Department of Chemistry and Lawrence Berkeley National Laboratory, University of California, Berkeley, California 94720-1460, USA.
J Am Chem Soc. 2009 Nov 25;131(46):16589-605. doi: 10.1021/ja9061954.
The challenge of chemistry in the 21st century is to achieve 100% selectivity of the desired product molecule in multipath reactions ("green chemistry") and develop renewable energy based processes. Surface chemistry and catalysis play key roles in this enterprise. Development of in situ surface techniques such as high-pressure scanning tunneling microscopy, sum frequency generation (SFG) vibrational spectroscopy, time-resolved Fourier transform infrared methods, and ambient pressure X-ray photoelectron spectroscopy enabled the rapid advancement of three fields: nanocatalysts, biointerfaces, and renewable energy conversion chemistry. In materials nanoscience, synthetic methods have been developed to produce monodisperse metal and oxide nanoparticles (NPs) in the 0.8-10 nm range with controlled shape, oxidation states, and composition; these NPs can be used as selective catalysts since chemical selectivity appears to be dependent on all of these experimental parameters. New spectroscopic and microscopic techniques have been developed that operate under reaction conditions and reveal the dynamic change of molecular structure of catalysts and adsorbed molecules as the reactions proceed with changes in reaction intermediates, catalyst composition, and oxidation states. SFG vibrational spectroscopy detects amino acids, peptides, and proteins adsorbed at hydrophobic and hydrophilic interfaces and monitors the change of surface structure and interactions with coadsorbed water. Exothermic reactions and photons generate hot electrons in metal NPs that may be utilized in chemical energy conversion. The photosplitting of water and carbon dioxide, an important research direction in renewable energy conversion, is discussed.
二十一世纪化学面临的挑战是在多步反应中实现所需产物分子 100%的选择性（“绿色化学”），并开发基于可再生能源的工艺。表面化学和催化在这一事业中起着关键作用。原位表面技术（如高压扫描隧道显微镜、和频产生（SFG）振动光谱、时间分辨傅里叶变换红外方法和常压 X 射线光电子能谱）的发展，使三个领域得到了快速发展：纳米催化剂、生物界面和可再生能源转化化学。在材料纳米科学中，已经开发出合成方法，可生产具有受控形状、氧化态和组成的 0.8-10nm 范围内的单分散金属和氧化物纳米粒子（NPs）；这些 NPs 可用作选择性催化剂，因为化学选择性似乎取决于所有这些实验参数。已经开发出在反应条件下运行的新光谱和显微镜技术，可揭示催化剂和吸附分子的分子结构在反应中间体、催化剂组成和氧化态变化的情况下随着反应的进行而动态变化。和频产生（SFG）振动光谱可检测疏水性和亲水性界面上吸附的氨基酸、肽和蛋白质，并监测表面结构的变化以及与共吸附水的相互作用。放热反应和光子在金属 NPs 中产生热电子，可用于化学能量转换。讨论了可再生能源转化的一个重要研究方向，即水和二氧化碳的光解。
