Progress and Prospect of Photothermal Catalysis

Recently, solar-driven synthesis due to its energy-saving and environmentally friendly advantages has attracted more and more attention, whereas the low solar-to-chemical conversion efficiency significantly hindered its development. New effective options that fully utilize full-band sunlight are urgently needed. Novel photothermal catalysis combined with the advantages of photocatalysis and thermalcatalysis can improve the utilization efficiency of solar energy and lower the reaction temperature, thus becoming a promising technology. This review divides photothermal catalysis into photo-assisted thermalcatalysis, thermal-assisted photocatalysis, and photothermal synergistic catalysis. Furthermore, the catalytic mechanical understanding of how photothermal affects the catalytic property of different applications(e.g., water splitting, CO₂/N₂ reduction, and environmental treatment) was also summed up and discussed in detail. The discussion ends with unsolved challenges in photothermal catalysis, particularly emphasizing the effect of temperature or sunlight on catalytic performance.     

光热效应增强的Au/RGO/Na2Ti3O7光催化加氢性能

将典型的光热等离激元石墨烯和纳米金简便地负载在钛酸钠(Na₂Ti₃O₇)载体上, 构建出具有较窄禁带宽度和较高光催化活性的Au/RGO/Na₂Ti₃O₇光热辅助光催化体系. 研究发现, 石墨烯片层与金纳米颗粒在光照下, 通过局域表面等离激元共振效应诱导产生大量的热电子, 以活化反应物并降低反应活化能, 其引发的光热效应还可精准提升光催化体系中反应位点附近的温度, 从而大幅提升光催化反应速率. 通过构建特殊微支结构, 进一步增强了Au/RGO/Na₂Ti₃O₇催化剂对光的捕获, 并限域锚定高表面能催化剂以增强体系的稳定性. 在光热、 光催化的高效协同增强下, Au/RGO/Na₂Ti₃O₇催化剂体系对对硝基苯酚和肉桂醛的加氢反应均表现出增强的光催化活性. 光热辅助下的Au/RGO/Na₂Ti₃O₇光催化剂在对硝基苯酚反应中的转换频率（TOF）值高达54.4 min^-1, 反应活化能显著降低至15.78 kJ/mol, 且其在长效测试中表现出良好的稳定性（4次循环催化后, 转化率的保持率近90%）.     

锐钛矿(001)与(101)晶面在光催化反应中的作用

采用水热法制备了(001)和(101)晶面暴露的单晶锐钛矿TiO₂颗粒. 利用光还原沉积贵金属(Au, Ag, Pt)和光氧化沉积金属氧化物(PbO₂, MnO_x)的方法研究了暴露的锐钛矿(001)和(101)晶面在光催化中的作用. 通过透射电子显微镜(TEM)、扫描电子显微镜(STM)、能量色散X射线光谱仪(EDX)和X射线光电子能谱(XPS)的表征, 发现发生光还原反应生成的贵金属粒子主要沉积在暴露的锐钛矿(101)晶面上, 而发生光氧化反应产生的金属氧化物颗粒主要沉积在暴露的锐钛矿(001)晶面上. 此结果表明光激发产生的电子与空穴主要并分别分布在单晶锐钛矿TiO₂的(101)与(001)晶面上, 并在其上参与光催化还原反应和氧化反应. 同时也表明暴露的不同晶面对光生电荷具有分离效应. 基于本研究可以认为同时暴露分别进行氧化和还原反应的晶面可以有效促进光催化反应.     

Au掺杂方式对锐钛矿TiO2光催化性能的影响

结合超临界乙醇干燥技术, 采用沉积-沉淀(DP)和共沉淀(CP)法分别制备了具有单一锐钛矿晶相的Au/TiO2和Au(0.2%, 原子分数)-TiO2光催化剂, 通过XRD、BET、TEM、XPS和Raman手段表征样品中Au的掺杂形态, 以光催化降解甲基橙为模型反应考察了样品的光催化活性. 结果表明, DP法制备的Au/TiO2在110 ℃干燥处理后, 表面存在的Au3+能有效地促进锐钛矿TiO2光催化性能, 其一级反应速率常数比纯锐钛矿TiO2提高了3.2倍, 比商用光催化剂Degussa-P25提高了4.1倍, 而当Au3+被还原为Au0后光催化活性下降. 用CP法制备的Au-TiO2并没有较大地提高锐钛矿TiO2光催化性能, 在焙烧温度达到800 ℃时, Au向表面迁移聚集, 造成锐钛矿TiO2晶格氧空位和缺陷位增加, 使光催化活性下降.     

基于单原子催化剂的光热催化转化：原理和应用

在以碳中和为目标的全球共识下,太阳能作为一种取之不竭用之不尽的绿色环保能源被认为是替代传统化石燃料最有潜力的方式。在各种太阳能转换技术中,光热催化不仅可以最大化利用太阳能,在光场和热场双重驱动力作用下,还可以显著提升化学反应速率,引起广泛的研究兴趣。以孤立的单个原子均匀分散在载体上形成的单原子催化剂具有100%原子利用率、优异的催化活性、热稳定性等优势。因此,将单原子催化剂应用于光热催化开始受到越来越多的关注。本综述介绍了光催化、热催化和光热催化的基本原理和特征,同时列举一些典型的例子。随后以不同载体作为分类标准,总结了单原子光热催化应用的前沿研究进展。最后,提出了该催化体系所面临的挑战和未来的发展方向。本文旨在全面了解单原子催化剂在太阳能驱动光热催化领域的研究现状并为未来发展提供可行的建议。     

Dispersion and Structure Studies of Molybdenum Oxide on Anatase TiO2

X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) were used to characterize the structure of the mixture of molybdenum oxide and anatase calcined at 723 K. The resuits indicate that molybdenum oxide can disperse onto the surface of anatase (TiO2) and the dispersion threshold is 11.2 mg in per gram of MoO3 or 4.8 Mo atoms/nm^2 TiO2. When the coment of MoO3 is below the dispersion threshold, MoO3 species is in highly dispersed state interacting strongly with TiO2 support and in discrete tetrahedral coordination. [MoO4], on the surface of TiO2. When the MoO3 loading is above this value, MoO3 exists in both dispersed phase and crystalline phase. MoO3 in dispersed phase is still a discrete [MoO4] tetrahedron; MoO3 in crystal phase is in octahedral coordination.     

方形锐钛矿TiO2纳米晶的合成及表征

在不添加任何模板剂或形状控制剂的条件下,以TiCl₄为前体,经氨水沉淀、乙醇洗涤和超临界干燥(AS制备法)选择性地合成了方形锐钛矿TiO₂纳米单晶.热稳定性研究结果表明,当焙烧温度不超过650℃时,方形锐钛矿TiO₂纳米晶的表面积、孔容、晶粒/颗粒尺寸基本保持不变.XRD和拉曼光谱分析表明,方形锐钛矿TiO₂纳米晶在800℃下焙烧后仍能保持晶相不变,表现出很强的抗晶相转变能力.但在1000℃焙烧后,样品可以完全转变成金红石相TiO₂.     

Fe3+/TiO2光催化降解溴化乙锭的研究

溴化乙锭(Ethidium Bromide,EB),是一种常见的阳离子荧光染料,能与双链核酸发生嵌入作用,使荧光强度显著增强[1],因此被广泛应用于生命科学尤其是分子生物学领域中核酸的定性、定量分析。但EB是一种强烈的诱变剂,具有中度毒性[2],且易逸入空气中,增加了危害性。半导体超细微粒如TiO2[3]、CdS[4]等在紫外光或者可见光光照下产生强烈的氧化作用,能把许多难分解有毒污染物氧化为CO2、H2O等无毒物质。其中TiO2已被广泛用于光催化法处理各种染料以及难分解的污染物[5,6]。当用波长小于或等于388nm的紫外光照射锐钛型TiO2时,可将电子从价…     

Recent advances in 1D nanostructured catalysts for photothermal and photocatalytic reduction of CO2

The development of photocatalysts that can efficiently convert CO₂ into other valuable chemicals via photocatalytic and photothermal processes is critical to the current energy and climate change problems. However, low separation of charge carriers, short light absorption, and low activation of CO₂ molecules in photocatalysis limit the catalysts’ performance. Designing 1D heterostructures containing multiple materials can be a viable solution as their unique properties, such as high surface area, short diffusion paths of charge carriers, and enhanced light absorption properties, can potentially promote the reaction rate and product selectivity. In this review, we summarize the general features of heterostructures involving nanotubes, nanowires, nanorods, and nanobelts. Next, the main synthesis strategies are briefly highlighted, followed by the most important findings concerning their catalytic activity in the photothermal and photocatalytic CO₂ reduction processes. The article concludes with some of the current challenges and potential solutions.     

Active Sites for Adsorption and Reaction of Molecules on Rutile TiO2(110) and Anatase TiO2(001) Surfaces (cited: 1)

The reactivity of specific sites on rutile TiO₂(110)-(1×1) surface and anatase TiO₂(001)-(1×4) surface has been comparably studied by means of high resolution scanning tunneling microscopy. At the rutile TiO₂(110)-(1×1) surface, we find the defects of oxygen vacancy provide distinct reactivity for O₂ and CO₂ adsorption, while the terminal fivefold-coordinated Ti sites dominate the photocatalytic reactivity for H₂O and CH₃OH dissociation. At the anatase TiO₂(001)-(1×4) surface, the sixfold-coordinated terminal Ti sites at the oxidized surface seem to be inert in both O₂ and H₂O reactions, but the Ti-rich defects which introduce the Ti³⁺ state into the reduced surface are found to provide high reactivity for the reactions of O₂ and H₂O. By comparing the reactions on both rutile and anatase surfaces under similar experimental conditions, we find the reactivity of anatase TiO₂(001) is actually lower than rutile TiO₂(110), which challenges the conventional knowledge that the anatase (001) is the most reactive TiO₂ surface. Our findings could provide atomic level insights into the mechanisms of TiO₂ based catalytic and photocatalytic chemical reactions.     

Hydrothermal synthesis and enhanced photocatalytic activity of mixed-phase TiO2 powders with controllable anatase/rutile ratio

In this study, mixed-phase TiO₂ powders were novelly synthesized via a facile and mild hydrothermal method without any post-heat treatment. TiOSO₄ and peroxide titanic acid (PTA) were used as inorganic titanium sources, while no special solvent or additive were introduced. The XRD and TEM results showed the mixed-phase TiO₂ powders were composed of anatase and rutile phases, and the PTA sol played an important role on forming the rutile nucleus. The proportion of rutile in the mixed-phase TiO₂ could be easily controlled in the range of 0%–70.5% by changing the amount of PTA sol used in the synthesis process. The UV-Visible absorption spectra indicated the prepared mixed-phase TiO₂ showed enhanced visible light absorption with the increase of rutile ratio. The photodegradation experiments revealed the mixed-phase TiO₂ exhibited the best photocatalytic activity at the rutile ratio of 41.5%, while a higher or lower rutile ratio both resulted in the decrease of photocatalytic activity.     

TiO2表面光催化基元过程

在过去的几十年里,得益于二氧化钛(TiO₂)作为光催化剂在光催化分解水、污染物降解方面的潜在应用,人们对TiO₂光催化剂的开发、改良以及TiO₂表面光催化机理的基础研究方面都投入了巨大的精力。因此,在超高真空环境下,利用不同的实验和理论方法,人们对TiO₂表面(特别是金红石TiO₂(110)表面)的热催化和光催化过程进行了大量的研究,以此来获得上述重要反应中的一些机理性的信息。本文中,将从TiO₂的物质结构以及电子结构开始,然后着重介绍TiO₂表面光生电荷(电子和空穴)的传输、捕获以及电子转移动力学方面的进展。在此基础上,总结了甲醇在金红石TiO₂(110)、TiO₂(011)以及锐钛矿TiO₂(101)表面光化学基元反应过程的一些实验结果。这些结果不仅能增进我们对表面光催化基元过程的认识,同时也能激励我们进一步去研究表面光催化基元过程。最后,基于现有光化学实验结果,简短地讨论了我们对光催化反应机理的一点看法,并提出了一个可能的光催化模型,这可以引起人们对光催化反应机理更全面的思考。     

Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

Template Synthesis and Characterization of Cu2O/TiO2 Coaxial Nanocable for Photocatalysis

Coaxial nanocable consisted of p-type Cu₂O nanowires and n-type TiO₂ nanotubes arrays was prepared in the porous anodic aluminum oxide(AAO) template via the sol-gel method and subsequent electrodeposition method. X-ray diffraction analysis identified an anatase structure of the TiO₂ nanotubes and cubic structure of the Cu₂O nanowires. The obtained samples were also characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and energy dispersive X-ray spectroscopy(EDS). The diffrence of open circuit potential of the coaxial nanocable electrode was larger than that of the TiO₂ nanotubes electrode under ultraviolet illumination, which means doping with Cu₂O could improve the photovoltage effectively. Meanwhile, nanocable arrays exhibited a high activity for photodegrading Rhodamine B under Xe lamp irradiation and the photocatalysis degradation efficiency was up to 98.69% after degradation for 7 h. The enhanced photocatalytic activity could be attributed to the high migration efficiency of photoinduced electrons, which may suppress the charge recombination effectively.     

溶胶-凝胶-水热晶化法制备锐钛矿TiO2纳米膜的耐蚀性能

以钛酸正丁酯为前驱体, 采用溶胶-凝胶-水热晶化法在不锈钢(SS)表面制备TiO₂纳米膜. 利用X射线衍射(XRD)、Raman光谱、场发射扫描电子显微镜(SEM)、原子力显微镜(AFM)和俄歇电子能谱(AES)表征了TiO₂纳米膜的晶型、表面形貌和表面化学组成. 通过极化曲线和电化学阻抗谱(EIS)研究了TiO₂纳米膜的耐蚀性能. 170 °C下水热晶化制备的锐钛矿TiO₂与450 °C焙烧制备的锐钛矿TiO₂的结晶度类似, 但两种TiO₂薄膜的表面结构存在明显差异, 水热晶化法制备的TiO₂纳米膜在3.5% (w) NaCl溶液中的耐蚀性能优于焙烧法制备的.     

Suppressive Strong Metal-Support Interactions on Ruthenium/TiO2 Promote Light-Driven Photothermal CO2 Reduction with Methane

Strong metal-support interactions (SMSI) have gained great attention in the heterogeneous catalysis field, but its negative role in regulating light-induced electron transfer is rarely explored. Herein, we describe how SMSI significantly restrains the activity of Ru/TiO₂ in light-driven CO₂ reduction by CH₄ due to the photo-induced transfer of electrons from TiO₂ to Ru. In contrast, on suppression of SMSI Ru/TiO₂−H₂ achieves a 46-fold CO₂ conversion rate compared to Ru/TiO₂. For Ru/TiO₂−H₂, a considerable number of photo-excited hot electrons from Ru nanoparticles (NPs) migrate to oxygen vacancies (OVs) and facilitate CO₂ activation under illumination, simultaneously rendering Ru^δ+ electron deficient and better able to accelerate CH₄ decomposition. Consequently, photothermal catalysis over Ru/TiO₂−H₂ lowers the activation energy and overcomes the limitations of a purely thermal system. This work offers a novel strategy for designing efficient photothermal catalysts by regulating two-phase interactions.     

Thiobencarb Degradation by TiO2 Photocatalysis: Parameter and Reaction Pathway Investigations

The present study deals with the photocatalytic degradation of the thiocarbamate herbicide, thiobencarb (TBC), in the presence of TiO₂ particles and UV‐A (λ = 365 nm) radiation. Results show rapid and complete oxidation of TBC after 90 min, and slightly over 70% of TBC was mineralized after 32‐h treatment. Factors such as solution pH, TiO₂ dosage, and the presence of anions are found to influence the degradation rate. The establishment of the reaction pathway is made possible by a thorough analysis of the reaction mixture identifying the main intermediate products generated. Results suggest that possible transformation pathways may include hydroxylation, dealkylation and C—S bond cleavage processes. The possible degradation pathways are proposed and discussed on the basis of the evidence of oxidative intermediate formation.     

Catalysis by Using TiO2 Nanoparticles and Nanotubes

TiO2 has attracted considerable attention due to its stability, non-toxicity, low cost, and great potential for use as a photocatalyst in environmental applications. Since strong metal-support interaction (SMSI) of titania-supported noble metals was first reported in 1978, titania supported catalyst has been intensively studied in heterogeneous catalysis. However, the effective catalytic activity was restricted due to the low surface area of TiO2. Recently, TiO2-based nanotubes were extensively investigated because of their potentials in many areas such as highly efficient photocatalysis and hydrogen sensor.In the present study, formation of titanium oxide (TiO2) nanotubes was carried out by hydrothermal method, with TiO2 nanoparticle-powders immersed in concentrated NaOH solution in an autoclave at 110 ℃. Preparation of nano-size Pt on TiO2-nanoparticles or TiO2-nanotubes was performed by photochemical deposition method with UV irradiation on an aqueous solution containing TiO2 and hexachloroplatinic acid or tetrachloroauric acid. The TEM micrographs show that TiO2-nanotubes exhibit ～300 nm in length with an inner diameter of ～ 6 nm and the wall thickness of ～ 2 nm, and homogeneous nanosize Pt particles (～ 2 nm) were well-dispersed on both nanoparticle- and nanotube- titania supports. It also shows the nanotube morphology was retained up2o n Pt-immobilization. Nitrogen adsorption isotherm at 77K resulted a high surface area (～ 200m/g) of TiO2-nanotubes, which is about 40 times greater than that of "mother" TiO2 nanoparticles (～5 m/g). All the spectroscopic results exhibited that the nanotube structure was not significantly affected by the immobilized Pt particles. Ti K-edge XANES spectra of TiO2 nanotube and Pt/TiO2-nanotube represent that most titanium are in a tetrahedral coordination with few retained in the octahedral structure.In the in-situ FT-IR experiments, an IR cell was evacuated to a pressure of 10-5 torr at room temperature as soon as the catalyst-pellet, Pt/TiO2 or Pt/TiO2-nanotube, was placed inside the cell.Then, 60 torr of hydrogen was introduced into the cell and subsequently the temperature was programmed to increase from room temperature to 300℃ at a constant heating rate of 5℃/min.For Pt/TiO2, an IR peak at 2083 em-1 started to appear at 200℃ with a maximum intensity at 250℃ and then decreasing as temperature increased. The 2083 em-1 IR peak corresponds to the linearly adsorption of CO on the well-dispersed Pt sites. Simultaneously, the IR bands of gaseous methane at 3016 em-1 started to appear at 225℃ and the peak intensity increased with temperature. The results reveal that Pt/TiO2 can adsorb gaseous CO2 and further catalyzes the reduction of CO2 by H2 through the intermediate CO, which further produces gaseous methane. While for the Pt/TiO2-nanotube catalyst, methane was produced at relatively low temperature, 100℃, and it catalyzed the direct conversion of CO2 to CH4. The absence of intermediate CO-adsorption signals durinng the temperature programmed process indicates that the prepared TiO2 nanotube-supported nanosize Pt possesses a potent capability for CO2 adsorption and highly catalytic activity in the hydrogenation of CO2, and was superior to the conventional Pt/TiO2 catalyst. The catalytic activity of Pt/TiO2-nanotube was indeed significantly enhanced by the high surface area of TiO2-nanotubes.Details will be discussed.     

介孔结构多酸掺杂-锐钛矿纳米晶Na4W10O32/TiO2的制备及其可见光光催化性能研究

作为一种先进的氧化技术 ,光催化化学在有机污染物的降解和精细有机合成中发挥着巨大的作用 .目前 ,光催化领域中广泛使用的两类绿色光催化剂分别为二氧化钛 (锐钛矿结构 )和多金属氧酸盐 [1～ 3] .但其还存在催化活性组分在反应过程中流失和催化剂必须采用近紫外光活化等不完善之处 ,而后者是影响光催化技术实际应用的最大障碍 .因为太阳光中仅存在 2 %～ 3%的紫外光 ,太阳能的利用率极低 .因此 ,有效利用太阳光来实现光能向化学能的转换 ,进而在温和的实验条件下顺利完成无机物或有机物的光催化反应 ,是对发展未来新型光催化材料的挑战 .…     

引入应力的锐钛矿TiO_2(001)薄膜的外延生长

锐钛矿TiO_2(001)(anataseTiO_2(001),简记为ATO)表面因其优异的催化活性受到了广泛的关注。理论计算结果表明,ATO表面应力导致的晶格畸变可能会增强该表面的催化活性。因此有必要研究应力对ATO表面结构的影响。本文利用BaTiO_3(001)(简记为BTO)与ATO之间存在较大的晶格失配度,将ATO薄膜外延生长在BTO衬底上从而引入应力,研究了存在应力情况下的ATO薄膜的结构特征。实验中,利用脉冲激光沉积方法在Nb掺杂的SrTi O_3(001)(简记为STO)单晶衬底上制备了ATO/BTO/STO外延薄膜。X射线衍射(XRD)和扫描透射电子显微术(STEM)结果表明,作为应力引入层的BTO薄膜厚度约为4–6nm时,能够部分地将应力引入到ATO薄膜中。X射线光电子能谱(XPS)结果显示,ATO薄膜合适的厚度应大于15 nm,从而降低从衬底反向扩散至表面的Sr和Ba原子的浓度;Ti 2p的高分辨XPS谱仅呈现出Ti~(4+)峰,表明ATO表面Ti原子为完全氧化的价态。ATO外延薄膜表面的扫描隧道显微术(STM)图像仍然呈现为(1×4)重构的结构,但在(1×4)重构的脊上存在明暗交替并具有一定周期性的特征。根据完全氧化的"增氧原子模型"(ad-oxygen model,AOM),脊上观察到的明暗交替特征可归因于表面应力导致的"TiO_2"空位缺陷结构。