单原子催化剂的合成及其能源电催化应用的研究进展

基于电化学反应的能源储存与转化技术为全球能源结构的转型提供了一条绿色、 可持续的途径, 高效的电催化剂在其中扮演着重要的角色. 得益于在物理、 化学性质上的独特优势, 单原子催化剂在电催化能源转化方面展现出巨大的应用前景. 本文综合评述了单原子催化剂的合成及其能源电催化应用的研究进展, 介绍了单原子催化剂的常见表征手段, 总结了单原子催化剂的合成方法(湿化学法、 高温热解法、 原子沉积法、 电化学沉积法等), 并介绍了该类材料在氧还原、 二氧化碳电还原、 电解水及氮气电还原反应中的研究进展, 重点探讨了催化剂微观结构与其性能之间的关系, 最后, 对单原子能源电催化领域所面临的挑战进行了总结, 并对该领域未来的发展方向进行了展望.     

单原子催化剂在CO2转化中的应用

单原子催化剂(SAC)是由互相隔离分散的原子级活性位点锚定在基底上而形成的一类新兴催化剂材料, 其具有最大化的原子利用率、 可调控的独特电子结构, 因而在热催化、 光催化及电催化等方面展现出良好的应用前景. 通过SAC的热/光/电催化CO₂转化反应(CCR)能将温室气体CO₂转化为燃料或具有附加值的化学品, 为解决严重的全球变暖和能源短缺问题提供了一种有效策略. 本文总结了近年来SAC在CO₂转化领域的研究进展, 讨论了其合成、 调控及催化各类CO₂转化反应的优缺点, 并对其未来的发展进行了展望.     

吡咯氮配位单原子铜催化剂的电催化二氧化碳还原性能

采用温度控制的浸渍-热解法, 合成了以碳纳米管为载体的一系列铜单原子催化剂. 扩展X射线吸收精细结构(EXAFS)分析表明, 催化剂中的单原子铜位点分别由吡啶氮和吡咯氮配位. 电催化性能测试表明, 所制备催化剂可用于电催化二氧化碳生成一氧化碳, 由吡啶氮配位的铜单原子催化剂的反应选择性较差, 而由吡咯氮配位的铜单原子催化剂则具有更强的活性, CO法拉第效率在-0.70 V(vs. RHE)时可达到96.3%; 吡咯氮配位的铜单原子中心对于析氢反应具有更好的抑制效果.     

基底表面构建单原子催化剂与催化性能研究进展

近年来,单原子催化剂因其较高的催化活性和选择性等优点而受到了人们的广泛关注.我们综述了以C,Si,Ti,Al为基底的单原子催化剂的制备方法,并对以不同材料基底制备单原子催化剂的制备方法、形成机理及优势特点进行了比较.通过对单原子制备、表征方法及催化活性的概述,以期对制备单原子催化剂提供一定的借鉴和指导.研究表明,单原子...     

Hydroformylation of 1-Octene over Nanotubular TiO2-supported Amorphous Co-B Catalysts

TiO₂ nanotubes supported amorphous Co-B(Co-B/TNTs) catalyst was prepared via impregnationchemical reduction procedure. The catalyst was characterized with transmission electron microscopy(TEM), ammonia temperature-programmed desorption(NH₃-TPD), thermogravimetry-differential thermal analysis(TG-DTA), Fourier transform infrared spectroscopy(FTIR) and Raman spectroscopy. The effects of temperature and ratio of CO to H₂ on the hydroformylation of 1-octene were studied. At an optimized reaction temperature(150℃) and volume ratio of CO to H₂(2:1), the conversion of 1-octene can reach 97.4% with a selectivity of 23.1% for total aldehydes and n/i-aldehyde molar ratio of 40:60. To obtain higher selectivity for linear aldehydes, Co-B/TNTs modified with triphenylphosphine for the hydroformylation of 1-octene were investigated. When molar ratio of P/Co was 4, the yield of total aldehydes was the highest(31.6%) with a good selectivity for linear product(n/i-aldehyde molar ratio was 70:30). In recycle use, the Co-B/TNTs catalyst modified with triphenylphosphine could be reused five times without reducing the activity and selectivity obviously. For a comparative study, all the Co-B/TNTs to catalyze the hydroformylation of other olefins exhibited high conversion under the optimized conditions.     

不同pH值制备的TiO2和TiO2/SiO2催化剂结构、表面性质及光催化活性

以TiOSO₄和SiO₂溶胶为原料, 采用沉淀法用氨水调节pH值制备TiO₂和TiO₂/SiO₂催化剂. 制备的催化剂用X射线衍射(XRD), 扫描电镜(SEM), N₂吸附(BET), 紫外-可见(UV-Vis)漫反射光谱, 程序升温脱附(NH₃-TPD), 傅里叶变换红外(FT-IR)光谱技术分析. XRD谱图显示纯TiO₂中锐钛型和金红石相共存, 且金红石相含量随pH值升高而增加. 但是, TiO₂/SiO₂催化剂只有锐钛型. 扫描电镜发现制备的催化剂呈类球形, 颗粒间相互交叠, 粒径在10-25 nm之间. TiO₂和TiO₂/SiO₂光催化剂的比表面积随pH值升高略有增大. SiO₂的添加会增大催化剂的比表面积. 程序升温脱附实验结果说明催化剂的表面酸量随pH值升高而增加. TiO₂/SiO₂的表面酸量比相同pH值制备的TiO₂大. 红外光谱分析说明Si掺杂和高pH值有利于催化剂表面生成更多的羟基. TiO₂和TiO₂/SiO₂光催化剂的催化活性随pH值升高而明显增强. TiO₂/SiO₂的光催化活性优于TiO₂. TiO₂/SiO₂催化剂具有较好的耐久性.     

单原子材料在二氧化碳催化中的技术经济分析与产业化应用前景

近年来, 随着科学研究的不断深入, 单原子催化剂由于具有高活性与高选择性等突出特点被广泛挖掘和应用. 作为连接多相与均相催化的桥梁, 单原子催化剂已经成为催化领域的重要研究对象之一, 具有广泛的工业化应用前景. 本文对单原子催化剂的发展历程、 特点及其在不同领域的应用进行了概括, 综合评述了当前CO₂还原领域的技术经济分析, 并首次对单原子材料催化转化CO₂进行了技术经济分析与计算. 最后, 对单原子催化剂在CO₂还原领域中工业化应用的未来发展方向及亟需解决的关键科学和技术问题进行了展望, 以期推动单原子催化材料的进一步广泛应用.     

单原子催化的关键进展与未来挑战

单原子催化剂(SACs)兼具均相与多相催化剂的双重优势, 表现出最大化的原子利用率、 超高的本征活性与选择性以及易与产物分离的特点, 受到人们的广泛关注. 然而, 由于单个原子较高的表面能以及不稳定性, 设计与制备单原子催化剂仍是一大挑战. 本文综合评述了近年来单原子催化剂的稳定化策略、 高载量催化剂的制备方法以及批量制备技术等方面的关键研究进展, 并简要分析了单原子催化剂未来发展所面临的问题与挑战, 最后对单原子催化的发展方向进行了展望.     

单原子催化中的活性位构建方法研究进展

近年来,单原子催化剂因具有多相催化剂的结构稳定、易分离和均相催化剂的“孤立位点”等潜在优点而受到了人们的广泛关注.因此我们着重对比说明了单原子催化剂多种制备方法的形成机制以及制备过程的优缺点,并结合相应反应对其催化活性、催化机理进行介绍.通过对单原子催化剂的制备研究现状的概述,以期对加快其工业化进程起到积极的促进作用.     

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.     

焙烧温度对TS/TiO2结构及光催化反应性能的影响

TS/TiO2是一种热稳定的光催化材料.将该样品分别在300、400、500、540、600和700℃下空气中焙烧,并用UV-Raman、XRD、BET及TPD等手段进行了表征.同时,以苯乙烯光催化氧化反应为探针,考察了其光催化氧化反应性能.结果表明,焙烧温度对催化剂的结构与表面性质有较大程度的影响,除TS/TiO2的晶型及比表面积外,其酸量也发生了较大程度的变化;并与催化剂性能进行了关联.     

TiO2-CeO2催化剂湿式氧化苯酚的活性研究

采用共沉淀法制备了湿式氧化降解苯酚的TiO2-CeO2催化剂，测定了反应过程中不同反应时间的COD去除率，结果表明，当Ti、Ce摩尔比为3：1时，在150℃、总压5MPa（其中氧分压4．5MPa）时，所制备的催化剂活性最高，反应90分钟COD去除率可以达到71％．对催化剂进行了比表面积、XRD和XPS测试，结果表明，高效的催化剂具有较多的活性位、催化剂粉末体系Ce的变价特性以及大量的表面吸附氧．     

树叶为模版制备网状TiO2和Fex/TiO2及光催化活性研究

以梧桐树叶为模板制备了具有网状结构的TiO2和Fex/TiO2光催化材料.通过扫描电镜(SEM)、X-射线衍射(XRD)、X-射线光电子能谱(XPS)、荧光发射光谱(PL)、紫外-可见吸收光谱(UV-Vis)等对这两类光催化材料的结构和物理性能进行了表征.结果表明,以树叶为模板制得的Fe0.005/TiO2呈网状结构.在600～800℃范围内,随煅烧温度的升高,网状TiO2和Fe0.005/TiO2中锐钛型TiO2的含量减少,Fe3+的掺杂能促进锐钛型向金红石型的转变.与Degussa P25相比,网状TiO2和Fex/TiO2的荧光光谱强度明显减弱,光生电子-空穴对的复合情况得到改善;吸收光谱范围明显红移,禁带宽度有不同程度的缩小.孔雀石绿的光催化降解实验表明,网状TiO2和Fex/TiO2具有比Degussa P25更强的催化活性.光催化活性的稳定性研究表明,网状Fe0.005/TiO2具有良好的稳定性,能多次重复使用.     

球形TiO2-Al2O3的制备、结构和理化性能研究

将Ti(SO4)2溶于稀盐酸合成酸性钛溶胶,再将其与铝溶胶和六次甲基四胺溶液混合后采用油柱成型法制备了球形TiO2-Al2O3复合氧化物。通过XRD、低温氮吸附-脱附与NH3-TPD等手段对样品进行表征,结果表明600℃焙烧得到的球形TiO2-Al2O3中TiO2以无定型形式存在;随TiO2含量的增加,球形TiO2-Al2O3的比表面积、孔容和平均孔径呈增加趋势;TiO2的引入没有对球形TiO2-Al2O3的强酸和弱酸中心的强度产生影响,弱酸中心数量显著增加,强酸中心数量稍有增加;球形TiO2-Al2O3的堆密度和压碎强度随TiO2含量的增加而减小,颗粒直径基本保持不变。     

以TiO2多孔微球为载体的CuO/TiO2催化剂的制备、表征及CO氧化催化性能

利用高分子反相悬浮聚合技术结合溶胶-凝胶法制备了纳米TiO2晶粒组成的多孔微球. 以TiO2多孔微球为载体, 利用浸渍法制备了CuO/TiO2催化剂, 用示差扫描量热法、热重分析、X 射线衍射和X射线光电子能谱(XPS)对TiO2多孔微球和催化剂进行了表征, 并对其进行了CO催化氧化性能的评价. 结果表明, 于500 ℃焙烧的TiO2多孔微球基本为锐钛矿型结构, 其粒径为19.5 nm. XPS结果表明, 催化剂中载体和活性组分存在相互作用, Cu除了以Cu2+的形式存在外, 还以部分Cu+和Cu0的形式存在. CO催化氧化研究结果表明, 催化剂的催化活性与浸渍液的浓度和催化剂的焙烧温度有关. 用0.5 mol/L Cu(NO3)2·3H2O溶液浸渍得到的催化剂和于200 ℃焙烧得到的催化剂具有较好的催化活性.     

Advanced TEM Characterization for Single-atom Catalysts: from Ex-situ Towards In-situ

Clean energy innovation has triggered the development of single-atom catalysts(SACs) due to their excellent catalytic activity, high tunability and low cost. The success of SACs for many catalytic reactions has opened a new field, where the fundamentals of catalytic property-structure relationship at atomic level await exploration, and thus raises challenges for structural characterization. Among the characterization techniques for SACs, aberration-corrected transmission electron microscopy(TEM) has become an essential tool for direct visualization of single atoms. In this review, we briefly summarize recent studies on SACs using advanced TEM. We first introduce TEM methods, which are particularly important for SACs characterization, and then discuss the applications of advanced TEM for SAC characterization, where not only atomic dispersion of single atoms can be studied, but also the distribution of elements and the valence state with local coordination can be resolved. We further extend our review towards in-situ TEM, which has increasing importance for the fundamental understanding of catalytic mechanism. Perspectives of TEM for SACs are finally discussed.     

Ag改性TiO2催化剂的制备、表征及其甲苯气相光催化降解性能

用溶胶-凝胶法制备Ag改性的TiO2催化剂,并用XRD、SEM、BET、O2-TPD和UV-Vis DRS等测试手段对其进行表征．结果表明,与TiO2相比,所制备催化剂颗粒直径明显减小,比表面积明显增大,对可见光的吸收明显增强,同时出现了表面吸附氧和Ag电子捕获中心．甲苯气相光催化降解结果显示,当Ag与Ti的摩尔比（n...     

锐钛矿型TiO2担载的Pd催化剂用于乙炔选择加氢的催化性能及其表征

Anatase TiO₂ nanospindles containing 89% exposed {101} facets (TiO₂-101) and nanosheets with 77% exposed {001} facets (TiO₂-001) were hydrothermally synthesized and used as supports for Pd catalysts. The effects of the TiO₂ materials on the catalytic performance of Pd/TiO₂-101 and Pd/TiO₂-001 catalysts were investigated in the selective hydrogenation of acetylene to polymer-grade ethylene. The Pd/TiO₂-101 catalyst exhibited enhanced performance in terms of acetylene conversion and ethylene yield. To understand these effects, the catalysts were characterized by H₂ temperature-programmed desorption (H₂-TPD), H₂ temperatureprogrammed reduction (H₂-TPR), transmission electron microscopy (TEM), pulse CO chemisorption, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The TEM and CO chemisorption results confirmed that Pd nanoparticles (NPs) on the TiO₂-101 support had a smaller average particle size (1.53 nm) and a higher dispersion (15.95%) than those on the TiO₂-001 support (average particle size of 4.36 nm and dispersion of 9.06%). The smaller particle size and higher dispersion of Pd on the Pd/TiO₂-101 catalyst provided more reaction active sites, which contributed to the improved catalytic activity of this supported catalyst.     

单原子催化剂在电化学合成氨中的理论研究进展

传统Haber-Bosch工艺合成氨需要大量的能源消耗和复杂的工厂基础设备。在可再生能源的推动下,将氮气电化学还原为氨被认为是替代Haber-Bosch工艺最有效的方法,这在科学界引起了极大的关注。然而,这个过程受到氨产量和法拉第效率低的影响,因此开发更有效的电催化剂对其实际应用至关重要。在之前报告的催化剂中,单原子催化剂（SACs）在高效利用原子和不饱和配位方面表现出显著优势,这为优化催化剂性能提供了巨大的空间。文章综述了单原子催化剂在电化学合成氨中的理论研究,详细分析了贵金属催化剂、非贵金属催化剂和非金属催化剂这3类单原子催化剂的性能表现,旨在为电化学合成氨技术的发展提供理论参考。