Many techniques have been employed for fabrication of flexible and transparent SERS substrates, which have been widely used in real applications and fundamental studies.
Plasmonic nanostructures have been widely used for photochemical conversions due to their unique and easy-tuning optical properties in visible and near-infrared range. Compared with the plasmon-generated hot electrons, the hot holes usually have a shorter lifetime, which makes them more difficult to drive redox reactions. This review focuses on the photochemistry driven by the plasmon-generated hot holes. First, we discuss the generation and energy distribution of the plasmon-generated hot carriers, especially hot holes. Then, the dynamics of the hot holes are discussed at the interface between plasmonic metal and semiconductor or adsorbed molecules. Afterwards, the utilization of these hot holes in redox reactions is reviewed on the plasmon-semiconductor heterostructures as well as on the surface of the molecule-adsorbed plasmonic metals. Finally, the remaining challenges and future perspectives in this field are presented. This review will be helpful for further improving the efficiency of the photochemical reactions involving the plasmon-generated hot holes and expanding the applications of these hot holes in varieties of chemical reactions, especially the ones with high conversion rate and selectivity.
The creation of crystal phase heterostructures of transition metal chalcogenides, e.g., the 1T/2H heterostructures, has led to the formation of metal/semiconductor junctions with low potential barriers. Very differently, post-transition metal chalcogenides are semiconductors regardless of their phases. Herein, we report, based on experimental and simulation results, that alloying between 1T-SnS2 and 1T-WS2 induces a charge redistribution in Sn and W to realize metallic Sn0.5W0.5S2 nanosheets. These nanosheets are epitaxially deposited on surfaces of semiconducting SnS2 nanoplates to form vertical heterostructures. The ohmic-like contact formed at the Sn0.5W0.5S2/SnS2 heterointerface affords rapid transport of charge carriers, and allows for the fabrication of fast photodetectors. Such facile charge transfer, combined with a high surface affinity for acetone molecules, further enables their use as highly selective 100 ppb level acetone sensors. Our work suggests that combining compositional and structural control in solution-phase epitaxy holds promises for solution-processible thin-film optoelectronics and sensors.
The reaction efficiency of reactants near plasmonic nanostructures can be enhanced significantly because of plasmonic effects. Herein, we propose that the catalytic activity of molecular catalysts near plasmonic nanostructures may also be enhanced dramatically. Based on this proposal, we develop a highly efficient and stable photocatalytic system for the hydrogen evolution reaction (HER) by compositing a molecular catalyst of cobalt porphyrin together with plasmonic gold nanoparticles, around which plasmonic effects of localized electromagnetic field, local heating, and enhanced hot carrier excitation exist. After optimization, the HER rate and turn-over frequency (TOF) reach 3.21 mol g−1 h−1 and 4650 h−1, respectively. In addition, the catalytic system remains stable after 45-hour catalytic cycles, and the system is catalytically stable after being illuminated for two weeks. The enhanced reaction efficiency is attributed to the excitation of localized surface plasmon resonance, particularly plasmon-generated hot carriers. These findings may pave a new and convenient way for developing plasmon-based photocatalysts with high efficiency and stability.
A surface
plasmon can drive many photochemical reactions, in which
effective charge separation and migration is a key. In analogy to
the plasmon–semiconductor interface, the plasmon–molecule
interface may also be used to improve the separation and migration
of hot carriers. In this work, by using in situ Raman spectroscopy,
molecular grafting on silver nanostructures is found essential for
modulating the charge separation and p-aminothiophenol
(PATP) oxidation reaction. When the LUMO of the grafted molecules
match well the energy distribution of the plasmon-generated hot electrons,
the PATP oxidation process accelerates significantly. Moreover, compared
with symmetrical grafting, asymmetrical grafting is more effective
in regulating the charge separation and plasmon-mediated chemical
reaction. This work provides an effective strategy for deep understanding
and fine modulation of plasmon-mediated photochemistry.
The debate between political liberalism and liberal perfectionism has taken center stage in contemporary literature on liberal political theory. According to political liberalism, the most sensible thing to do for political philosophy is to apply "the principle of toleration" to itself in order to arrive at a public conception of justice that is independent of controversial moral, philosophical, and religious doctrines. According to liberal perfectionism, basic liberal ideals and principles are compatible with the view that the state should direct citizens to live good or meaningful lives, and discourage them from pursuing bad or worthless ones. Both political liberalism and liberal perfectionism have developed substantial arguments to support their positions, and the debate between them has helped to shape the intellectual landscape of contemporary political philosophy.At the periphery of the mainstream liberal discourse, there has been growing interest in establishing and maintaining at least some liberal and democratic ideals and institutions in the burgeoning and increasingly pluralistic region of East Asia. One of the recent developments has led to sophisticated attempts to bring out the political side of Confucianism, the dominant source of cultural influence in the region. As some Confucian scholars have pointed out, East Asian societies, like their Western counterparts, are under the influence of reasonable pluralism, which diversifies and even divides the population in a region that used to be highly homogeneous. Thus, a plausible political theory and a timely model of democracy for East Asia must reflect this crucial I also wish to thank my committee members. Both Professor Alessandro Ferrara and Professor Sungmoon Kim offered me invaluable philosophical insights and intellectual encouragement, without which I would not be able to complete this dissertation. Professor Vanessa Rumble's lecture on Søren Kierkegaard pointed me toward a deeper understanding of morality, religion, and politics, which laid the very foundation for this project.Last but not least, special thanks to my beloved wife Ran An, who has believed in me throughout my years as a graduate student. This dissertation would not be possible without your loving support.1 For an anthology of works from both camps, see Perfectionism and Neutrality: Essays in Liberal Theory, eds.
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