Boosting Plasmonic Hot Electron Utilization for Visible-Light Photocatalysis Using Polarized Ag-TiO 2 Nanoparticles

At a Glance

Metadata	Details
Publication Date	2022-10-13
Journal	CCS Chemistry
Authors	Yonglong Li, Linfeng Yu, Ying Wang, Cancan Zhang, Yangxuan Gao
Institutions	Advanced Energy Materials (United States), Nankai University
Citations	9

Abstract

Open AccessCCS ChemistryRESEARCH ARTICLES7 Nov 2022Boosting Plasmonic Hot Electron Utilization for Visible-Light Photocatalysis Using Polarized Ag-TiO2 Nanoparticles Yonglong Li†, Linfeng Yu†, Ying Wang, Cancan Zhang, Yangxuan Gao, Teng Wang and Wei Xie Yonglong Li† Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071 , Linfeng Yu† Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071 , Ying Wang Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071 , Cancan Zhang Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071 , Yangxuan Gao Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071 , Teng Wang Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071 and Wei Xie *Corresponding author: E-mail Address: [email protected] Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071 https://doi.org/10.31635/ccschem.022.202202296 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Plasmonic hot electrons have long been regarded as a promising energy source for inducing chemical transformations. However, because of the mismatch between the electron cloud of reactant molecules and the hot-electron gas of metal nanoparticles (NPs), the highly localized and short-lived hot electrons are difficult to utilize in bulk synthesis when the reactant molecules do not have a strong affinity for the metal surface. Here, we propose the concept of polarized nanocatalysts to mimic chemical polarity at the nanometer scale. Under plasmonic photorecycling conditions, the rationally designed asymmetric Ag-TiO2 hybrid NPs enable six-electron reduction of molecules in bulk solution. This hot-electron-driven reaction does not require a conventional hydrogen or hydride reducing agent. As a proof-of-concept, one-pot photocatalytic syntheses of amides, such as paracetamol, using nitro reactants were performed. This provides a new opportunity to enable challenging multielectron transformations in organic chemistry. Download figure Download PowerPoint Introduction Heterogeneous photocatalysis provides a promising pathway to drive solar-to-chemical energy conversion.1 Metal nanoparticles (NPs) having strong interactions with visible light through localized surface plasmon resonances (LSPR) are emerging heterogeneous photocatalysts.2-11 The nonradiative decay of plasmons generates localized energetic charge carriers (hot electrons and holes), which are surface redox centers on the metal NP surface.12,13 Upon photoexcitation, a plasmonic metal NP accomplishes two aligned redox transformations, that is, hot-electron-driven reduction and hot-hole-driven oxidation.14,15 A prominent example is the plasmonicconversions between 4-nitrothiophenol (4-NTP), 4-aminothiophenol (4-ATP) and 4,4′-dimercaptoazobenzene (4,4′-DMAB).16 These model reactions were studied by surface-enhanced Raman spectroscopy (SERS), a chosen analytical tool with high surface sensitivity to detect chemical species on plasmonic metals, enabling deep mechanistic understanding of the hot-carrier-driven reactions.17-27 Nevertheless, in most cases the chemicals involved in hot-carrier-driven reactions are anchored on the metal surface via a thiol or other surface-seeking group. Synthetic chemistry involving substances without surface-seeking groups on plasmonic catalysts remains challenging because the short-lived hot carriers cannot be utilized by the molecules diffusing from bulk solution.28 Heterojunctions of metal and semiconductor can enhance hot-electron-hole separation via the charge transfer at the Schottky barrier interfaces.28-35 Therefore, metal-semiconductor hybrid nanomaterials usually exhibit high photocatalytic activity under plasmonic excitation.36-41 Examples are the hot-electron-driven reductions of C-X and C=O groups in organic synthesis, typically involving one- or two-electron transfer between molecules and catalysts.32,41 So far, plasmonic hybrid nanomaterials have not been able to catalyze reactions beyond four-electron transfer. We previously reported that six-electron 4-NTP (-NO2) to 4-ATP (-NH2) reduction occurs on plasmonic Ag NPs when halide anions (Cl−, Br−, or I−) are present.42,43 Because the formation and photodissociation of AgX consume plasmonic holes on Ag, more hot electrons can be transferred to adjacent molecules. However, when the reactant molecules do not have a surface-seeking group to anchor on the plasmonic metal, this six-electron reduction cannot occur under otherwise identical conditions. Inspired by chemical polarity that can help attract and align reactant molecules, we propose the concept of designing polarized plasmonic catalysts. Localized and short-lived hot electrons are difficult to inject in the lowest unoccupied molecular orbitals (LUMOs) of reactants in bulk solution due to the mismatch between the electron cloud of reactant molecules and hot-electron gas of metal NPs. An analogy is molecular hydrogen, which does not react with hydroxide anion in aqueous alkaline solution: when one H is replaced by F, a strong charge separation forms in H(δ+)···F(δ−), and thus the electron-cloud overlap between HF and OH− becomes easy (Figure 1). In this work, we designed and synthesized an asymmetric Ag-TiO2 hybrid nanoparticle to polarize the plasmonic catalyst. Under visible-light irradiation, the plasmonic hot electrons on the Ag surface were transferred across the Schottky barrier (φSB) and accumulated in the conduction band of TiO2, resulting in a nanoscale-polarized hot-carrier dipole: Ag(δ+)···TiO2(δ−). Photorecycling of the Ag surface using halide anions further inhibited charge-carrier recombination and enabled six-electron reduction in bulk synthesis. As a proof-of-concept, one-pot hot-electron-driven syntheses of amide compounds using nitro reactants were performed. Figure 1 | Conceptual design of polarized plasmonic photocatalyst. A six-electron photorecycling process on Ag-TiO2 hybrid nanostructure. Download figure Download PowerPoint Experimental Methods Synthesis of polarized Ag-TiO2 NPs A modified method from Ref. 44 was used to synthesize Ag-TiO2 heterostructures. In a typical synthesis, ∼90 nm quasi-spherical Ag NPs were synthesized by a reported method.43 To prepare Ag-TiO2 heterostructures, 0.15 mL HCl solution of 15% TiCl3 was diluted with 4 mL N2-saturated H2O (nitrogen gas was introduced into deionized water for more than 20 min) in a 20 mL glass vial. NaHCO3 (0.6 mL, 1M) was added to the solution dropwise. Afterwards, 10 mL Ag core solution was concentrated to 0.5 mL and mixed with 1 mL N2-saturated H2O and 400 μL of 0.2 M cetyltrimethylammonium bromide (CTAB). The mixture was added into the above solution, and then the solution became blue grey. After 60 min, Ag-TiO2 heterostructures were washed with ethanol twice. Replacing CTAB solution with the same volume of degassed water led to the formation of Ag-TiO2 core-shell NPs under the same reaction conditions. Photocatalytic reduction of 4-nitrophenol A 20 mL quartz tube equipped with a stir bar was charged with 150 μL of 10 mM 4-nitrophenol (4-NP) aqueous solution, diluted sulfuric acid, metal-semiconductor nanocomposites as catalysts, and aqueous halide ions solution of certain concentration, and then the solution was diluted with deionized water to 4 mL. Supporting Information shows the experimental details. Subsequently, the reaction mixture was stirred and sonicated until fine dispersion of the solid catalysts was obtained. The mixture was degassed by a vacuum pump for 3-5 min and then filled with N2 gas using a balloon with needle. The mixture was irradiated with a white light-emitting diode (powder intensity ∼165 mW/cm2, wavelength region of 400-700 nm). After the respective reaction time, an aliquot of the reaction mixture (∼600 μL) was centrifuged. For UV-vis analysis, the reaction mixture (150 μL) was mixed with 450 μL of 1 M NaOH diluted with 1 mL deionized water, filtered by nylon syringe filter with 2.2 μm aperture, and subjected to UV-vis analysis. Preparation of Ag/Au-TiO2 photocatalysts Metal-loaded semiconductor (TiO2) was prepared by a photodeposition method.45 A 2 g amount of semiconductor powder, metal precursor (130 mg AgNO3 or 24 mL of 25 mM HAuCl4), and 65 mg sodium citrate were added to a 250 mL beaker with 50 mL deionized water under vigorous stirring, followed by irradiation with UV and visible light from a mercury vapor lamp (power density 200 mW/cm2) at room temperature for 120 min. Then, the suspension was centrifuged at 6577 g for 10 min and washed with water. The procedure was repeated five times to remove metal precursor and sodium citrate. The metal-loaded solid catalysts were dried under infrared heat lamp and ground to powder. Electrochemical measurements To prepare the electrodes, Au/Ag colloid suspension was centrifuged and then resuspended in ethanol. Plasmonic colloid suspensions were then dip-coated on the pretreated indium tin oxide surface and allowed to dry for 30 min under an infrared heat lamp. Electrochemical measurements were carried out in a three-electrode electrochemical cell with a Pt wire counter electrode and a Hg/Hg2Cl2 (3.5 M KCl) reference electrode.46 All electrochemical experiments were conducted in 50 mL of 0.5 M NaClO4 and 120 μM potassium iodide (KI) solutions with a pH value tuned to 3.0 using H2SO4. To measure open-circuit potential (OCP) of the Au and Ag electrode in the presence of iodide, the working electrode was immersed in the above mixture solution containing KI until its rest potential stabilized. The 300 W xenon lamp was employed as the light source in the OCP measurements. Photocatalytic synthesis of amides from aromatic nitro compounds (typical procedure A) A 20 mL quartz tube equipped with a stir bar was charged with the nitro compounds (0.05 mmol, 1.0 equiv), Ag-TiO2 (50 mg, ∼0.14 wt %), and CTAB (5 mg). Subsequently, acid anhydride (0.1-0.5 mmol, 2.0-10.0 equiv, i.e., 0.1 mmol benzoic anhydride, 0.25 mmol succinic anhydride, and 0.5 mmol acetic anhydride) and isopropanol (6 mL) were added and the quartz tube was equipped with an air vent valve. The reaction mixture was stirred and then sonicated until fine dispersion of the solid catalysts was achieved. The mixture was degassed by a vacuum pump for 3 min and then equipped with a balloon filled with N2 gas. The reaction solution was irradiated by a xenon lamp (powder intensity of ∼150 mW/cm2, wavelength region of 320-800 nm) at room temperature under rapid stirring. After the respective reaction time, an aliquot of the reaction mixture (∼650 μL) was centrifuged, filtered by nylon syringe filter with 2.2 μm aperture and then subjected to gas chromatography-mass spectrometry (GC-MS) analysis. For quantitative analysis, a certain amount of the internal standard was added for 1H NMR or GC measurements. Photocatalytic synthesis of amides from alkyl nitro compounds (typical procedure B) A 20 mL quartz tube equipped with a stir bar was charged with the alkyl nitro compounds (0.05-0.1 mmol, i.e., 0.05 mmol nitrocyclohexane and (nitromethyl)benzene, 0.1 mmol nitromethane and 1-nitropropane), Ag-TiO2 (50 mg, ∼0.14 wt %), and CTAB (5 mg). Subsequently, acid anhydride (0.25-0.5 mmol, i.e., 0.25 mmol benzoic anhydride and 0.5 mmol acetic anhydride) and isopropanol (8 mL) were added and the quartz tube was equipped with an air vent valve. The following steps were the same as the typical procedure A. Photocatalytic synthesis of 4-acetamido phenol (paracetamol) from 4-NP The experimental methods are modified from typical procedure A. A 20 mL quartz tube equipped with a stir bar was charged with the 4-NP compounds (0.05 mmol, 1.0 equiv), Ag-TiO2 (80 mg, ∼0.14 wt %), and CTAB (20 mg). Subsequently, acetic anhydride (0.5 mmol, 10.0 equiv) and isopropanol (8 mL) were added and the quartz tube was equipped with an air vent valve. The following steps were the same as typical procedure A. Results and Discussion Synthesis of polarized plasmonic Ag-TiO2 photocatalysts We prepared a specific Ag-TiO2 asymmetric nanostructure to prolong the lifetime of hot electrons to be injected into the LUMOs of surface adsorbates. We used a wet-chemistry method using CTAB as a soft template and by controlling the degree of TiCl3 hydrolysis (as shown in Figure 2a).44 The anisotropic overgrowth of TiO2 on Ag NPs is shown by transmission electron microscopy (TEM) and high angle annular dark field-scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (HAADF-STEM-EDX) analyses (Figure 2b,c). Bilayers of surface-capping agents like CTAB are densely packed on metallic NP surfaces and frequently utilized for the anisotropic overgrowth CTAB-capped NPs with metal or metal oxide.44,47,48 To understand the role of CTAB during the synthesis, a negative control experiment was performed without adding CTAB aqueous solution. Agcore-TiO2shell NPs with a TiO2 shell fully covered on the Ag core ( Supporting Information Figure S1) were obtained instead of the Ag-TiO2 heterostructures (Figure 2d, Supporting Information Figure S2). In the wet-chemistry synthesis, CTAB acts as a protective agent selectively adsorbed to the Ag metal surfaces and leads to the anisotropic overgrowth of TiO2 on Ag NP surfaces.44 The Ag-TiO2 heterostructures were used as photocatalysts in the six-electron reduction of 4-nitrophenol (without a surface-seeking group), which does not require conventional hydrogen or hydride reducing agents. After several hours, the chemical transformation of 4-NP to 4-aminophenol catalyzed by the polarized photocatalysts were observed in the UV-vis absorption spectra; in contrast, Agcore-TiO2shell NPs show very low activity in this photocatalytic reaction ( Supporting Information Figure S3). The most exciting feature of the designed Ag-TiO2 heterostructures is that Ag surfaces are exposed to the reaction solution, which enables hot-electron recycling on the Ag surface via the formation and subsequent optical field-accelerated dissociation of silver halide. Figure 2 | (a) Synthesis of polarized plasmonic Ag-TiO2 photocatalysts. Elemental map (b) and corresponding elemental profiles (c) of a single polarized Ag-TiO2 nanoparticle. (d) SEM image of many Ag-TiO2 photocatalysts. (The inset is a TEM picture of the Ag-TiO2 photocatalysts). Download figure Download PowerPoint Photocatalytic performance To show the general applicability of utilizing polarized plasmonic photocatalysts, we prepared Ag-TiO2 nanocomposites via photodeposition of Ag on TiO2 ( Supporting Information Figure S4). We designed 36 sets of control experiments (Figure 3a, Supporting Information Tables S1-S6), to uncover the role of metallic Ag, TiO2 semiconductor, halogen ion, and illumination. Remarkably, halogen ions can significantly accelerate the bulk reduction reaction catalyzed by the Ag-TiO2 photocatalyst. The promotion of the reaction rate after adding halogen ion (Figure 3b) is negligible if Au is used instead of Ag (for the corresponding characterization data see Supporting Information Figure S5). 4-NP reduction rate at different Br− concentrations are shown in Figure 3c. With the same concentration of Br− and Cl−, a higher 4-NP reduction rate is achieved in the Br− containing solution (Figure 3d). In particular, I− shows an extremely high activity in the bulk phase reduction reaction, even at much lower concentrations compared with Br− and Cl− (Figure 3d, Supporting Information Table S2 gives the experimental operating details), which is consistent with their activity trend in the model surface reaction studied by SERS.42,43 Supporting Information Figure S6 shows the characterization results of Ag-TiO2 nanocomposites after reaction to illustrate the high stability of the photocatalyst. Wavelength-dependence results are shown in Supporting Information Figure S7. The determination of the conversion concentration of 4-NP is carried out with UV-vis external standard method ( Supporting Information Figure S8). This hot-electron-driven reaction used water as the hydrogen source, which offers advantages over current technologies using hydrogen or hydride reducing agent. Figure 3 | (a) Thirty-six sets of control experiments demonstrating 4-NP reduction catalyzed by polarized Ag-TiO2 photocatalysts. (b) 4-NP photocatalytic reduction on Ag-TiO2 and Au-TiO2, with and without the presence of Br−. 4-NP photocatalytic reduction reaction on Ag-TiO2 nanocomposites in the presence of Br− at different concentrations (c) and in the presence of different halide ions (d). Download figure Download PowerPoint Mechanism characterization According to the proposed mechanism, it is crucial to understand the interaction between hot holes and halide ions on plasmonic Ag surface. Taking advantage of the strong surface affinity of X− for the plasmon-generated Ag holes, we detected the adsorbed halide ions on the surface of Ag NPs in the low wavenumber region (from 120 to 250 cm−1) of SERS spectra (Figure 4a).49 Figure 4b shows typical light scattering spectra of single Ag and Au NPs in aqueous KI solution to compare the different transformation process of halide ions on metallic holes. Under continuous laser illumination, a redshift of about 35 nm was observed due to the formation of photosensitive AgI on the Ag surface, and then the photodissociation of AgI led to an approximate 25 nm blueshift of the LSPR peak. For a single Au nanoparticle, there is only a slight redshift, which can be attributed to the physical adsorption of iodides on the Au surface. In addition, a photoelectrochemical method is utilized to study the anodic OCP shift on an electrode with Ag and Au nanostructures in the presence of iodides.46 As shown in Figure 4c, the anodic OCP on Au electrode decreases upon plasmonic excitation, indicating that the hot holes are trapped by anions, mainly including I− from the bulk electrolyte. This contrasts the cathodic OCP shift observed on the Ag electrode, where the concentration of adsorbed I− deceases due to the plasmon-promoted AgI dissociation. Figure 4 | (a) SERS spectra of AgX on plasmonic Ag surface. (b) Light scattering band shift of single Ag and Au NPs in an aqueous solution of 120 μM KI. (c) OCP of Ag and Au nanocrystal-modified electrodes in the KI solution. (d) SERS spectra of 4-NTP on Ag-TiO2 (blue curve) and Ag NP (yellow curve) surfaces in an aqueous solution of 0.5 M H2SO4. (e) EPR light-minus-dark difference spectra of TiO2 and Ag-TiO2 under visible light illumination. Note: the difference spectrum was obtained by subtracting the EPR spectrum measured in the dark from the EPR spectrum under light. (f) Schematic illustration of the excitation of hot electrons in the polarized catalyst-molecule hybrid system. Download figure Download PowerPoint We immobilized 4-NTP molecules on the metallic Ag surface of the Ag-TiO2 nanocomposites, to construct both metal-semiconductor and metal-molecule interfaces in the plasmonic photocatalytic system. Under laser illumination, the hot electrons on the Ag surface are transferred to the conduction band of TiO2 instead of the LUMOs of 4-NTP, which prevents the formation of 4,4′-DMAB (Figure 4d). Light illumination on plasmonic Ag-TiO2 also leads to distinct electron paramagnetic resonance (EPR) bands (Figure 4e), which are attributed respectively to hot electrons trapped at oxygen vacancies (VO, g = 2.006) and the formation of Ti3+ (g = 1.966).35 However, no discernible contributions from light-induced Ti3+ EPR signal in pure TiO2 can be detected under the identical visible-light illumination, indicating that the plasmonic hot electrons were not directly generated in TiO2.35 Collectively, these results (including the photocurrent responses in Supporting Information Figure S9) validate the plasmon-mediated electron transfer in the Ag-TiO2 heterostructures (Figure 4f) and confirm that the transferred hot electrons were trapped in TiO2 ( Supporting Information Figure S10) with prolonged lifetime. Photocatalytic amide synthesis from nitro compounds By using the polarized photocatalysts, amide bond-formation reactions were performed via the photorecycling process (Figure 5). Isopropanol was used as organic solvent to dissolve various substrate molecules with different groups in this plasmonic photocatalytic synthesis. Additionally, control experiments were carried out to demonstrate hot electrons from the photorecycling process also can be utilized in isopropanol (see Supporting Information Figure S11). Paracetamol, suitable for relieving mild to moderate pain, was synthesized under mild reaction conditions (without using noble metal catalyst and conventional reductant or applying electrochemical potential and elevated temperature). In addition, a series of nitroaromatic compounds (1-5) can be smoothly converted to the corresponding amide products. Significantly, nitro groups on aromatic rings carrying another unsaturated unit, such as ester, cyano, or alkynyl group, could be selectively reduced to the corresponding anilines and then functionalized to amide products (6-8). By using benzoic anhydride and succinic anhydride, other kinds of amides (9 and 10) were also prepared in our experiments. For alkyl nitro-reactants, the polarized Ag-TiO2 is also an efficient photocatalyst for synthesizing amide products in halide media. Compound A and B containing the N-cyclohexyl amide moiety (Figure 5) are very By using the Ag-TiO2 catalysts, could be synthesized with nitrocyclohexane and benzoic anhydride as the and obtained in moderate Supporting Information and show the 1H NMR and GC results of typical products. Figure | of aromatic and alkyl The of amides was by 1H NMR or GC Download figure Download PowerPoint Polarized plasmonic photocatalyst is proposed and used in the bulk synthesis of amide The plasmonic hot electrons transferred from Ag to TiO2 are by the adjacent reactant molecules, and halide anions the charged Ag surface (hot via the which the electron cloud of Ag-TiO2 nanostructure and the photocatalyst. The proposed is by a single scattering method and the photoelectrochemical method more than amide compounds have been synthesized by the polarized Ag-TiO2 catalysts under light illumination. 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DOI: https://doi.org/10.31635/ccschem.022.202202296