyst with Black Pinecone-Shaped Carbon Nitride Loaded with Lanthanum Oxide.

Photothermal catalysis combines the advantages of photocatalysis and thermal activation, which provides a new research angle for CO2 catalytic reduction. In this study, Black carbon nitride with a three-dimensional (3D) pinecone-shaped structure (BPCN) was prepared by a simple solvothermal method using melamine as a precursor without the aid of a template. Lanthanum oxide doping on the BPCN catalysts (BPCN-La) was achieved by ultrasonic impregnation. This unique pinecone-shaped structure consists of self-assembled and interlaced carbon nitride rods (by SEM). The lanthanum element was distributed on the surface of the CN framework in the form of La2O3 (by XPS). The chemical structures of the samples were characterized by solid-state 13C nuclear magnetic resonance (13C NMR) and elaborated by density functional theory (DFT) analysis. This black carbon nitride expanded the light absorption band edge into the near-infrared (NIR) (300-1400 nm, by UV-vis absorption spectra) and had excellent photothermal conversion activity. La atom doping can significantly boost photogenerated electron excitation (by photocurrent test) and promote carrier separation and transfer (by PL). Upon incorporation of La atoms into BPCN, the highest occupied molecular orbital (HOMO) orbital is more concentrated on the oxygen atoms of La2O3. BPCN-La considerably narrowed the band gap width, exhibited an exceptional photothermal effect, and provided a large surface area, which significantly enhanced the photocatalytic reduction of CO2 reactions. The yields of CO reached 58.2 and 104.9 μmol·h-1·g-1 for BPCN and BPCN-La, respectively, with GCN as the control (6.3 μmol·h-1·g-1). Theoretical reaction pathways and selectivity for the photoreduction of CO2 on BPCN and BPCN-La were studied by DFT simulation. This work provides a new vision for the design of photothermal synergistic without extra-thermal input and full spectral response photocatalysts with high efficiency.

Photothermal Induced Dual-Interface: Accelerating Sustainable Hydrogen Evolution from Formic Acid.

Formic acid (FA), a liquid hydrogen storage carrier, can release hydrogen via photothermal catalysis, providing a clean and sustainable solution toward a carbon-neutral energy cycle. Despite recent advances in the design of efficient catalysts, the development of advanced systems with high H2 yield, stability, and durability remains challenging due to the inefficient photothermal conversion and mass transfer in the traditional liquid-solid bulk system, as well as the trade-off between hydrogen storage density and dehydrogenation rate. Here, we address these challenges by creating a photothermal-induced dual-interface characterized by high spectral absorption and low heat loss, a facile supply of FA, and vaporization of FA to minimize the energy barrier of the reaction. As a result, a record hydrogen evolution rate (200.9 mmol g-1 h-1) is achieved in a high concentration (26 M) of FA, which is about 15 times higher than the liquid-solid bulk system. In addition, it can be operated continuously for more than 192 h without additive addition and energy consumption, providing a strategy for accelerating interfacial mass transfer to improve catalytic activity, and also presents a reference for sustainable hydrogen production.

Towards Photothermal Acid Catalysts Using Eco-Sustainable Sulfonated Carbon Nanoparticles—Part II: Thermal and Photothermal Catalysis of Biodiesel Synthesis

The main goal of this work is to evaluate the ability of sulfonated carbon nanoparticles (SCNs) to induce photothermal catalysis of the biodiesel synthesis reaction (transesterification of natural triglycerides (TGs) with alcohols). Carbon nanoparticles (CNs) are produced by the carbonization of cross-linked resin nanoparticles (RNs). The RNs are produced by condensation of a phenol (resorcinol or natural tannin) with formaldehyde under ammonia catalysis (Stober method). The method produces nanoparticles, which are carbonized into carbon nanoparticles (CNs). The illumination of CNs increases the temperature proportionally (linear) to the nanoparticle concentration and exposure time (with saturation). Solid acid catalysts are made by heating in concentrated sulfuric acid (SEAr sulfonation). The application of either light or a catalyst (SCNs) (at 25 °C) induced low conversions (<10%) for the esterification reaction of acetic acid with bioethanol. In contrast, the illumination of the reaction medium containing SCNs induced high conversions (>75%). In the case of biodiesel synthesis (transesterification of sunflower oil with bioethanol), conversions greater than 40% were observed only when light and the catalyst (SCNs) were applied simultaneously. Therefore, it is possible to use sulfonated carbon nanoparticles as photothermally activated catalysts for Fischer esterification and triglyceride transesterification (biodiesel synthesis).

Nano-thermometry in photothermal catalysis

Nano-thermometry in photothermal catalysis

Corrigendum to “Heterogeneous Cu-Sn-PPy mediated synergistic photo-Fenton and photothermal catalysis for dye elimination” [Mater. Chem. Phys. 308 (2023) 128251

Corrigendum to “Heterogeneous Cu-Sn-PPy mediated synergistic photo-Fenton and photothermal catalysis for dye elimination” [Mater. Chem. Phys. 308 (2023) 128251

Strong Metal-Support Interaction Induced Excellent Performance for Photo-thermal Catalysis Methane Dry Reforming over Ru-Cluster-Ceria Catalyst

Strong Metal-Support Interaction Induced Excellent Performance for Photo-thermal Catalysis Methane Dry Reforming over Ru-Cluster-Ceria Catalyst

Photothermal Catalytic Degradation of VOCs: Mode，System and Application.

Human production and living processes emit excessive VOCs into the atmosphere, posing significant threats to both human health and the environment. The photothermal catalytic oxidation process is an organic combination of photocatalysis and thermocatalysis. Utilizing photothermal catalytic degradation of VOCs can achieve better catalytic activity at lower temperatures, resulting in more rapid and thorough degradation of these compounds. Photothermal catalysis has been increasingly applied in the treatment of atmospheric VOCs due to its many advantages. A brief introduction on the three modes of photothermal catalysis is presented. Depending on the main driving force of the reactions, they can be categorized into thermal-assisted photocatalysis (TAPC),photo-assisted thermal catalysis (PATC) and photo-driven thermal catalysis (PDTC). The commonly used catalyst design methods and reactor types for photothermal catalysis are also briefly introduced. This paper then focuses on recent developments in specific applications for photothermal catalytic oxidation of different types of VOCs and their corresponding principles. Finally, the problems and challenges facing VOC degradation through this method are summarized, along with prospects for future research.

Plasmonic Copper‐Ruthenium Superstructure for Efficient Photothermal Conversion and Plastic Recycling

AbstractPlasmonic superstructures offer broad prospects in photothermal catalysis, yet their controllable synthesis remains a challenge. Here, a controlled synthesis method for Cu‐Ru plasmonic superstructures via a one‐step polyol reduction process is presented, where Cu nanoparticles serve as the core, while the shell is formed from Ru nanoclusters. Through a comprehensive investigation of the growth mechanism, precise control over the composition and size of the superstructures is achieved. Finite‐difference time‐domain simulations and photothermal conversion experiments demonstrated that the optimized Cu3Ru1 superstructures possess strong light absorption capabilities and efficient photothermal conversion performance. These properties are effectively utilized in the photothermal recycling of waste polyethylene and polyethylene terephthalate, marking a significant advance in employing Cu‐based plasmonic materials for sustainable catalytic technology.

Photothermal synergistic catalytic oxidation mechanism of toluene by Ce-doped SrTiO3 via one-pot hydrothermal synthesis

Industrial volatile organic compounds (VOCs) emissions pose significant environmental and human health risks, with photothermal catalysis degradation emerging as a promising VOCs treatment technology. The light response range and catalysis degradation efficiency of photocatalysts, however, need to be improved. This study prepared Ce-doped SrTiO3 perovskite catalysts via a one-pot hydrothermal method. The synergistic photic/thermal degradation mechanism of toluene was uncovered via XPS, Uv–Vis, EPR, and in-situ DRIFTS analysis. It was found that the toluene removal rate and CO2 yield reached their maximums at 200 °C, reaching 95 % and 90 %, respectively, at a Ce doping ratio of 50 %. During the catalytic process, the prerequisite to trigger toluene oxidation, and light promote the generation of reactive oxygen species (·OH and ·O2–), which facilitates the formation of intermediates and thus accelerates the deep oxidation of toluene. The doped Ce increases surface oxygen vacancies while lowering the energy band gap of the catalyst, facilitating the separation of holes and photogenerated electrons. Furthermore, in situ DRIFTS studies demonstrated that toluene undergoes a ring-opening process, producing intermediates such as benzaldehyde and benzoic acid. This study will assist in promoting the use of photothermal synergistic catalytic degradation technology to remove VOCs from industrial sources.

Light-driven methanol-to-olefins catalysis over W18O49/SAPO-34 hierarchical nanocomposite with strong photothermal effect

Solar-light-driven photothermal catalysis attracts attention because of the significant energy savings and environmental friendliness compared with thermal catalysis. In the present work, W18O49/SAPO-34 composite materials with hierarchical pore networks were constructed by a simple hydrothermal method, and applied into photothermal catalysis for methanol-to-olefins transformation. In combination of the broaden light absorption of W18O49 and moderate acid site of SAPO-34, the W18O49/SAPO-34 composite showed a rapid temperature rise on the surface of the catalysts due to the strong photo-to-thermal effect of W18O49. Methanol conversion of ∼ 90 % and ethylene selectivity of ∼ 60 % were achieved for the optimized W18O49/SAPO-34 catalyst, much higher than that of bare W18O49 and SAPO-34. The excellent methanol dehydration performance was attributed to the strong plasmonic absorption in the visible and near infrared light, the efficient photothermal conversion effect by localized plasmon heating on the W18O49 nanorods, and synergistic catalysis between W18O49 and SAPO-34. This photothermal catalyst showed great potential in the industrial applications of photocatalytic methanol-to-olefins conversion.

Generation of oxygen vacancies in CuO/TiO2 heterojunction induced by diatomite for highly efficient UV–Vis-IR driven photothermal catalytic oxidation of HCHO

Photothermal catalytic oxidation is a promising and sustainable method for the degradation of indoor formaldehyde (HCHO). However, the excessively high surface temperature of existing photothermal catalysts during catalysis hinders the effective adsorption and degradation of formaldehyde under static conditions. Catalyst loading and oxygen vacancies (OVs) modulation are commonly employed strategies to reduce the photothermal catalytic temperature and enhance the efficiency of photothermal catalytic oxidation. In this work, a p-n type CuO/TiO2 heterojunction is successfully loaded onto diatomite using a wet precipitation method. Under the irradiation of a 300W xenon lamp, the prepared composite material achieved a 100% removal rate of HCHO within 2 h, with a 98% conversion rate to CO2, surpassing the performance of both individual photocatalysts and thermocatalysts. Additionally, by adjusting conditions such as light irradiation and temperature, we have demonstrated that this material exhibits synergistic photothermal catalytic properties. Based on HRTEM, XPS, Raman, and EPR analyses, the introduction of diatomite as a catalyst support was shown to effectively increase the number of OVs. Experimental results, along with O2-TPD, photoelectrochemical characterization, and radical detection, demonstrate that the presence of OVs enhances the oxidative efficiency of both photocatalysis and thermocatalysis, as well as the UV–Vis-IR photothermal catalytic performance. The ternary composite material generates weak hydroxyl (•OH) and superoxide (•O2−) radical under high-temperature with dark conditions, indicating its catalytic oxidation activity under this condition. The increase in temperature and the expansion of the spectral range both enhance the generation of these radicals. In summary, this work demonstrates that the use of diatomite as a support increases the material's specific surface area and OVs content, thereby enhancing adsorption and photothermal catalysis. It elucidates the enhanced catalytic degradation mechanism of this mineral-based photothermal catalyst.

Photothermal Oxidation of Volatile Organic Compounds Over Co3O4‐Based Inverse Opal

AbstractThe growing preference for photothermal catalysis stems from its minimal energy consumption and heightened catalytic efficacy. Nonetheless, material photon utilization efficiency is frequently hindered by catalyst structural design constraints and bandgap limitations. Herein, we present a Co3O4‐based inverse opal featuring a three‐dimensional ordered macroporous (3DOM‐Co3O4) architecture tailored for photothermal VOCs oxidation. The 3DOM‐Co3O4 exhibits superior catalytic performance in carbon monoxide oxidation, methane oxidation, and toluene oxidation, with a photothermal enhancement of more than 100 %. Further experimental and theoretical analyses reveal that the three‐dimensional periodic array of pores facilitates the slow photon effect, augmenting the light absorption capabilities of the catalyst. Thus, it generates more photoexcited electrons, promoting VOCs molecular activation. Additionally, the well‐ordered porous structure facilitates the diffusion of reactants and products, further accelerating the catalytic reaction. This work highlights promising prospects for leveraging inverse opals as an innovative strategy towards enhancing photothermal catalytic VOCs oxidization efficiency.

Photothermal Effect and Fenton‐Like Oxidation for Synergistic Removal of Fluoroquinolones Antibiotics under Near‐Neutral Conditions

AbstractDefect‐enriched mesoporous CuO nanosheets (NSs) were constructed to investigate the cooperative photo‐Fenton and photothermal‐Fenton catalysis on degradation of fluoroquinolones (FQ) antibiotics. The oxygen vacancies provide abundant active sites to bind the substrates and inhibit charge recombination, by all means to enhance Fenton‐like activity. Two disparate spectral selective functions of photoexcitation and photothermal conversion were achieved on CuO NS, which to promote the Fenton activity synergistically. Visible light induced photoexcitation to facilitate the generation of Cu+ and ⋅OH, while near‐infrared light converted into heat to promote charge separation and accelerate medium transport. Ultimately, as a unitary catalyst system, the CuO NS integrated the Lewis acid catalysis, Fenton‐like catalysis and photothermal catalysis that rapidly and sustainably degraded antibiotics under near‐neutral conditions.

Optically selective catalyst design with minimized thermal emission for facilitating photothermal catalysis

Converting solar energy into fuels is pursued as an attractive route to reduce dependence on fossil fuel. In this context, photothermal catalysis is a very promising approach through converting photons into heat to drive catalytic reactions. There are mainly three key factors that govern the photothermal catalysis performance: maximized solar absorption, minimized thermal emission and excellent catalytic property of catalyst. However, the previous research has focused on improving solar absorption and catalytic performance of catalyst, largely neglected the optimization of thermal emission. Here, we demonstrate an optically selective catalyst based Ti3C2Tx Janus design, that enables minimized thermal emission, maximized solar absorption and good catalytic activity simultaneously, thereby achieving excellent photothermal catalytic performance. When applied to Sabatier reaction and reverse water-gas shift (RWGS) as demonstrations, we obtain an approximately 300% increase in catalytic yield through reducing the thermal emission of catalyst by ~70% under the same irradiation intensity. It is worth noting that the CO2 methanation yield reaches 3317.2 mmol gRu−1 h−1 at light power of 2 W cm−2, setting a performance record among catalysts without active supports. We expect that this design opens up a new pathway for the development of high-performance photothermal catalysts.

Comprehensive Insight into Indium Oxide‐Based Catalysts for CO2 Hydrogenation: Thermal, Photo, and Photothermal Catalysis

Comprehensive Insight into Indium Oxide‐Based Catalysts for CO₂ Hydrogenation: Thermal, Photo, and Photothermal Catalysis

Constructing homo/hetero-nuclear carbon and oxygen atoms co-doped graphitic carbon nitride assisted by ionic liquid for photothermal synergistic catalytic oxidation of cyclohexane

The adoption of photothermal synergistic catalysis for cyclohexane oxidation can balance the advantages of high conversion of thermal catalysis and high selectivity of photocatalytic technology to achieve better catalytic performance. Here, we prepared functional carbon nitride (BCA-CN) by self-assembly strategy of ionic liquid [Bmim]CA (1-Butyl-3-methylimidazole citrate) with melamine and cyanuric acid utilizing abundant elements and anionic/cationic hydrogen bonding interactions. The introduction of [Bmim]CA embeds C-C (carbon and carbon band) and C-O-C (ether bond) structures into graphitic carbon nitride (g-C3N4) framework, significantly improving light absorption capacity and migration of photo generated charge carriers. Compared to g-C3N4, both BCA-CN increases cyclohexane conversion and KA oil (the mixture of cyclohexanol and cyclohexanone) selectivity by 1.3 times under photothermal catalysis. The surface reactions are facilitated by changing adsorption sites of cyclohexane to increase adsorption energy and obtaining more hydroxyl radicals and superoxide radicals. Furthermore, the enhanced selectivity is attributed to the difficulty in generating cyclohexanone radicals. This work offers the reference scheme for the development of efficient photothermal catalysts in the selective oxidation of cyclohexane.

Promoting photothermal catalytic N2 reduction through dynamic mass transfer and accelerated charge transfer dynamics

The effective adsorption and mass transfer of N2 at the catalytic active site, along with efficient photogenerated charge transfer at the interface are the prerequisites for the photothermal catalysis N2 reduction. Here, the hydrophobic-hydrophilic biphasic heterojunction Bi2WO6/ Bi2Sn2O7 (BWSO-20) was prepared by solvothermal method, and a strong interfacial internal electric field (IEF) was formed. The effects of N2 dynamic mass transfer and interface charge transfer kinetics on the performance of photothermal catalytic N2 reduction (PTC-NRR) was investigated. The results from in-suit DRIFTS, DFT, and molecular dynamics simulations (MD) indicated that a biphasic structure enhanced the dynamic mass transfer of N2 in the hydrophobic phase (BSO) and H2O in the hydrophilic phase (BWO) simultaneously. Additionally, the IEF that accelerates the transfer kinetics of photo-generated charges. Therefore, more photo-generated electrons and holes could transfer to the surface of the hydrophobic/hydrophilic phase catalyst and undergo redox semi-reactions with N2 and H2O. The PTC-NRR reached 366.1 μmoL·g−1 when using BWSO-20 without adding sacrificial agent. This work provides a new way to achieve efficient photothermal N2 reduction based on the interfacial charge transfer kinetics accelerated by the interfacial internal electric field and the dynamic mass transfer enhanced by hydrophobic – hydrophilic two-phase heterojunction.

Ferrocene Derivatives for Photothermal Applications.

Ferrocene (Fc) and Fc derivatives have gained popularity in recent years due to their unique structure and characteristics. Among Fc's diverse performances, photothermal conversion, as a primary source of energy conversion, has sparked substantial study attention. This Review summaries Fc and Fc derivatives with photothermal characteristics, as well as their applications developed recently. First, methods for the synthesis of Fc-based materials are systematically discussed. Then, the photothermal conversion mechanism based on nonradiative relaxation is summarized. Furthermore, the most recent advances in Fc-based materials in photothermal applications are described, including photothermal degradation, photothermal antibacterial, photothermal therapies, photothermal catalysis, solar-driven water production, and photothermal CO2 separation. Finally, a summary and insights on the photothermal application of Fc-based materials are provided. This paper seeks to provide researchers with a better knowledge of photothermal behavior while also highlighting the potential of Fc and its derivatives in photothermal fields.

Efficient solar-driven: Photothermal catalytic reduction of atmospheric CO2 at the gas-solid interface by CuTCPP/MXene/TiO2

Directly capturing atmospheric CO2 and converting it into valuable fuel through photothermal synergy is an effective way to mitigate the greenhouse effect. This study developed a gas–solid interface photothermal catalytic system for atmospheric CO2 reduction, utilizing the innovative photothermal catalyst (Cu porphyrin) CuTCPP/MXene/TiO2. The catalyst demonstrated a photothermal catalytic performance of 124 μmol·g−1·h−1 for CO and 106 μmol·g−1·h−1 for CH4, significantly outperforming individual components. Density functional theory (DFT) results indicate that the enhanced catalytic performance is attributed to the internal electric field between the components, which significantly enhances carrier utilization. The introduction of CuTCPP reduces free energy of the photothermal catalytic reaction. Additionally, the local surface plasmon resonance (LSPR) effect and high-speed electron transfer properties of MXene further boost the catalytic reaction rate. This well-designed catalyst and catalytic system offer a simple method for capturing atmospheric CO2 and converting it in-situ through photothermal catalysis.

A Comprehensive Review of Solar Photocatalysis & Photothermal Catalysis for Hydrogen Production from Biomass: from Material Characteristics to Engineering Application.

Biomass photoreforming is a promising way of producing sustainable hydrogen thanks to the abundant sources of biomass feedstocks. Solar energy provides the heat and driven force to initial biomass oxidation coupled with H2 evolution. Currently, biomass photoreforming is still far from plant-scale applications due to the lower solar energy utilization efficiencies, the low H2 yield, and the lack of appropriate photoreactors. The production of H2 from photoreforming of native biomass and platform molecules was summarized and discussed with particular attention to the prospects of scaling up the catalysis technology for mass hydrogen production. The types of photoreforming, including photocatalysis and photothermal catalysis, were discussed, consequently considering the different requirements for photoreactors. We also reviewed the photoreactors that support biomass photoreforming. Numerical simulation methods were implemented for the solid-liquid two-phase flow and inter-particle radiative transfer involved in the reaction process. Developing concentrated photothermal catalytic flowed reactors is beneficial to scale-up catalytic hydrogen production from biomass.