FeNi层状双氢氧化物/TiO2复合光催化剂的制备及其制氢性能

层状双氢氧化物(LDH)的光生电子-空穴对易复合,虽然纳米薄片的结构促进了载流子分离,但其光催化效率仍然较低。我们利用LDH薄片结构的优势,将FeNi LDH和TiO₂通过静电自组装复合,设计制备出新型高效的FeNi LDH/TiO₂复合光催化材料,评价了其光催化分解水产氢性能。对其结构、光催化性能和光电化学等进行了详细表征。结果表明,FeNi LDH的高比表面积、复合物的异质结结构都有利于光生电荷的转移。光催化产氢结果表明,FeNi LDH/TiO₂复合材料的产氢速率(22.6mmol·g^-1·h^-1)分别比纯TiO₂(0.1 mmol·g^-1·h^-1)和FeNi LDH(0.05 mmol·g^-1·h^-1)提高了226和452倍,表明了异质结在提高LDH光催化效率方面的重要作用。     

用于甲醇水溶液制氢的光催化剂纳米TiO2的改性进展

综述了用于甲醇水溶液制氢的光催化剂纳米TiO2的改性进展。参考文献34篇。     

高比表面TiO2光催化剂的制备及产氢性能研究

以钛酸四丁酯为前驱体，十六烷基三甲基溴化铵(CTAB)为模板剂合成了高比表面的TiO₂超细纳米粉体。采用XRD、TEM、BET分析方法对催化剂的物相、颗粒粒径及比表面积进行了表征，结果显示TiO₂的晶粒尺寸和比表面积与CTAB添加量和焙烧温度有关。重点考察了不同条件下制备的TiO₂系列光催化剂无氧条件下的光催化分解水产氢性能。实验结果表明，当CTAB与Ti的投料的物质的量之比为0.15，焙烧温度为450 ℃时，获得的晶粒尺寸为5.73 nm、比表面为150 m²·g^-1的TiO₂粉体具有最好的光催化产氢活性，测得的3 h内平均产氢速率为12.5 mL·h^-1。     

Fabrication of Highly Textured 2D SnSe Layers with Tunable Electronic Properties for Hydrogen Evolution

Hydrogen is regarded to be one of the most promising renewable and clean energy sources. Finding a highly efficient and cost-effective catalyst to generate hydrogen via water splitting has become a research hotspot. Two-dimensional materials with exotic structural and electronic properties have been considered as economical alternatives. In this work, 2D SnSe films with high quality of crystallinity were grown on a mica substrate via molecular beam epitaxy. The electronic property of the prepared SnSe thin films can be easily and accurately tuned in situ by three orders of magnitude through the controllable compensation of Sn atoms. The prepared film normally exhibited p-type conduction due to the deficiency of Sn in the film during its growth. First-principle calculations explained that Sn vacancies can introduce additional reactive sites for the hydrogen evolution reaction (HER) and enhance the HER performance by accelerating electron migration and promoting continuous hydrogen generation, which was mirrored by the reduced Gibbs free energy by a factor of 2.3 as compared with the pure SnSe film. The results pave the way for synthesized 2D SnSe thin films in the applications of hydrogen production.     

微波辅助快速制备2D/1D ZnIn2S4/TiO2 S型异质结及其光催化制氢性能

The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO₂ has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO₂ nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO₂ NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO₂ NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO₂ NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn₂S₄). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO₂ NFs, we report a 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn₂S₄nanosheets decorated on 1D TiO₂ NFs. The loading of ZnIn₂S₄ nanoplates on the TiO₂ NFs could be easily controlled by adjusting the molar ratios of ZnIn₂S₄ precursors to TiO₂ NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn₂S₄/TiO₂ composites was significantly improved, and the obtained ZnIn₂S₄/TiO₂ composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn₂S₄/TiO₂= 0.5) sample was 8774 μmol·g^-1·h^-1, which is considerably higher than those of pure TiO₂ NFs (3312 μmol·g^-1·h^-1) and ZnIn₂S₄nanoplates (3114 μmol·g^-1·h^-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn₂S₄ and TiO₂ was proposed to interpret the enhanced HER activity of the ZnIn₂S₄/TiO₂heterojunctionphotocatalysts.      

Photocatalytic Hydrogen Evolution Coupled with Production of Highly Value-Added Organic Chemicals by a Composite Photocatalyst CdIn2S4@MIL-53-SO3Ni1/2

Photocatalytic water splitting coupled with the production of highly value-added organic chemicals is of significant importance, which represents a very promising pathway for transforming green solar energy into chemical energy. Herein, we report a composite photocatalyst CdIn₂S₄@MIL-53-SO₃Ni_1/2, which is highly efficient on prompting water splitting for the production of H₂ in the reduction half-reaction and selective oxidation of organic molecules for the production of highly value-added organic chemicals in the oxidation half-reaction under visible light irradiation. The superior photocatalytic properties of the composite photocatalyst CdIn₂S₄@MIL-53-SO₃Ni_1/2 should be ascribed to coating suspended ion catalyst (SIC), consisting of redox-active Ni^II ions in the anionic pores of coordination network MIL-53-SO₃⁻, on the surface of photoactive CdIn₂S₄, which endows photogenerated electron-hole pairs separate more efficiently for high rate production of H₂ and selective production of highly value-added organic products, demonstrating great potential for practical applications.     

Transformation Kinetics of LiBH4–MgH2 for Hydrogen Storage

The reactive hydride composite (RHC) LiBH₄–MgH₂ is regarded as one of the most promising materials for hydrogen storage. Its extensive application is so far limited by its poor dehydrogenation kinetics, due to the hampered nucleation and growth process of MgB₂. Nevertheless, the poor kinetics can be improved by additives. This work studied the growth process of MgB₂ with varying contents of 3TiCl₃·AlCl₃ as an additive, and combined kinetic measurements, X-ray diffraction (XRD), and advanced transmission electron microscopy (TEM) to develop a structural understanding. It was found that the formation of MgB₂ preferentially occurs on TiB₂ nanoparticles. The major reason for this is that the elastic strain energy density can be reduced to ~4.7 × 10⁷ J/m³ by creating an interface between MgB₂ and TiB₂, as opposed to ~2.9 × 10⁸ J/m³ at the original interface between MgB₂ and Mg. The kinetics of the MgB₂ growth was modeled by the Johnson–Mehl–Avrami–Kolmogorov (JMAK) equation, describing the kinetics better than other kinetic models. It is suggested that the MgB₂ growth rate-controlling step is changed from interface- to diffusion-controlled when the nucleation center changes from Mg to TiB₂. This transition is also reflected in the change of the MgB₂ morphology from bar- to platelet-like. Based on our observations, we suggest that an additive content between 2.5 and 5 mol% 3TiCl₃·AlCl₃ results in the best enhancement of the dehydrogenation kinetics.     

Bipolar Electrochemistry Exfoliation of Layered Metal Chalcogenides Sb2S3 and Bi2S3 and their Hydrogen Evolution Applications

Efficient exfoliation and downsizing of Sb₂S₃ and Bi₂S₃ layered compounds by using scalable bipolar electrochemistry on their suspensions in aqueous media are here demonstrated. The resulting samples were characterized in detail by transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy; their electrochemistry toward hydrogen evolution was also investigated. Hydrogen evolution ability of exfoliated Sb₂S₃ and Bi₂S₃ was investigated and compared to the bulk counterparts.     

Hierarchical β‐Mo2C Nanotubes Organized by Ultrathin Nanosheets as a Highly Efficient Electrocatalyst for Hydrogen Production

Production of hydrogen by electrochemical water splitting has been hindered by the high cost of precious metal catalysts, such as Pt, for the hydrogen evolution reaction (HER). In this work, novel hierarchical β‐Mo₂C nanotubes constructed from porous nanosheets have been fabricated and investigated as a high‐performance and low‐cost electrocatalyst for HER. An unusual template‐engaged strategy has been utilized to controllably synthesize Mo‐polydopamine nanotubes, which are further converted into hierarchical β‐Mo₂C nanotubes by direct carburization at high temperature. Benefitting from several structural advantages including ultrafine primary nanocrystallites, large exposed surface, fast charge transfer, and unique tubular structure, the as‐prepared hierarchical β‐Mo₂C nanotubes exhibit excellent electrocatalytic performance for HER with small overpotential in both acidic and basic conditions, as well as remarkable stability.     

Structural Tunability and Diversity of Two-Dimensional Lead Halide Benzenethiolate

Two-dimensional (2D) organic-inorganic hybrid materials are currently of great interest for applications in electronics and optoelectronics. Here, the synthesis and optical properties of a new type of halide-organothiolate-mixed 2D hybrid material, Pb₂X(S-C₆H₅)₃, are reported, in which X is a halide (I, Br, or Cl). Different from conventional lead-based 2D layered materials, these compounds feature unusual five-coordinated lead centers with a stereochemically active electron lone pair on the lead atoms and four-coordinated iodine atoms. The Pb₂X(S-C₆H₅)₃ materials feature an indirect bandgap, strongly emissive long-lived self-trap states, and an extremely large Stokes shift. Interestingly, the optical bandgap of the materials can be tuned through variation of the halides; however, the photoluminescence is less sensitive to the composition and is more likely dominated by lead-sulfur lattice interactions or the lead lone-pair electrons. Our results support that a halide–organothiolate mixed anion hybrid structure offers a unique platform for discovering new exciting 2D electronic materials.     

CeO2 Particles Anchored to Ni2P Nanoplate for Efficient Photo-catalytic Hydrogen Evolution

Photocatalytic hydrogen evolution can convert intermittent and dispersive solar energy into hydrogen with high energy density,which is expected to fundamentally solve the problems of environmental pollution and energy shortages.In this experiment,the performance of the catalyst is modified by introducing cocatalyst and morphology control.Ni(OH)2 nanoflowers are used as substrates to derive nanoplate stack Ni₂P by high-temperature phosphating method,and a great many of CeO₂ nanoparticles are anchored in the Ni₂P.This unique 3D/0D combination effectively inhibits the agglomeration of CeO₂ nanoparticles and shortens the electron transfer path.Secondly,the introduction of metal-like performance of Ni₂P broadens the light absorption range of the catalyst and reduces the overpotential of the catalyst,which is a key factor in enhancing the catalytic activity.The design ideas of this experiment have reference significance for the design of efficient and environmentally friendly photocatalysts.     

Amorphous and Crystalline 2D Polymeric Carbon Nitride Nanosheets for Photocatalytic Hydrogen/Oxygen Evolution and Hydrogen Peroxide Production

Photocatalytic reactions, including hydrogen/oxygen generation, water splitting and hydrogen peroxide production, are regarded as a renewable and promising method to harvest and use solar energy. The key to achieving this goal is to explore efficient photocatalysts with high productivity. Recently, two‐dimensional (2D) polymeric carbon nitride nanosheets were reported as efficient photocatalysts toward various products because of their outstanding properties, such as high specific surface area, more reactive sites, the quantum effect in thickness and unique electronic properties. This minireview attempts to overview recent advances in the preparation, structure and properties of crystalline and amorphous carbon nitride nanosheets, and their applications in photocatalytic hydrogen/oxygen evolution, water splitting and hydrogen peroxide production. We also thoroughly discuss the effect of defects, dopants and composites on the photocatalytic efficiency of these carbon nitride nanosheets. Finally, we outlook the ongoing opportunities and future challenges for 2D carbon nitride nanosheets in the field of photocatalysis.     

金属性二维过渡金属硫化物的溶剂热合成及电催化析氢性能

采用溶剂热法制备了多种二维过渡金属硫化物(TMDCs), 在合成过程中通过调控反应前驱体的滴加速率来控制所得TMDCs的形貌和结构. 然后采用高温热处理来提高TMDCs的结晶性, 从而提升了其电催化活性. 在酸性电解液中进行电催化析氢性能测试. 结果表明, “花状”结构的金属性二维二硫化铌(NbS₂)具有最佳的催化活性和稳定性, 在电流密度为10 mA/cm²时, 其过电位仅为146 mV, 持续工作24 h后电流密度几乎不衰减. 研究发现, 可充分暴露面内活性位点的“花状”结构以及高温处理后材料导电性的提高是二维NbS₂具有优异电催化性能的主要因素.     

还原氧化石墨烯/介孔TiO2复合材料的合成及其光解水制氢性能

采用溶胶凝胶法,以钛酸四异丙酯(TTIP)为钛源,十六烷基三甲基溴化铵(CTAB)为模板剂合成了介孔二氧化钛样品mTiO_2,考察了合成温度、水量、模板剂用量和焙烧温度对其在紫外光条件下光催化产氢活性的影响。结果显示,在350℃下焙烧后,样品由无定形结构转变为锐钛矿相;随着焙烧温度的提高,锐钛矿相结构产物的结晶度提高,当焙烧温度超过550℃后,样品大部分转变为金红石相。以合成温度为30℃,模板剂用量(nCTAB/nTiO_2)为0.2,水量(nH2O/nTiO_2)为100,焙烧温度为450℃条件下合成的m-TiO_2样品为催化剂,当催化剂用量为0.4 g·L-1,体系中甲醇浓度高于20%(V/V)时,其紫外光条件下的光催化产氢活性达170 mmol·g-1·h-1。采用水热法将氧化石墨烯(GO)与m-TiO_2复合制备了一系列还原氧化石墨烯/介孔TiO_2复合材料(rGO/m-TiO_2),其晶相结构为锐钛矿相。当r GO复合量(wGO/wTiO_2)为0.01时,样品在紫外光下的产氢活性为241 mmol·g-1·h-1,能量转化效率达7.4%,较未复合样品提高了42.3%;在可见光条件下,其产氢活性达9 mmol·g-1·h-1。     

Fundamental Insights into the Covalent Silane Functionalization of NiFe Layered Double Hydroxides

Layered double hydroxides (LDHs) are a class of 2D anionic materials exhibiting wide chemical versatility and promising applications in different fields, ranging from catalysis to energy storage and conversion. However, the covalent chemistry of this kind of 2D materials is still barely explored. Herein, the covalent functionalization with silanes of a magnetic NiFe-LDH is reported. The synthetic route consists of a topochemical approach followed by anion exchange reaction with surfactant molecules prior to covalent functionalization with the (3-aminopropyl)triethoxysilane (APTES) molecules. The functionalized NiFe-APTES was fully characterized by X-ray diffraction, infrared spectroscopy, electron microscopy, thermogravimetric analysis coupled with mass spectrometry and ²⁹Si solid-state nuclear magnetic resonance, among others. The effect on the electronic properties of the functionalized LDH was investigated by a magnetic study in combination with Mössbauer spectroscopy. Moreover, the reversibility of the silane-functionalization at basic pH was demonstrated, and the quality of the resulting LDH was proven by studying the electrochemical performance in the oxygen evolution reaction in basic media. Furthermore, the anion exchange capability for the NiFe-APTES was tested employing Cr^VI, resulting in an increase of 200 % of the anion retention. This report allows for a new degree of tunability of LDHs, opening the door to the synthesis of new hybrid architectures and materials.     

Molecular Engineering of Conjugated Polybenzothiadiazoles for Enhanced Hydrogen Production by Photosynthesis

The search for metal‐free organic photocatalysts for H₂ production from water using visible light remains a key challenge. Reported herein is a molecular structural design of pure organic photocatalysts, derived from conjugated polybenzothiadiazoles, for photocatalytic H₂ evolution using visible light. By alternating the substitution position of the electron‐withdrawing benzothiadizole unit on the phenyl unit as a comonomer, various polymers with either one‐ or three‐dimensional structures were synthesized and the effect of the molecular structure on their catalytic activity was investigated. Photocatalytic H₂ evolution efficiencies up to 116 μmol h^?1 were observed by employing the linear polymer based on a phenyl‐benzothiadiazole alternating main chain, with an apparent quantum yield (AQY) of 4.01 % at 420 nm using triethanolamine as the sacrificial agent.     

稀土离子掺杂对纳米TiO2光催化制氢活性的影响

采用溶胶-凝胶技术制备了纳米TiO2和一系列稀土离子掺杂的TiO2光催化剂,通过X射线衍射、透射电镜及N2吸附等技术对其进行了表征,考察了样品光催化分解水制氢的性能.结果表明,稀土离子掺杂有效抑制了TiO2粒子的生长,提高了粒子的分散性,增大了催化剂的比表面积,从而大幅度提高了其光催化分解水制氢的性能.其中,Gd3 掺杂的TiO2样品粒径最小,分散性最好,比表面积最大(是未掺杂TiO2的35倍).掺杂离子的电子构型对样品的光催化制氢活性有较大影响,具有全空电子构型的La3 和半充满电子构型的Gd3 掺杂的样品具有较高的光催化制氢活性(分别是未掺杂TiO2的3.69倍和3.72倍).     

二维/二维FeNi-LDH/g-C3N4复合光催化剂用于促进CO2光还原反应

Photocatalytic reduction of carbon dioxide into chemical fuels is a promising route to generate renewable energy and curtail the greenhouse effect. Therefore, various photocatalysts have been intensively studied for this purpose. Among them, g-C₃N₄, a 2D metal-free semiconductor, has been a promising photocatalyst because of its unique properties, such as high chemical stability, suitable electronic structure, and facile preparation. However, pristine g-C₃N₄ suffers from low solar energy conversion efficiency, owing to its small specific surface area and extensive charge recombination. Therefore, designing g-C₃N₄ (CN) nanosheets with a large specific surface area is an effective strategy for enhancing the CO₂ reduction performance. Unfortunately, the performance of CN nanosheets remains moderate due to the aforementioned charge recombination. To counter this issue, loading a cocatalyst (especially a two-dimensional (2D) one) can enable effective electron migration and suppress electron-hole recombination during photo-irradiation. Herein, CN nanosheets with a large specific surface area (97 m²·g^-1) were synthesized by a two-step calcination method, using urea as the precursor. Following this, a 2D/2D FeNi-LDH/g-C₃N₄ hybrid photocatalyst was obtained by loading a FeNi layered double hydroxide (FeNi-LDH) cocatalyst onto CN nanosheets by a simple hydrothermal method. It was found that the production rate of methanol from photocatalytic CO₂ reduction over the FeNi-LDH/g-C₃N₄ composite is significantly higher than that of pristine CN. Following a series of characterization and analysis, it was demonstrated that the FeNi-LDH/g-C₃N₄ composite photocatalyst exhibited enhanced photo-absorption, which was ascribed to the excellent light absorption ability of FeNi-LDH. The CO₂ adsorption capacity of the FeNi-LDH/g-C₃N₄ hybrid photocatalyst improved, owing to the large specific surface area and alkaline nature of FeNi-LDH. More importantly, the introduction of FeNi-LDH on the CN nanosheet surface led to the formation of a 2D/2D heterojunction with a large contact area at the interface, which could promote the interfacial separation of charge carriers and effectively inhibit the recombination of the photogenerated electrons and holes. This subsequently resulted in the enhancement of the CO₂ photo-reduction activity. In addition, by altering the loading amount of FeNi-LDH for photocatalytic performance evaluation, it was found that the optimal loading amount was 4% (w, mass fraction), with a methanol production rate of 1.64 μmol·h^-1·g^-1 (approximately 6 times that of pure CN). This study provides an effective strategy to improve the photocatalytic CO₂ reduction activity of g-C₃N₄ by employing 2D layered double hydroxide as the cocatalyst. It also proposes a protocol for the successful design of 2D/2D photocatalysts for solar energy conversion.      

热处理对TiO2纳米管结构相变的影响

TiO₂纳米管为无定形结构,焙烧后则由无定形转变为锐钛矿型,纳米管的管状结构被破坏,晶型转变是TiO₂纳米管的管状结构破坏的根本原因.经热处理,原来的TiO₂纳米管部分转变为长棒状的金红石型晶柱结构,而原料TiO₂在较大温度范围内焙烧均未出现长棒状晶柱结构;TiO₂由A→R的相变温差很大,TiO₂纳米管的A→R相变温度比原料约低350℃;合成的TiO₂纳米管的比表面积和孔体积很大.     

ZnIn2S4/TiO2/Ag复合光催化剂的制备及分解水制氢性能

首先采用溶剂热法将1D TiO_2纳米带均匀地穿插到片层结构组装而成的3D ZnIn_2S_4微球中,所形成的异质结构能有效抑制光生电子-空穴对。其次利用光沉积法将0D Ag纳米粒子负载在3D ZnIn_2S_4/1D TiO_2异质结构上。得益于0D Ag纳米粒子的等离子体效应及电子助催化剂作用,三元3D ZnIn_2S_4/1D TiO_2/0D Ag复合光催化剂在分解水制氢方面表现出优异的性能。在模拟太阳光照射下,ZnIn_2S_4/TiO_2/Ag复合光催化剂的产氢速率达到715μmol·g~(-1)·h~(-1),相对于ZnIn_2S_4/TiO_2、ZnIn_2S_4/P25、ZnIn_2S_4、TiO_2和P25分别提高了2.7倍、3.3倍、3.8倍、184倍和518倍。同时借助于X射线衍射、扫描电子和透射电子显微镜、X射线光电子能谱和紫外可见漫反射光谱等表征手段进一步论证了复合催化剂的优异性能。