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多相催化技术在环境修复、炼油工艺、能源转化、汽车制造和发电行业等[1-3]领域发挥着至关重要的作用,因此催化技术的发展进步对经济发展和环境保护产生重大的积极影响。自1986年纳米技术的首次提出以来,纳米催化技术得到了快速发展。纳米催化剂由于粒径小、分布均匀、高效的催化效果等特点在各个领域备受欢迎。然而,在这些催化反应过程中,活性位的结构和化学价态变化之间相互影响,很大程度上决定了纳米催化剂的催化性能,往往需要借助先进的表征技术对催化剂的物理化学性质和“质构-能效”关系进行分析。近年来,国内外学者致力于研究提高金属纳米颗粒催化性能的方法,如通过调控金属纳米颗粒的尺寸和形状[4-7]、金属与载体的相互作用[8-14]及金属的氧化状态和配位结构等[2, 15-16]。其中,减小活性相的颗粒尺寸来增大其比表面积和分散度[17],让纳米结构中更多的活性位如表面缺陷、低配位和不饱和原子[18]暴露出来,是目前最常用的方法之一。然而,多数催化反应对纳米结构十分敏感,当金属纳米粒子小于10 nm时,这一点变得尤为明显,因为特定的表面位置,如顶角位、台阶位,以及高度不饱和配位原子[19],使颗粒尺寸成为影响催化性能的主导因素。因此,在分子或原子水平上调控纳米金属颗粒的性质和尺寸,是提高催化性能的关键步骤[17]。
可控合成金属纳米粒子及其在大气污染防治领域的应用进展
Controllable synthesis of metal nanoparticles and their application in air pollution control
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摘要: 近年来,由于更严格的环境标准和工业需求,催化技术得到突飞猛进的发展。金属纳米粒子由于其独特的性质,如高表面能、等离子体激发、量子限制效应等,成为环境、电子、材料等科学领域的关键元件。随着金属纳米颗粒尺寸的减小和分散性的提高,活性中心的结构缺陷逐渐凸显,同时产生的尺寸效应极大的改善了催化反应活性和选择性。因此,为了充分利用纳米催化剂的优势,本文结合调控金属粒径大小的研究现状,依据不同的合成原理,重点介绍了反胶束法、物理气相沉积法、化学气相沉积法、喷雾热解法和光刻法的原理和特点及其他调控方法,总结了纳米颗粒尺寸大小在大气污染防治领域的典型应用,并展望了金属纳米粒子的发展趋势和应用前景,为高性能催化剂的设计和制备提供参考.Abstract: In recent years, due to more stringent environmental standards and industrial needs, catalytic technology has been developed rapidly. Due to their unique properties, such as high surface energy, plasma excitation, quantum confinement effect, metal nanoparticles have become the key components in the field of environment, electronics, materials and other scientific fields. With the decrease of metal nanoparticles size and the increase of dispersion, the structural defects of the active center are gradually highlighted, and the size effect greatly improves the catalytic activity and selectivity. Therefore, in order to make full use of the advantages of nanocatalysts, the principle and characteristics of reverse micelle method, physical vapor deposition method, chemical vapor deposition method, spray pyrolysis and photolithography method and other control methods are introduced in this paper according to the research status of controlling metal particle size and different synthesis principles. The typical application of nanoparticle size in the field of air pollution control is summarized, and the development trend and application prospect of metal nanoparticles are prospected, which provides reference for the design and preparation of high performance catalysts.
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Key words:
- metal /
- nanocatalyst /
- synthesis method /
- particle size /
- application
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图 2 (A) TiO2@g‐CN纳米结构,(B)TiO2纳米颗粒阵列的表面和截面形态,(C)TiO2@g‐CN-12 min, (D)TiO2@g‐CN-24 min, (E)TiO2@g‐CN-60 min, (F)TiO2@g‐CN-120 min[41]
Figure 2. (A)Formation diagram of TiO2@g‐CN, (B)surface and cross‐sectional morphologies of TiO2 nanorods arrays (NRs), (C)TiO2@g‐CN-12 min, (D)TiO2@g‐CN-24 min, (E)TiO2@g‐CN-60 min, and (F)TiO2@g‐CN120 min[41]
图 3 在不同温度下制备的Pd/C催化剂的大小分布,以及Pd纳米颗粒的平均粒径和Pd/C-0催化剂来自不同区域的HAADF-STEM图像和高分辨率TEM图像[50]
Figure 3. TEM images, the corresponding size distribution, and the mean particle size of Pd nanoparticles for Pd/C catalysts prepared at different temperatures. A HAADF-STEM image and high-resolution TEM images from different regions are additionally provided for the Pd/C-0 catalyst[50]
表 1 利用反胶束法合成不同粒径的纳米催化剂
Table 1. Synthesis of Nanocatalysts with Different Particle Size by Reverse Micelle Method
反应条件
Reaction condition材料
Material尺寸大小
Particle size文献
Reference十二烷基硫酸钠和正己烷的混合溶液体系 Th纳米粒子 2.8 nm [28] 钨酸钠、氯化铁和氢氧化钠混合体系 W纳米粒子 13 nm [29] 以3-巯基丙酸为含羧基的纳米粒子稳定剂,通过酰胺键形成共价堆积到多孔基底 羧基化Ag纳米粒子 5.2 nm [30] 硫酸锌/氢氧化钠水溶液/异辛烷体系 ZnO纳米粒子 2.8 nm [31] 水/AOT/己烷体系、W=10 ZnO纳米粒子 6 nm [32] CO-520/水/环己烷体系、W=4 LaAlO3纳米粒子 (19±3) nm [33] (1-十六烷基)三甲基溴化铵作为表面活性剂,1-丁醇作为助表面活性剂,
2,2,4-三甲基戊烷作为油相BaSnO3、SrSnO3
纳米粒子4.2 nm、8.3 nm [34] H2O/NP-6/C6H12体系、W=9 PdO-SnO2纳米粒子 10 nm [35] W (W=H2O/CTAB)=5.01 CdS纳米粒子 4 nm [36] H2O/AOT/C7H16体系、W=10 ZnS:Mn2+纳米粒子 4.4 nm [37] 表 2 合成方法的影响因素及优缺点
Table 2. Influence factors and advantages and disadvantages of synthetic methods
方法
Method影响因素
Influencing factor优缺点
Advantages and disadvantages反胶束法 W (W=水/表面活性剂)的物质的量比值、
水相pH值、温度和离子强度等合成的尺寸分布窄、均匀,不需要特殊仪器或极端条件,
但不适合大批量生产物理气相沉积法 沉积位置、沉积温度和沉积时间等 对环境无污染,方法简单,耗材少,沉积速率大,
但偶尔会有一些大颗粒产生化学气相沉积法 反应物成分等 方法简单,但沉积速率小,会产生一些环境污染物 喷雾热解法 合成温度和前驱体浓度等 颗粒均匀,粒径可控制性强,原料消耗少 光刻法 显影时间等 粒径可控,但成本高昂,不适合合成小于20 nm的材料。 表 3 不同Cu粒径的Cu / C催化剂系列的部分物理性质[5]
Table 3. The physical properties of the Cu/C catalyst series of different Cu sizes[5]
催化剂
CatalystCu负载量/% wt
Cu loading温度/°C
T粒径大小/ nm
Particle sizeCu/OC 6.3 250 3.1 Cu/OC 6.3 330 4.2 Cu/OC 6.3 350 5.2 Cu/OC 6.3 400 7.3 Cu/OC 16.4 230 8.0 Cu/PC 6.3 230 8.6 Cu/PC 7.0 230 9.1 Cu/PC 8.0 230 9.5 Cu/PC 9.0 230 9.8 Cu/PC 10.0 230 10.0 Cu/PC 11.0 230 11.7 Cu/PC 11.7 230 13.4 -
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