Developing highly efficient and stable photocatalysts for the CO2 reduction reaction (CO2RR) remains a great challenge. We designed a Z‐Scheme photocatalyst with N−Cu1−S single‐atom electron bridge ...(denoted as Cu‐SAEB), which was used to mediate the CO2RR. The production of CO and O2 over Cu‐SAEB is as high as 236.0 and 120.1 μmol g−1 h−1 in the absence of sacrificial agents, respectively, outperforming most previously reported photocatalysts. Notably, the as‐designed Cu‐SAEB is highly stable throughout 30 reaction cycles, totaling 300 h, owing to the strengthened contact interface of Cu‐SAEB, and mediated by the N−Cu1−S atomic structure. Experimental and theoretical calculations indicated that the SAEB greatly promoted the Z‐scheme interfacial charge‐transport process, thus leading to great enhancement of the photocatalytic CO2RR of Cu‐SAEB. This work represents a promising platform for the development of highly efficient and stable photocatalysts that have potential in CO2 conversion applications.
Copper single‐atom electron bridges (SAEB) were constructed at the contact interface between Cu1/MoS2 and MIL‐125‐NH2 to achieve a highly active and stable catalyst for CO2 photoreduction. Empowered by the N−Cu1−S SAEB species, the Z‐Scheme charge‐transfer process was significantly promoted, leading to enhancement of the photocatalytic CO2RR.
Nonmetallic plasmonic heterostructure TiO2‐mesocrystals/WO3−x‐nanowires (TiO2‐MCs/WO3−x‐NWs) are constructed by coupling mesoporous crystal TiO2 and plasmonic WO3−x through a solvothermal procedure. ...The continuous photoelectron injection from TiO2 stabilizes the free carrier density and leads to strong surface plasmon resonance (SPR) of WO3−x, resulting in strong light absorption in the visible and near‐infrared region. Photocatalytic hydrogen generation of TiO2‐MCs/WO3−x‐NWs is attributed to plasmonic hot electrons excited on WO3−x‐NWs under visible light irradiation. However, utilization of injected photoelectrons on WO3−x‐NWs has low efficiency for hydrogen generation and a co‐catalyst (Pt) is necessary. TiO2‐MCs/WO3−x‐NWs are used as co‐catalyst free plasmonic photocatalysts for CO2 reduction, which exhibit much higher activity (16.3 µmol g−1 h−1) and selectivity (83%) than TiO2‐MCs (3.5 µmol g−1 h−1, 42%) and WO3−x‐NWs (8.0 µmol g−1 h−1, 64%) for methane generation under UV–vis light irradiation. A photoluminescence study demonstrates the photoelectron injection from TiO2 to WO3−x, and the nonmetallic SPR of WO3−x plays a great role in the highly selective methane generation during CO2 photoreduction.
Nonmetallic plasmonic TiO2‐MCs/WO3−x‐NWs heterostructures are constructed by coupling mesoporous crystal TiO2 and WO3−x nanowires, which have a continuous photoelectron injection leading to stable surface plasmon resonance (SPR) of WO3−x. The synergetic effect of photoelectron injection of TiO2 and SPR of WO3−x boosts hot electrons generation, which leads to highly efficient and selective methane generation in carbon dioxide reduction over TiO2‐MCs/WO3−x‐NWs under UV–vis light irradiation.
Anisotropic Ag2S‐edged Au‐triangular nanoprisms (TNPs) are constructed by controlling preferential overgrowth of Ag2S as plasmonic photocatalysts for hydrogen generation. Under visible and ...near‐infrared light irradiation, Ag2S‐edged Au‐TNPs exhibit almost fourfold higher efficiency (796 µmol h−1 g−1) than those of Ag2S‐covered Au‐TNPs (216 µmol h−1 g−1) and pure Au‐TNPs in hydrogen generation. A single‐particle photoluminescence study demonstrates that the plasmon‐induced hot electrons transfer from Au‐TNPs to Ag2S for hydrogen generation. Finite‐difference‐time‐domain simulations verify that the corners/edges of Au‐TNPs are high‐curvature sites with maximum electric field distributions facilitating hot electron generation and transfer. Therefore, Ag2S‐edged Au‐TNPs are efficient plasmonic photocatalyst with the desired configurations for charge separation boosting hydrogen generation.
Anisotropic Ag2S‐edged Au‐triangular nanoprisms (TNPs), exhibiting almost four‐fold higher efficiency than Ag2S‐covered ones in hydrogen generation under visible‐NIR light irradiation, are synthesized by controlling preferential overgrowth of Ag2S. Single‐particle photoluminescence and finite‐difference‐time‐domain studies demonstrate that Ag2S‐edged Au‐TNPs have the desired configuration for plasmon‐induced hot electron transfer and charge separation, leading to highly efficient hydrogen generation.
Plasmonic Bi2WO6 with strong localized surface plasmon resonance (LSPR) around the 500–1400 region is successfully constructed by electron doping. Oxygen vacancies on W–O–W (V1) and Bi–O–Bi (V2) ...sites are precisely controlled to obtain Bi2WO6-V1 with LSPR and Bi2WO6-V2 with defect absorption. Density functional theory (DFT) calculation demonstrates that the V1-induced energy state facilitates photoelectron collection for a long lifetime, resulting in LSPR of Bi2WO6. Photoelectron trapping on V1 sites is demonstrated by a single-particle photoluminescence (PL) study, and 93% PL quenching efficiency is observed. With strong LSPR, plasmonic Bi2WO6-V1 exhibits highly selective methane generation with a rate of 9.95 μmol g–1 h–1 during the CO2 reduction reaction (CO2-RR), which is 26-fold higher than 0.37 μmol g–1 h–1 of BiWO3-V2 under UV–visible light irradiation. LSPR-dependent methane generation is confirmed by various photocatalytic results of plasmonic Bi2WO6 with tunable LSPR and different light excitations. Furthermore, the DFT-simulated pathway of CO2-RR and in situ Fourier transform infrared spectra on the surface of Bi2WO6 prove that V1 sites facilitate CH4 generation. Our work provides a strategy to obtain nonmetallic plasmonic materials by electron doping.
Localized surface plasmon resonance (LSPR) enhanced photocatalysis has fascinated much interest and considerable efforts have been devoted toward the development of plasmonic photocatalysts. In the ...past decades, noble metal nanoparticles (Au and Ag) with LSPR feature have found wide applications in solar energy conversion. Numerous metal-based photocatalysts have been proposed including metal/semiconductor heterostructures and plasmonic bimetallic or multimetallic nanostructures. However, high cost and scarce reserve of noble metals largely limit their further practical use, which drives the focus gradually shift to low-cost and abundant nonmetallic nanostructures. Recently, various heavily doped semiconductors (such as WO3-x, MoO3-x, Cu2–xS, TiN) have emerged as potential alternatives to costly noble metals for efficient photocatalysis due to their strong LSPR property in visible-near infrared region. This review starts with a brief introduction to LSPR property and LSPR-enhanced photocatalysis, the following highlights recent advances of plasmonic photocatalysts from noble metal to semiconductor-based plasmonic nanostructures. Their synthesis methods and promising applicability in plasmon-driven photocatalytic reactions such as water splitting, CO2 reduction and pollution decomposition are also summarized in details. This review is expected to give guidelines for exploring more efficient plasmonic systems and provide a perspective on development of plasmonic photocatalysis.
Display omitted This review highlights the development of nanostructured materials with localized surface plasmon resonance advancing from noble metals to nonmetallic semiconductor-based composites and their applications for photocatalysis.
Plasmonic semiconductors with broad spectral response hold significant promise for sustainable solar energy utilization. However, the surface inertness limits the photocatalytic activity. Herein, a ...novel approach is proposed to improve the body crystallinity and increase the surface oxygen vacancies of plasmonic tungsten oxide by the combination of hydrochloric acid (HCl) regulation and light irradiation, which can promote the adsorption of tert‐butyl alcohol (TBA) on plasmonic tungsten oxide and overcome the hindrance of the surface depletion layer in photocatalytic alcohol dehydration. Additionally, this process can concentrate electrons for strong plasmonic electron oscillation on the near surface, facilitating rapid electron transfer within the adsorbed TBA molecules for C‐O bond cleavage. As a result, the activation barrier for TBA dehydration is significantly reduced by 93% to 6.0 kJ mol−1, much lower than that of thermocatalysis (91 kJ mol−1). Therefore, an optimal isobutylene generation rate of 1.8 mol g−1 h−1 (selectivity of 99.9%) is achieved. A small flow reaction system is further constructed, which shows an isobutylene generation rate of 12 mmol h−1 under natural sunlight irradiation. This work highlights the potential of plasmonic semiconductors for efficient photocatalytic alcohol dehydration, thereby promoting the sustainable utilization of solar energy.
The high‐active surface of plasmonic tungsten oxide is tuned by simultaneously increasing the body crystallinity and surface oxygen vacancies to overcome the hindrance of the surface depletion layer in photocatalytic alcohol dehydration. The activation barrier for TBA dehydration is significantly reduced by 93% to 6.0 kJ mol−1, and highly selective isobutylene generation reaches 1.8 mol g−1 h−1.
Plasmonic photocatalysts, which have intensive light absorption and high charge‐separation efficiencies, are regarded as promising candidates to solve energy and environmental issues in the future. ...In this Review, we summarize recent developments in the synthesis, activity, and mechanism of plasmonic photocatalysts, with the aim of stimulating improvements in photocatalytic activities and promoting the development of photocatalysis. The materials systems, energy‐transfer mechanisms, and factors that influence the photocatalytic activities of plasmonic photocatalysts are discussed. Some perspectives for the future development of the design of highly efficient plasmonic photocatalysts are proposed.
Plasmonic boom: Continuous advances in and improved understandings of the synthesis, mechanism, and activity of plasmonic photocatalysis point towards a breakthrough in the field to promote their application in energy and environmental issues. We discuss the synthesis, activity, and mechanism of plasmonic photocatalysts, including materials systems, and energy‐transfer mechanisms, to highlight recent developments and upcoming challenges.
Plasmonic hot carriers have the advantage of focusing, amplifying, and manipulating optical signals via electron oscillations which offers a feasible pathway to influence catalytic reactions. ...However, the contribution of nonmetallic hot carriers and thermal effects on the overall reactions are still unclear, and developing methods to enhance the efficiency of the catalysis is critical. Herein, we proposed a new strategy for flexibly modulating the hot electrons using a nonmetallic plasmonic heterostructure (named W
O
-nanowires/reduced-graphene-oxides) for isopropanol dehydration where the reaction rate was 180-fold greater than the corresponding thermocatalytic pathway. The key detail to this strategy lies in the synergetic utilization of ultraviolet light and visible-near-infrared light to enhance the hot electron generation and promote electron transfer for C-O bond cleavage during isopropanol dehydration reaction. This, in turn, results in a reduced reaction activation barrier down to 0.37 eV (compared to 1.0 eV of thermocatalysis) and a significantly improved conversion efficiency of 100% propylene from isopropanol. This work provides an additional strategy to modulate hot carrier of plasmonic semiconductors and helps guide the design of better catalytic materials and chemistries.
The gradual emissions of tetrabromobisphenol A (TBBPA) from the primitive recycling of E-waste create human health threats, which urgently require to develop an efficient, rapid yet simple detection ...method. The present study conducts a highly sensitive molecularly imprinted photoelectrochemical sensor (MIPES) containing molecularly imprinted (MI)-TiO
2
, Au, and reduced graphene oxide for the trace detection of TBBPA in indoor dust and surface water from an E-waste recycling area. The photocurrent response is used to evaluate the sensing performance of the MIPES toward TBBPA detection. The working potential for amperometry is 0.48 V. The wavelength range for photoelectrochemical detection is 320–780 nm. The sensor shows a detection range of 1.68 to 100 nM with a low limit of detection of 0.51 nM (LOD = 3
s
b
/
S
) and a limit of quantification of 1.68 nM (LOQ = 3.3 LOD). In addition, the MIPES sensor exhibits rapid, excellent reproducibility, selectivity, and long-term stability toward TBBPA detection. The relative standard deviation of three measurements for real samples is less than 7.0%, and the recovery range is 90.0–115%. The surface of molecular imprinting contributes to the high charge separation and sensing photocurrent response of TBBPA, which is confirmed by single-particle photoluminescence spectroscopy. The present study provides a new facile sensor with highly sensitive yet rapid response to detect environmental pollutants in E-waste by using the MIPES.
Graphical abstract
