Ni‐Nanocluster Modified Black TiO2 with Dual Active Sites for Selective Photocatalytic CO2 Reduction

One of the key challenges in artificial photosynthesis is to design a photocatalyst that can bind and activate the CO₂ molecule with the smallest possible activation energy and produce selective hydrocarbon products. In this contribution, a combined experimental and computational study on Ni‐nanocluster loaded black TiO₂ (Ni/TiO_2[Vo]) with built‐in dual active sites for selective photocatalytic CO₂ conversion is reported. The findings reveal that the synergistic effects of deliberately induced Ni nanoclusters and oxygen vacancies provide (1) energetically stable CO₂ binding sites with the lowest activation energy (0.08 eV), (2) highly reactive sites, (3) a fast electron transfer pathway, and (4) enhanced light harvesting by lowering the bandgap. The Ni/TiO_2[Vo] photocatalyst has demonstrated highly selective and enhanced photocatalytic activity of more than 18 times higher solar fuel production than the commercial TiO₂ (P‐25). An insight into the mechanisms of interfacial charge transfer and product formation is explored.     

Cocatalysts in Semiconductor‐based Photocatalytic CO2 Reduction: Achievements,Challenges, and Opportunities

Ever‐increasing fossil‐fuel combustion along with massive CO₂ emissions has aroused a global energy crisis and climate change. Photocatalytic CO₂ reduction represents a promising strategy for clean, cost‐effective, and environmentally friendly conversion of CO₂ into hydrocarbon fuels by utilizing solar energy. This strategy combines the reductive half‐reaction of CO₂ conversion with an oxidative half reaction, e.g., H₂O oxidation, to create a carbon‐neutral cycle, presenting a viable solution to global energy and environmental problems. There are three pivotal processes in photocatalytic CO₂ conversion: (i) solar‐light absorption, (ii) charge separation/migration, and (iii) catalytic CO₂ reduction and H₂O oxidation. While significant progress is made in optimizing the first two processes, much less research is conducted toward enhancing the efficiency of the third step, which requires the presence of cocatalysts. In general, cocatalysts play four important roles: (i) boosting charge separation/transfer, (ii) improving the activity and selectivity of CO₂ reduction, (iii) enhancing the stability of photocatalysts, and (iv) suppressing side or back reactions. Herein, for the first time, all the developed CO₂‐reduction cocatalysts for semiconductor‐based photocatalytic CO₂ conversion are summarized, and their functions and mechanisms are discussed. Finally, perspectives in this emerging area are provided.     

Engineering Single Cu Sites into Covalent Organic Framework for Selective Photocatalytic CO2 Reduction

Photocatalytic CO₂ conversion into value-added chemicals is a promising route but remains challenging due to poor product selectivity. Covalent organic frameworks (COFs) as an emerging class of porous materials are considered as promising candidates for photocatalysis. Incorporating metallic sites into COF is a successful strategy to realize high photocatalytic activities. Herein, 2,2′-bipyridine-based COF bearing non-noble single Cu sites is fabricated by chelating coordination of dipyridyl units for photocatalytic CO₂ reduction. The coordinated single Cu sites not only significantly enhance light harvesting and accelerate electron–hole separation but also provide adsorption and activation sites for CO₂ molecules. As a proof of concept, the Cu-Bpy-COF as a representative catalyst exhibits superior photocatalytic activity for reducing CO₂ to CO and CH₄ without photosensitizer, and impressively, the product selectivity of CO and CH₄ can be readily modulated only by changing reaction media. Experimental and theoretical results reveal the crucial role of single Cu sites in promoting photoinduced charge separation and solvent effect in regulating product selectivity, which provides an important sight onto the design of COF photocatalysts for selective CO₂ photoreduction.     

Hierarchical Porous O‐Doped g‐C3N4 with Enhanced Photocatalytic CO2 Reduction Activity

Artificial photosynthesis of hydrocarbon fuels by utilizing solar energy and CO₂ is considered as a potential route for solving ever‐increasing energy crisis and greenhouse effect. Herein, hierarchical porous O‐doped graphitic carbon nitride (g‐C₃N₄) nanotubes (OCN‐Tube) are prepared via successive thermal oxidation exfoliation and curling‐condensation of bulk g‐C₃N₄. The as‐prepared OCN‐Tube exhibits hierarchically porous structures, which consist of interconnected multiwalled nanotubes with uniform diameters of 20–30 nm. The hierarchical OCN‐Tube shows excellent photocatalytic CO₂ reduction performance under visible light, with methanol evolution rate of 0.88 µmol g^?1 h^?1, which is five times higher than bulk g‐C₃N₄ (0.17 µmol g^?1 h^?1). The enhanced photocatalytic activity of OCN‐Tube is ascribed to the hierarchical nanotube structure and O‐doping effect. The hierarchical nanotube structure endows OCN‐Tube with higher specific surface area, greater light utilization efficiency, and improved molecular diffusion kinetics, due to the more exposed active edges and multiple light reflection/scattering channels. The O‐doping optimizes the band structure of g‐C₃N₄, resulting in narrower bandgap, greater CO₂ affinity, and uptake capacity as well as higher separation efficiency of photogenerated charge carriers. This work provides a novel strategy to design hierarchical g‐C₃N₄ nanostructures, which can be used as promising photocatalyst for solar energy conversion.     

Recent Advances and Perspectives of Core-Shell Nanostructured Materials for Photocatalytic CO2 Reduction

Photocatalytic CO₂ conversion into solar fuels is a promising technology to alleviate CO₂ emissions and energy crises. The development of core-shell structured photocatalysts brings many benefits to the photocatalytic CO₂ reduction process, such as high conversion efficiency, sufficient product selectivity, and endurable catalyst stability. Core-shell nanostructured materials with excellent physicochemical features take an irreplaceable position in the field of photocatalytic CO₂ reduction. In this review, the recent development of core-shell materials applied for photocatalytic reduction of CO_{2 is introduced}. First, the basic principle of photocatalytic CO₂ reduction is introduced. In detail, the classification and synthesis techniques of core-shell catalysts are discussed. Furthermore, it is also emphasized that the excellent properties of the core-shell structure can greatly improve the activity, selectivity, and stability in the process of photocatalytic CO₂ reduction. Hopefully, this paper can provide a favorable reference for the preparation of efficient photocatalysts for CO₂ reduction.     

金属掺杂对TiO2光催化还原CO2制甲酸甲酯活性的影响

采用溶胶-凝胶法制备掺杂金属改性的TiO2光催化剂,并研究其光催化还原CO2制甲酸甲酯的反应效果。以钛酸丁酯为主要原料,制备纳米TiO2。通过改变金属掺杂量、焙烧温度、前躯体pH等,确定出适宜的催化剂制备条件。结合SEM、XRD、UV-vis等对催化剂进行了形貌、结构和吸光行为的表征。进而考察了其光催化还原CO2的活性。结果表明:溶胶-凝胶法制备掺杂金属的TiO2,可使金属均匀地分布于TiO2表面,经催化活性评价,获得适宜的掺杂元素和掺杂量,优选的制备条件为溶胶pH=2.5～3、凝胶焙烧温度500℃,在催化剂用量1mg/mL,光照强度2880μw/cm2的反应条件下,可有效地促进TiO2光催化还原CO2制甲酸甲酯。     

硫化物负载ZnO/ZnAl2O4复合空心球及其光催化还原CO2

采用一步水热法制备了ZnO/ZnAl₂O₄纳米复合物, 通过浸渍法负载CuS、CdS和Bi₂S₃对其进行修饰, 并在模拟太阳光照射下研究负载样品的光催化活性。用XRD、SEM、TEM、BET和FL等技术对所得样品进行表征, 以NaOH 和Na₂SO₃作为光催化还原二氧化碳过程的牺牲剂, 考察了硫化物种类及其负载量对ZnO/ZnAl₂O₄光催化还原活性的影响。结果表明, 负载CuS和CdS均可提高ZnO/ZnAl₂O₄光催化还原活性, 而负载Bi₂S₃却有所降低。当CuS负载量为1wt%时, 样品光催化还原活性最佳, 反应6 h后所得还原产物甲醇的生成量为8.21 mmol/g_cat, 在相同条件下较原样提高了约3.2倍。对CuS/ZnO/ZnAl₂O₄的光催化机理进行了初步探讨。     

In Situ Grown Monolayer N‐Doped Graphene on CdS Hollow Spheres with Seamless Contact for Photocatalytic CO2 Reduction

Photocatalytic CO₂ reduction is an effective way to simultaneously mitigate the greenhouse effect and the energy crisis. Herein, CdS hollow spheres, on which monolayer nitrogen‐doped graphene is in situ grown by chemical vapor deposition, are applied for realizing effective photocatalytic CO₂ reduction. The constructed photocatalyst possesses a hollow interior for strengthening light absorption, a thin shell for shortening the electron migration distance, tight adhesion for facilitating separation and transfer of carriers, and a monolayer nitrogen‐doped graphene surface for adsorbing and activating CO₂ molecules. Achieving seamless contact between a photocatalyst and a cocatalyst, which provides a pollution‐free and large‐area transport interface for carriers, is an effective strategy for improving the photocatalytic CO₂ reduction performance. Therefore, the yield of CO and CH₄, as dominating products, can be increased by four and five times than that of pristine CdS hollow spheres, respectively. This work emphasizes the importance of contact interface regulation between the photocatalyst and the cocatalyst and provides new ideas for the seamless and large‐area contact of heterojunctions.     

Ultrathin Anatase TiO2 Nanosheets for High‐Performance Photocatalytic Hydrogen Production

An ethanol solvothermal route has been developed to prepare ultrathin anatase TiO₂ nanosheets with dominant {001} facets (≈97%), a thickness of ≈2.5 nm, and a side length of ≈200 nm. The introduction of ethanol solvent significantly enhances the content of surface chemisorbed F^? on the TiO₂ nanosheet, which has a higher stability and further lowers the surface energy of {001} facets, giving rise to the large percentage of active {001} facets. Adopting well‐defined morphology, such nanosheets loaded with 1 wt% Pt exhibit an H₂ evolution rate as high as 17.86 mmol h^?1 g^?1, and the corresponding apparent quantum efficiency has been determined to be 34.2%.     

基于超薄纳米结构的光催化二氧化碳选择性转化

21世纪以来,能源短缺和环境污染一直是人类面临的重大挑战?光催化二氧化碳(CO2)还原,通过半导体捕获光能,获得碳氢化合物太阳能燃料是解决能源危机并推动碳循环的有前景的策略之一?然而,活性低?产物选择性差又极大地限制了这一技术的实际应用?因此,调控产物选择性并提高光催化效率、加深对CO2还原反应机理的理解具有重要意义?...     

不同N源无定形TiO2/g-C3N4光催化还原Re(VII)性能

为探究不同N源对无定形TiO₂/g-C₃N₄(TCN)复合材料光催化还原Re(VII)的影响, 通过热分解不同前驱体(尿素Urea、硫脲Thiourea和三聚氰胺Melamine)制备g-C₃N₄, 再分别与无定形TiO₂复合, 制备了三种TCN复合光催化剂。通过不同分析手段对材料进行表征, 并比较了不同TCN复合材料光催化还原去除Re(VII)的活性差异。结果表明, U-TCN(尿素为N源)具有更均匀的表观形貌, 最大的比表面积(474 m²/g), 最优异的光吸收性能, 对Re(VII)的光催化还原效率(90%)明显高于T-TCN(20%)和M-TCN(15%)。通过复合材料的瞬态光电流和电化学阻抗(EIS)分析光催化机理, 证明U-TCN光生电子空穴分离效率最高; 电子顺磁共振波谱(EPR)分析表明U-TCN产生的羟基自由基(?OH)更多, 因此与甲酸反应产生的强还原性?CO₂^-自由基更多, 从而更有利于Re(VII)的还原; 利用同步辐射X射线吸收光谱分析Ti元素价态及配位环境, 表明U-TCN还具有优异的光化学稳定性。本研究揭示了不同N源对所制备TCN复合材料光催化性能的影响, 并发现了一种可用于实际废水中光催化还原去除Tc(VII)的优选材料。