Plasmonic Photocatalysis with Nonthermalized Hot Carriers

Active Site Engineering on Plasmonic Nanostructures for Efficient Photocatalysis

“…These techniques mainly include electron energy loss spectroscopy (EELS), , photoemission electron microscopy (PEEM), ultrafast spectroscopy (e.g., transient absorption), dark-field microscopy, , single-particle photoluminescence spectroscopy (PL), and surface-enhanced Raman spectroscopy (SERS). In photocatalysis, in situ /quasi in situ surface-sensitive analytic techniques, for instance, near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), ,, and SERS, are commonly used to study the reaction process on the photocatalyst surface. ,, These characterization techniques have been well summarized in their respective fields. , In this section, we mainly take SERS, an intersection characterization technique of the two fields, as an example to highlight the key characterization objects in plasmonic photocatalysis, including i) the energy coupling process of LSPR to surface reactions and ii) the activation and conversion process of surface reactants (i.e., reaction pathway). ,,, …”

“…180,191 In this section, we mainly take SERS, an intersection characterization technique of the two fields, as an example to highlight the key characterization objects in plasmonic photocatalysis, including i) the energy coupling process of LSPR to surface reactions and ii) the activation and conversion process of surface reactants (i.e., reaction pathway). 180,190,192,193 SERS has been one of the most extensively employed characterization techniques in plasmonic photocatalysis. 194−197 Theoretically, the Raman signal intensity is proportional to the fourth power of the electric field intensity (E 4 ).…”

Promoting plasmonic photocatalysis with ligand-induced charge separation under interband excitation

“…[4][5][6][7] Upon photon excitation, plasmons decay non-radiatively into highly energetic electron-hole pairs that can subsequently drive chemical reactions. [8][9][10][11][12][13][14][15][16] Due to these excellent properties, plasmonic nanoparticles have been demonstrated as photocatalysts or photoelectrocatalysts to drive various reactions, such as NH 3 decomposition, 17,18 CO 2 reduction, [19][20][21][22][23][24][25][26] hydrogen generation, [27][28][29] and NH 3 formation. [30][31][32][33] Photoexcitation of plasmonic nanoparticles through interband and intraband transitions generates hot carriers with various energies.…”

Plasmon-Mediated Hydrogen Dissociation with Symmetry Tunability

“…1−5 Localized surface plasmon resonance (LSPR) could occur in noble metal nanoparticles (NPs) and enhances light−matter interaction, which can greatly improve energy conversion efficiency. 6−8 The high catalytic activity of plasmonic metal has been attributed to (i) field enhancement (FE) owing to an elevated electric field near the nanostructure, 7,9,10 (ii) the transfer of electrons to foreign molecules by nonradiative plasmon decay, 5,11 and (iii) a localized thermal effect by plasmon decay. 12−14 For hot carrier-driven catalysis, hot electrons generated by plasmon decay can be transferred to the reactant through indirect electron transfer or direct electron excitation.…”

“…Plasmon-induced photocatalytic reactions have attracted considerable attention due to possible applications in solar energy conversions for solving the global energy crisis. − Localized surface plasmon resonance (LSPR) could occur in noble metal nanoparticles (NPs) and enhances light–matter interaction, which can greatly improve energy conversion efficiency. − The high catalytic activity of plasmonic metal has been attributed to (i) field enhancement (FE) owing to an elevated electric field near the nanostructure, ,, (ii) the transfer of electrons to foreign molecules by nonradiative plasmon decay, , and (iii) a localized thermal effect by plasmon decay. − For hot carrier-driven catalysis, hot electrons generated by plasmon decay can be transferred to the reactant through indirect electron transfer or direct electron excitation . The initially generated hot electrons undergo a thermalization process to form a thermal Fermi–Dirac distribution and then transfer into the adsorbed molecule, known as indirect electron transfer. , When a strong interaction exists between an adsorbent and plasmonic metal, a hybrid surface state is formed at the interface and provides an additional pathway for the direct generation of hot electrons in the adsorbent, known as direct charge transfer .…”