二氧化钛负载单原子催化剂用于光催化反应的研究

Titania (TiO₂) has been among the most widely investigated and used metal oxides over the past years, as it has various functional applications. Extensive research into TiO₂ and industrial interest in this material have been triggered by its high abundance, excellent corrosion resistance, and low cost. To improve the activity of TiO₂ in heterogeneous catalytic reactions, noble metals are used to accelerate the reactions. However, in the case of nanoparticles supported on TiO₂, the active sites are usually limited to the peripheral sites of the noble metal particles or at the interface between the particle and the support. Thus, highly dispersed single metal atoms are desired for the effective utilization of precious noble metals. The study of oxide-supported isolated atoms, the so-called single-atom catalysts (SACs), was pioneered by Zhang's group. The high dispersion of precious noble metals results helps reduce the cost associated with catalyst preparation. Because of the presence of active centers as single atoms, the deactivation of metal atoms during the reaction, e.g., by coking for large agglomerates, is retarded. The unique coordination environment of the noble metal center provides special sites for the reaction, consequently increasing the selectivity of the reaction, including the enantioselectivity and stereoselectivity. Hence, supported SACs can bridge homogenous and heterogeneous reactions in solution as they provide selective reaction sites and are recyclable. Moreover, owing to the high site homogeneity of the isolated metal atoms, SACs are ideal models for establishing the structure-activity relationships. The present review provides an overview of recent works on the synthesis, characterization, and photocatalytic applications of SACs (Pt₁, Pd₁, Ir₁, Rh₁, Cu₁, Ru₁) supported on TiO₂. The preparation of single atoms on TiO₂ includes the creation of surface defective sites, surface modification, stabilization by high-temperature shockwave treatment, and metal-ligand self-assembly. Conventional characterization methods are categorized as microscopic imaging and spectroscopic methods, such as aberration-corrected scanning transmission electron microscopy (STEM), scanning tunneling microscopy (STM), extended X-ray absorption fine structure analysis (EXAFS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). We attempted to address the critical factors that lead to the stabilization of single-metal atoms on TiO₂, and elucidate the mechanism underlying the photocatalytic hydrogen evolution and CO₂ reduction. Although many fascinating applications of TiO₂-supported SACs in photocatalysis could only be addressed superficially and in a referencing manner, we hope to provide interested readers with guidelines based on the wide literature, and more specifically, to provide a comprehensive overview of TiO₂-supported SACs.     

Anchoring Single Nickel Atoms on Carbon-vacant Carbon Nitride Nanosheets for Efficient Photocatalytic Hydrogen Evolution

Polymeric carbon nitride(PCN) has emerged as a promising candidate for photocatalytic hydrogen evolution, but its dependence on scarce and high-cost noble metal co-catalysts severely limits its extensive application. It will be of great promise to develop non-noble metal single-atom co-catalysts with low-cost and high atom utilization to improve the photocatalytic performance over PCN. Herein, single Ni atoms are successfully anchored onto carbon-vacant PCN nanosheets(CCN-SANi) via a two-step ammonia thermal treatment and photo-deposition process. Theoretical calculations and experimental results demonstrate that the optical absorption property and the charge transfer ability of CCN-SANi have been significantly improved with the introduction of single Ni atoms to form Ni-N₃ sites. In comparison to carbon-vacant PCN(CCN) loaded with Ni clusters, the obtained CCN-SANi exhibits 11.4 times increased photocatalytic performance, with the highest hydrogen evolution rate reaching 511 μmol/(g·h), which is even 1.7 times higher than that of CCN loaded with Pt clusters. This research proposes an inspiring and reliable strategy to design novel single-atom semiconducting polymers with electronic structures manipulated for efficient photocatalysis.     

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.      

Effect of ZrS2 load single/dual-atom catalysts on the hydrogen evolution reaction: A first-principles study

The hydrogen evolution effect of ZrS₂ carrier loaded with transition metal single-atom (SA) was explored by first-principles method. ZrS₂ was constructed with transition metal single-atom and dual-atom. The structure–activity relationship of supported single-atom catalysts was described by electronic properties and hydrogen evolution kinetics. The results show that the ZrS₂ carrier-loaded atomic-level catalysts are more likely to occur in acidic environments, where the Mo SA load has a higher hydrogen precipitation capacity than the Pt SA. In the case of dual-atom adsorption, most of the hydrogen reduction processes are higher than that of single atom loading, which indicates that the outer orbital hybridization is more likely to lead to the interfacial charge recombination of the catalyst. Thereinto, Ni/Pt @ZrS₂ has the lowest Gibbs free energy (0.08 eV), and the synergistic effect of transition metals induces the deviation of the center of the d-band from the Fermi level and improves the dissociation ability of H ions. The design provides a new catalytic model for the HER and provides some ideas for understanding the two-site catalysis.     

TiO2-supported Single-atom Catalysts: Synthesis,Structure, and Application

In recent years, single-atom catalysts(SACs) have attracted increasing attention in catalysis. However, their stability is considerably challenging. As a result, fine-tuning the interaction of metal single atoms(SA) with different types of supports has emerged as an effective strategy for improving their thermal and chemical stabilities. Owing to its non-toxicity, cost-effectiveness, high abundance, and excellent stability, as well as presence of rich, tunable, and reliable anchor sites for metal SA, TiO₂ has been extensively explored as a superior support for SACs. In this review, recent advances of TiO₂-supported SACs(M₁/TiO₂) are discussed, and synthetic strategies, structure elucidation, and catalytic applications are summarized. First, the recently developed synthetic strategies for M₁/TiO₂arehighlighted and summarized, identifying the major challenges for the precise fabrication of M₁/TiO₂. Subsequently, key characterization techniques for the structure identification of M₁/TiO₂are discussed. Next, catalytic applications of M₁/TiO₂ are highlighted, viz. photocatalysis, electrocatalysis, and thermocatalysis. In addition, the mechanism via geometric structures and electronic states of metal centers facilitate catalytic reactions is outlined. Finally, opportunities and challenges of M₁/TiO₂ in catalysis are discussed, which may inspire the future development of M₁/TiO₂ for multifunctional catalytic applications.     

MoS_2/TiO_2复合催化剂的制备及其在紫外光下的光催化制氢活性

为了研究复合光催化剂在光催化中的制氢效率,采用水热法制备了Mo S2纳米片,然后通过水热法在Mo S2纳米片上负载了TiO_2纳米颗粒,形成了Mo S2/TiO_2异质结复合催化剂。采用冷场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、紫外-可见吸收光谱(UV-Vis)、拉曼光谱(Raman),X射线光电子能谱(XPS)对材料的结构和光学性能表征并进行分析。通过光催化制氢测试对光催化剂进行评价,实验结果表明,在波长为365 nm的紫外光照射下,最高光催化制氢速率为1004μmol·h-1·g-1,对应的催化剂的Mo S2含量为30%,其催化速率远大于单一的Mo S2和TiO_2,表明Mo S2/TiO_2复合催化剂在紫外光照下能显著提高光催化产氢性能。基于Mo S2/TiO_2复合光催化剂优越的光催化产氢性能,本文对复合光催化剂的产氢机理做了研究和分析。     

羧基功能化石墨烯增强TiO2光催化产氢性能

The use of semiconductor photocatalysts (CdS, g-C₃N₄, TiO₂, etc.) to generate hydrogen (H₂) is a prospective strategy that can convert solar energy into hydrogen energy, thereby meeting future energy demands. Among the numerous photocatalysts, TiO₂ has attracted significant attention because of its suitable reduction potential and excellent chemical stability. However, the photoexcited electrons and holes of TiO₂ are easily quenched, leading to limited photocatalytic performance. Furthermore, graphene has been used as an effective electron cocatalyst in the accelerated transport of photoinduced electrons to enhance the H₂-production performance of TiO₂, owing to its excellent conductivity and high charge carrier mobility. For an efficient graphene-based photocatalyst, the rapid transfer of photogenerated electrons is extremely important along with an effectual interfacial H₂-production reaction on the graphene surface. Therefore, it is necessary to further optimize the graphene microstructures (functionalized graphene) to improve the H₂-production performance of graphene-based TiO₂ photocatalysts. The introduction of H₂-evolution active sites onto the graphene surface is an effective strategy for the functionalization of graphene. Compared with the noncovalent functionalization of graphene (such as loading Pt, MoS_x, and CoS_x on the graphene surface), its covalent functionalization can provide a strong interaction between graphene and organic molecules in the form of H₂-evolution active sites that are produced by chemical reactions. In this study, carboxyl-functionalized graphene (rGO-COOH) was successfully modified via ring-opening and esterification reactions on the TiO₂ surface by using an ultrasound-assisted self-assembly method to prepare a high-activity TiO₂/rGO-COOH photocatalyst. The Fourier transform infrared (FTIR) spectra, X-ray photoelectron spectroscopy (XPS), and thermogravimetric (TG) curves revealed the successful covalent functionalization of GO to rGO-COOH by significantly enhanced ―COOH groups in FTIR and increased peak area of carboxyl groups in XPS. A series of characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), XPS, and UV-Vis adsorption spectra, were performed to demonstrate the successful synthesis of TiO₂/rGO-COOH photocatalysts. The experimental data for the hydrogen-evolution rate showed that the TiO₂/rGO-COOH displayed an extremely high hydrogen-generation activity (254.2 μmol∙h⁻¹∙g⁻¹), which was 2.06- and 4.48-fold higher than those of TiO₂/GO and TiO₂, respectively. The enhanced photocatalytic activity of TiO₂/rGO-COOH is ascribed to the carboxyl groups of carboxyl-functionalized graphene, which act as effective hydrogen-generation active sites and enrich hydrogen ions owing to their excellent nucleophilicity that facilitates the interfacial hydrogen production reaction of TiO₂. This study provides novel insights into the development of high-activity graphene-supported photocatalysts in the hydrogen-generation field.      

Isoelectric point-controlled preferential photodeposition of platinum on Cu2O-TiO2 composite surfaces

Isoelectric point-controlled preferential adsorption of[PtCl₆]^2- on Cu₂O/TiO₂ composite surfaces is revealed to play a key role in the photodeposition process.     

Dirac Nodal Arc Semimetal PtSn4: An Ideal Platform for Understanding Surface Properties and Catalysis for Hydrogen Evolution

Conductivity, carrier mobility, and a suitable Gibbs free energy are important criteria that determine the performance of catalysts for a hydrogen evolution reaction (HER). However, it is a challenge to combine these factors into a single compound. Herein, we discover a superior electrocatalyst for a HER in the recently identified Dirac nodal arc semimetal PtSn₄. The determined turnover frequency (TOF) for each active site of PtSn₄ is 1.54 H₂ s^?1 at 100 mV. This sets a benchmark for HER catalysis on Pt‐based noble metals and earth‐abundant metal catalysts. We make use of the robust surface states of PtSn₄ as their electrons can be transferred to the adsorbed hydrogen atoms in the catalytic process more efficiently. In addition, PtSn₄ displays excellent chemical and electrochemical stabilities after long‐term exposure in air and long‐time HER stability tests.     

光催化全解水助催化剂的设计与构建

能源和环境危机是当今社会面临的两大关键课题,利用太阳光驱动化学反应、将太阳能转化为化学能是解决上述问题的重要措施。通过光催化分解水是直接利用太阳能生产氢燃料的有效策略。光催化水分解过程可以分为三个基元步骤:光吸收、电荷分离与迁移、以及表面氧化还原反应。助催化剂可有效提高电荷分离效率、提供反应活性位点并抑制催化剂光腐蚀的发生,进而提高水分解效率。助催化剂也可以通过活化水分子以提高表面氧化还原动力学,进而提升整体光催化反应的太阳能转换效率。本文综述了助催化剂在光催化反应中的重要作用以及目前常用的助催化剂类型,详细说明了在光催化全解水过程中双助催化剂体系的构建及作用机理,并根据限制全解水的关键因素提出了新型助催化剂的设计策略。     

不同半导体体系中磷化镍光催化甲酸分解的助催化作用

研究了在不同的半导体体系(TiO₂, CdS和C₃N₄)中, Ni₂P光催化甲酸(HCOOH)分解制氢的助催化效应. 作为助催化剂, Ni₂P与3种半导体形成的复合光催化剂均表现出良好的HCOOH分解制氢活性. Ni₂P/TiO₂, Ni₂P/CdS, Ni₂P/C₃N₄ 3种光催化剂最优的产氢活性分别为41.69, 22.45和47.67 μmol·mg^-1·h^-1, 分别为纯TiO₂, CdS和C₃N₄的3.8倍、 10倍和210倍, 表明Ni₂P在光催化HCOOH分解制氢体系中具有普适性. 研究了光催化HCOOH分解制氢的机理, Ni₂P的加入使光生电子从半导体转移至Ni₂P, 提高了光生电子-空穴对的分离效率; Ni₂P还促进了活性物种·OH的生成, 提高了光催化HCOOH分解的产氢速率.     

Au/TiO_2/MoS_2等离子体复合光催化剂的制备及其增强光催化产氢活性

采用尿素沉积法制备了Au/Ti O_2/Mo S_2等离子体复合光催化剂。通过光催化产氢实验,在10%(φ,体积分数)甘油水溶液为牺牲剂条件下,研究了不同Mo S_2含量、Au固载2%(w,质量分数)时,Au/Ti O_2/Mo S_2(ATM)复合样品的光催化产氢活性。结果表明,当Mo S_2含量为0.1%(w)时,复合样品ATM0.1显示出最高的光催化产氢活性,其产氢速率达到708.85μmol·h~(-1),是Ti O_2/Mo S_2(TM)两相复合样品中光催化活性最高样品TM6.0产氢速率的11倍。三相复合样品显示增强光催化产氢活性主要是由于吸附在Ti O_2/Mo S_2层状复合材料上的Au纳米颗粒具有表面等离子共振效应,能强烈吸收波长范围550–560 nm的可见光,诱导产生光生电子,金纳米颗粒上的电子受到激发后转移到Ti O_2导带上,Ti O_2导带上的电子传递给片状Mo S_2,最终在Mo S_2上催化氢气产生。     

TiO2/Bi2O3纳米复合体的制备及可见光催化产氢性能

首先采用相分离的水解-溶剂热法制备了Bi₂O₃纳米粒子,然后利用简单的湿化学法在Bi₂O₃表面负载不同比例的TiO₂纳米颗粒,进而得到TiO₂/Bi₂O₃纳米复合体。通过气氛调控的表面光电压谱(SPS)等测试表明,表面负载适量的TiO₂后能够提高Bi₂O₃光生电荷分离。可见光催化产氢和降解污染物测试结果进一步证明,表面负载适量的TiO₂后可显著提高其可见光催化活性,其中Ti/Bi摩尔比为7%时具有最高的光催化活性。这主要归因于TiO₂具有较为合适的导带能级位置,可以接收Bi₂O₃在可见光激发下所产生的高能级电子,从而抑制光生电子-空穴对复合,并且维持了高能级电子较高的还原能力。     

Pt/H-TiO2催化剂制备及其甲醇电催化氧化性能

以四氯化钛为前驱体,采用水热法合成二氧化钛纳米棒（TiO₂,白色）,在纯H₂气氛,将其550 ^oC热处理2 h,即得有氧缺陷和Ti³⁺填隙原子的二氧化钛纳米棒（H-TiO₂,灰黑色）. 将Pt纳米粒子（~ 1.9 nm）负载于此两种二氧化钛纳米棒上,制得Pt/TiO₂和Pt/H-TiO₂催化剂. XRD和XPS测试表明,氢处理TiO₂晶型没有变化,仍属金红石型,但增加了Ti-OH表面物种. 电化学测试表明,H-TiO₂载体能够增强氧在Pt表面的吸脱附能力,从而提高其甲醇电催化氧化活性,Pt/H-TiO₂电极甲醇氧化峰电流密度为Pt/TiO₂电极的1.6倍、Pt/C电极的2.1倍.     

氮掺杂超薄碳纳米片复合铂钌单原子合金催化剂的电化学析氢性能

为了减少贵金属的用量, 降低成本, 提高大规模生产的可能性, 构建单原子合金(SAA)是一个非常可行的解决方案. 设计了一种超小PtRu单原子合金物种均匀分散在掺氮超薄碳纳米片上的电催化剂(PtRu SAA/NC), 并通过基于同步辐射的X射线吸收精细结构(XAFS)光谱进行了结构确认. 与纯Ru团簇和氮掺杂的碳片相比, PtRu SAA/NC具有更高的析氢反应(HER)催化活性和特殊的稳定性, 在0.5 mol/L H₂SO₄溶液中进行HER时, 表现出较小的Tafel斜率(43 mV/dec), 且在10 mA/cm²电流密度下过电位仅为54 mV.     

新型核壳Ag@AgSeX纳米粒子析氢助剂:原位表面硒化以提升TiO2的光催化产氢活性

纯相光催化材料的产氢性能主要受限于较低的电荷分离效率和缓慢的界面催化反应速率.表面负载助催化剂因其能够实现快速转移光生电子和提供界面催化活性中心被认为是促进电荷分离和提升界面催化反应的有效手段.贵金属类材料,尤其是金属铂(Pt),被认为是光催化产氢领域的理想助剂,但储量低和价格昂贵严重制约了其大规模实际应用.因此,发展...     

单原子催化剂在氧还原反应中的分子级调控

氧还原反应(ORR)在电化学能量存储和转换系统以及精细化学制剂的清洁合成中发挥着重要作用. 然而, ORR过程的动力学极其缓慢, 需要使用铂族贵金属催化剂加快其反应动力学速率. 铂基催化剂的高成本严重阻碍了其大规模的商业化. 由于单原子催化剂(SACs)具有结构明确、 本征活性高和原子效率高的特点, 有望取代昂贵的铂族贵金属催化剂. 迄今, 在进一步提高SACs的ORR活性方面已有大量的研究报道, 包括定制金属中心的配位结构、 丰富金属中心的浓度以及设计衬底的电子结构和孔隙率等. 本文综合评述了近年来SACs在ORR性能以及与ORR相关的H₂O₂生产、 金属-空气电池和低温燃料电池等方面的应用研究进展. 总结了通过引入其它金属或配体来调整孤立金属中心的配位结构、 通过增加金属负载来增加单原子位点的浓度以及通过优化载体的孔隙度来优化催化性能和电子传输等方面的研究进展, 并对SCAs的未来发展方向和面临的挑战提出了展望.     

Stable Isolated Metal Atoms as Active Sites for Photocatalytic Hydrogen Evolution

The process of using solar energy to split water to produce hydrogen assisted by an inorganic semiconductor is crucial for solving our energy crisis and environmental problems in the future. However, most semiconductor photocatalysts would not exhibit excellent photocatalytic activity without loading suitable co‐catalysts. Generally, the noble metals have been widely applied as co‐catalysts, but always agglomerate during the loading process or photocatalytic reaction. Therefore, the utilization efficiency of the noble co‐catalysts is still very low on a per metal atom basis if no obvious size effect exists, because heterogeneous catalytic reactions occur on the surface active atoms. Here, for the first time, we have synthesized isolated metal atoms (Pt, Pd, Rh, or Ru) stably by anchoring on TiO₂, a model photocatalystic system, by a facile one‐step method. The isolated metal atom based photocatalysts show excellent stability for H₂ evolution and can lead to a 6–13‐fold increase in photocatalytic activity over the metal clusters loaded on TiO₂ by the traditional method. Furthermore, the configurations of isolated atoms as well as the originality of their unusual stability were analyzed by a collaborative work from both experiments and theoretical calculations.     

Catalytic Reduction of Nitric Oxide on SiO2/AlO3-supported Transition Metal Catalysts

Selective reduction of nitric oxide in pressence of oxygen is one of the major challenges in the automobile exhaust after-treatment for lean-bum gasoline engines and diesel engines. Besides Cu-ZSM-5, Pt and Pd based noble metal catalysts, alumina-supported silver catalysts show high activities on NOx conversion to nitrogen^[1,2]. However, NO conversion activities over silver on binary oxides have rarely been studied in detail^[3], although copper on SiO₂-Al₂O₃ catalyst was reported to have a high activity^[4] Here, NOx reduction activities on SiO₂-Al₂O₃-supported transition metal catalysts prepared by sol-gel method was investigated.     

Pt/TiO2纳米纤维的制备及其对甲醇的电催化氧化活性

采用静电纺丝技术结合还原浸渍法制备了Pt/TiO₂纳米纤维电催化剂, 通过X射线衍射(XRD)分析、扫描电镜(SEM)、透射电镜(TEM)和X射线能谱(EDS)等测试手段对样品的晶相、形貌、微结构和化学组成进行了表征. 测试结果表明, TiO₂纳米纤维为锐钛矿和金红石组成的混晶, Pt 纳米颗粒均匀地分布于TiO₂纳米纤维的表面, 且Pt 颗粒大小较均一, 平均粒径为4.0 nm, Pt/TiO₂纳米纤维中Pt 的质量分数约为20%. 采用三电极体系的循环伏安和计时电流电化学分析方法研究了样品在酸性溶液中对甲醇的电催化氧化活性, 结果表明, 与负载相同质量分数Pt 的Pt/P25 和商业Pt/C 催化剂相比较, Pt/TiO₂纳米纤维催化剂对甲醇呈现出较高的电催化氧化活性和更好的稳定性.