Photoexcited Electrons Research Articles

Anti-Site Defect-Induced Cascaded Sub-Band Transition in CuInS2 Enables Infrared Light-Driven CO2 Reduction.

Photocatalytic CO2 conversion is a promising approach to simultaneously mitigate climate change and alleviate the energy crisis. However, infrared light, which constitutes nearly half of the solar energy, has not been effectively utilized yet. In this work, we discover a photogenerated charge transition mechanism in CuInS2 with intrinsic InCu antisite defects for synergistic utilization of full-spectrum photons. Femtosecond transient absorption spectroscopy and DFT calculation unveil an intermediate band induced by the intrinsic antisite defects, where cascaded sub-band transition could be realized by high-energy photons (UV-vis) and low-energy (IR), thus improving the absorption range of infrared light as well as the utilization efficiency of photogenerated carriers. In situ Kelvin probe force microscopy demonstrates that the generation of photoexcited electrons could be greatly enhanced through this synergistic utilization of full spectrum light. Moreover, in situ X-ray photoelectron spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy reveal that infrared photons could also enhance the adsorption and activation of CO2 and H2O on the catalyst surface. As a result, the CO production rate under full spectrum light reaches 19.9 μmol g-1 h-1, which is more than a 7-fold increase over that under UV-vis irradiation.

Engineering the electron localization of metal sites on nanosheets assembled periodic macropores for CO2 photoreduction

Photocatalytic conversion of CO2 into syngas is highly appealing, yet still suffers from the undesirable product yield due to the sluggish carrier transfer and the uncontrollable affinity between catalytic sites and intermediates. Here we report the fabrication of Co sites with tunable electron localization capability on two dimensional (2D) nanosheets assembled three dimensional (3D) ordered macroporous framework (3DOM-NS). The as-prepared Co-based 3DOM-NS catalysts exhibit attractive photocatalytic performances toward CO2 reduction, among which the cobalt sulfide one (3DOM Co-SNS) shows the highest syngas generation rate up to 347.3 μmol h−1 under the irradiation of visible light and delivers a remarkable catalytic activity (1150.7 μmol h−1) in a flow reaction system under natural sunlight. Mechanism studies reveal that the high electron localization of metal sites in 3DOM Co-SNS strengthens the interaction between Co and HCOO* via the orbital interactions of dyz/dxz-p and s-s, thus facilitating the cleaving process of C-O bond. Additionally, the ordered macroporous framework with nanosheet subunits elevates the transfer efficiency of photoexcited electrons, which contributes to its high activity.

High-efficiency PMS activation by difunctional Co-Fe PBA/g-C3N4 S-scheme heterojunction for oxytetracycline degradation: Performance evaluation and mechanism insight

The utilization of sulfate radical-based advanced oxidation processes (SR-AOPs) has captivated the academic community due to their minimal energy requirements and superior efficacy in peroxomonosulfate (PMS) activation for pollutant decomposition. Notwithstanding these advantages, engineering an effective and economical catalyst for PMS activation presents a considerable hurdle. In the present study, a metal-organic framework of CoFe PBA is ingeniously anchored onto g-C3N4 nanosheets, resulting in the formation of an innovative CoFe PBA/g-C3N4 S-scheme heterojunction that demonstrates remarkable efficiency in PMS activation. Intriguingly, the catalytic efficiency of CoFe PBA/g-C3N4 surpasses that of g-C3N4 and CoFe PBA by 7-fold and 2.33-fold, respectively. The heightened activity of CoFe PBA/g-C3N4 heterojunction is attributed to the enhanced charge transfer efficiency, a consequence of the successful heterojunction formation. Concurrently, the ability of photoexcited electrons to reduce Co3+/Fe3+ to Co2+/Fe2+ bolsters PMS activation. Significantly, this heterojunction retains unparalleled stability in degrading oxytetracycline without discernible performance attenuation, heralding its commendable prospects in real-world applications. Besides, mechanism exploration indicates that SO4−, h+, and electron transfer contribute to oxytetracycline degradation in the CoFe PBA/g-C3N4 system. This investigation serves as a beacon for the strategic development of highly active and stable catalysts for PMS activation, aiming at environmental decontamination.

Photochromism in the periodic nanospace of zeolite LTA by the transfer of photoexcited electrons of adsorbed Na atoms.

Cationic sodium (Na) clusters incorporated into a dehydrated Na-form LTA (Na-LTA) zeolite by the adsorption of Na atoms exhibit diamagnetism regardless of their adsorption amount. These clusters preferentially form in β-cages under the condition of dilute adsorption. In this study, photochromism was observed on the dilute Na-adsorbed Na-LTA, which showed a color change from yellow-green to dark blue-green at room temperature. This phenomenon resulted in dissociation of the diamagnetic Na clusters in β-cages upon light irradiation and thereby in the formation of two metastable Na43+ clusters with C3v symmetry in α-cages from the photoabsorption and electron spin resonance spectra. We also observed photochromism in a sample of insufficiently dehydrated Na-LTA with dilute Na adsorption-i.e., the initial white color changed to blue, then blue-green and finally dark moss-green upon irradiation with UV light. This phenomenon consists of two steps. First, products in the β-cages, formed by the reaction of residual water molecules with adsorbed Na atoms, release electrons upon irradiation. The electrons transfer to the α-cages, forming the metastable Na43+ clusters. Next, the diamagnetic Na clusters are formed in vacant β-cages by the thermal transfer of electrons from the Na43+ clusters in the α-cages. Na clusters including multiple electrons were also formed in the α-cages by long exposure to UV light irradiation, which had a similar effect to increasing the adsorption amount of Na atoms onto the dehydrated Na-LTA. After termination of irradiation, the sample required a week to change its color to light yellow.

Interface dipole evolution from the hybrid coupling between nitrogen-doped carbon quantum dots and polyethylenimine featuring the electron transport thin layer at Al/Si interfaces

The assessment of electron transport layer (ETL) for rear-contact engineering of silicon (Si) based optoelectronics has been considered as one of the critical challenges that leverage the performance improvement and device reliability. In this work, the hybrid design of ETL, obtained from the solution-processed nitrogen-doped carbon quantum dots (NCQDs) incorporated with organic polyethylenimine (PEI) demonstrates the feasible contact characteristics for the modification of Si/Al contacts, which greatly facilitates the transport and collection of photoexcited electrons in the Si-based optoelectronics. The aspects of microstructures, functional groups, chemical features, interfacial characteristics and band structures of NCQD/PEI are explicated, visualizing that the evolution of interface dipoles mediated by the overall outcome of physisorption and chemisorption effects, modifies the surface potential difference and results in the explicit reduction of the Al work function from 4.3 eV for pristine Al to 3.23 eV based on the optimized constitutional design (0.10 % NCQD in PEI). These findings are practically employed on the Si-based hybrid solar cells at Si/Al interfaces, fulfilling the conversion-efficiency improvement by 30.9 % compared with reference cells without ETL employment, which are experimentally interpreted by the efficient electron transport across the Si/Al heterojunction and charge collection.

Efficient photoreduction of CO2 to CO by Co-ZIL-L derived NiCo-OH with ultrathin nanosheet assembled 2D leaf superstructure.

The photocatalytic reduction of CO2 into valuable chemicals and fuels is considered a promising solution to address the energy crisis and environmental challenges. In this work, we introduce a Co-ZIL-L mediated in situ etching and integration process to prepare NiCo-OH with an ultrathin nanosheet-assembled 2D leaf-like superstructure (NiCo-OH UNLS). The resulting catalyst demonstrates excellent photocatalytic performance for CO2 reduction, achieving a CO evolution rate as high as 309.5 mmol g-1 h-1 with a selectivity of 91.0%. Systematic studies reveal that the ultrathin nanosheet structure and 2D leaf-like architecture not only enhance the transfer efficiency of photoexcited electrons but also improve the accessibility of active reaction sites. Additionally, the Ni-Co dual sites in NiCo-OH UNLS accelerate CO2 conversion kinetics by stabilizing the *COOH intermediate, significantly contributing to its high activity. This work offers valuable insights for designing advanced photocatalysts for CO2 conversion.

Aeration‐Free Photo‐Fenton‐Like Reaction Mediated by Heterojunction Photocatalyst toward Efficient Degradation of Organic Pollutants

The regulation of peroxymonosulfate (PMS) activation by photo‐assisted heterogeneous catalysis is under in‐depth investigation with potential as a replaceable advanced oxidation process in water purification, yet it remains a significant challenge. Herein, we demonstrate a strategy to construct polyethylene glycol (PEG) well‐coupled dual‐defect VO‐M‐Co3O4@CNx S‐scheme heterojunction to degrade organic pollutants without aeration, which dramatically provides abundant active sites, excellent photo‐thermal property, and distinct charge transport pathway for PMS activation. The degradation rate of VO‐M‐Co3O4@CNx in anaerobic conditions shows a higher efficient rate (4.58 min‐1 g‐2) than in aerobic conditions (1.67 min‐1 g‐2). Experimental evidence reveals that VO‐M‐Co3O4@CNx promotes more rapid redox conversion of photoexcited electrons induced by defects with PMS under anaerobic conditions compared to aerobic conditions. Additionally, in situ experiments and DFT provide mechanistic insights into the regulation pathway of PMS activation via synergistic defect‐induced electron, revealing the competitive effect between O2 and PMS over VO‐M‐Co3O4@CNx during the reaction process. The continuous flow reactor and flow cytometry results demonstrated that the VO‐M‐Co3O4@CNx/PMS/Vis system has remarkably enhanced stability and purification capability for removing organic pollutants. This work provides valuable insights into regulating the heterologous catalysis oxidation process without aeration through the photoexcitation synergistic PMS activation.

Aeration-Free Photo-Fenton-Like Reaction Mediated by Heterojunction Photocatalyst toward Efficient Degradation of Organic Pollutants.

The regulation of peroxymonosulfate (PMS) activation by photo-assisted heterogeneous catalysis is under in-depth investigation with potential as a replaceable advanced oxidation process in water purification, yet it remains a significant challenge. Herein, we demonstrate a strategy to construct polyethylene glycol (PEG) well-coupled dual-defect VO-M-Co3O4@CNx S-scheme heterojunction to degrade organic pollutants without aeration, which dramatically provides abundant active sites, excellent photo-thermal property, and distinct charge transport pathway for PMS activation. The degradation rate of VO-M-Co3O4@CNx in anaerobic conditions shows a higher efficient rate (4.58 min-1 g-2) than in aerobic conditions (1.67 min-1 g-2). Experimental evidence reveals that VO-M-Co3O4@CNx promotes more rapid redox conversion of photoexcited electrons induced by defects with PMS under anaerobic conditions compared to aerobic conditions. Additionally, in situ experiments and DFT provide mechanistic insights into the regulation pathway of PMS activation via synergistic defect-induced electron, revealing the competitive effect between O2 and PMS over VO-M-Co3O4@CNx during the reaction process. The continuous flow reactor and flow cytometry results demonstrated that the VO-M-Co3O4@CNx/PMS/Vis system has remarkably enhanced stability and purification capability for removing organic pollutants. This work provides valuable insights into regulating the heterologous catalysis oxidation process without aeration through the photoexcitation synergistic PMS activation.

Nanobiohybrid Extracellular Vesicle Nanoreactor with Improving Metabolical Activity for Biocatalytic Therapy.

Extracellular vesicles (EVs) hosting enzymatic activities that function as independent metabolic units are attractive natural biocatalytic platforms. However, directly using these metabolically active nanoreactors for effective biocatalytic applications remains challenging, mainly due to their constrained catalytic capabilities. Here, we construct an EV-templated nanobiohybrid system by engineering an EV surface with a photoresponsive zeolitic imidazolate framework (ZIF). The deposition of ZIF nanostructures on EVs not only contributes to improved biocatalytic stability but also enables interfacial coupling between photoexcited electrons from the ZIF and the enzymatic reaction of metabolically active EVs. Nearly 300% of biomass conversion efficiency increment could be achieved by EVs derived from macrophages. This enhanced biocatalysis, high catalytic stability, and low cytotoxicity endowed the EV@ZIF nanosystem with robust biosynthesis and antimicrobial activity. When evaluated in a mouse periodontitis model, we show that the autologous biocatalytic EV@ZIF demonstrated efficient therapeutic capability by killing bacteria and inhibiting inflammation. This nanoengineering strategy will benefit the future optimization of metabolically active EV nanoreactors as biocatalysts for a broad range of therapeutics.

Novel Syntheses of Wide-Band Gap Semiconducting CdxZnx−1Co2O4 of Spinel Nanostructure: Characterization and Optical Properties

AbstractCadmium doped zinc cobaltite spinel structure in the form of CdxZnx-1Co2O4 (0 ≤ x ≤ 1) are synthesized by sol-gel method. The energy dispersive X-ray spectra confirm the synthesis of pure ZnCo2O4 and Cd doped samples nanoparticles. Scanning and transmission electron microscopes images of Cd ZnCo2O4 samples show the cubic crystal structure of the nanoparticles. A good crystallinity of the ZnCo2O4 and its dopants samples are indicated by the sharpness and strong peaks of X-ray diffraction patterns. The particle size is independent of the ratio of incorporated Cd into the ZnCo2O4 matrix. The FT-IR transmission spectrum of each Cdx Zn1-xCo2O4 complex shows two strong vibration peaks that are ascribed to the spinel structure’s octahedral and tetrahedral. The absorption spectra reveal three distinct absorption characteristics for Cdx Znx-1Co2O4 peaking at 268, 532 and 778 nm due to the photoexcitation of electrons from O 2p to Co 3d transitions and d-d transition of Co 3d. N2 adsorption–desorption isotherms for Cdx Znx-1Co2O4 indicate are carried out.

Photoassisted electron emission from planar-type electron source based on graphene/oxide/silicon structure

This paper reports on photoassisted electron emission from a planar-type electron emission source based on a graphene/oxide/p-Si structure under visible laser light irradiation. The electron source is expected to be useful as a photocathode with a high quantum efficiency and an ultrafast pulsed electron beam. The electron emission efficiency is found to be 12%, independent of laser light irradiation. Without a negative electron affinity surface, the emission current generated by irradiation shows an increase of several orders of magnitude compared with that in the dark, and a quantum efficiency of 0.3% is achieved. This electron source exhibits advanced photoassisted electron emission characteristics with high photosensitivity in the order of milliamps per watt. The photoassisted emission from the device shows a photoresponse with a rise and fall time of 70 μs at a wavelength of 633 nm, which is determined by the diffusion process of photoexcited electrons in the bulk. The use of a heavily doped p-type silicon substrate provides a practical route for further improvement.

Core–Shell–Satellite Au@CeO2–Pd Plasmonical Photocatalysts for Suzuki–Miyaura Coupling Reaction

ABSTRACTIntegration of localized surface plasmon resonance (LSPR) metallic nanocrystals into photocatalysis is an intriguing approach for light‐driven organic transformations. However, uncertain direction of hot carriers is a grand challenge, which fails to take full advantage of the LSPR excitation. In this work, core–shell gold@ceria nanosphere–supported segregated palladium species (Au@CeO2–Pd) have developed to steer the light absorption capability and charge carrier migration. Under simulated solar light irradiation, the core–shell–satellite Au@CeO2–Pd exhibited efficient light harvesting and colossal activity in the Suzuki coupling reaction. The plasmon‐induced hot electrons overpassed the Schottky barrier at the Au@CeO2 interfaces and migrated from Au core to CeO2 shell accordingly. Subsequently, the photogenerated electrons and hot electrons migrated from Au@CeO2 core–shells to Pd, which acted as an electron acceptor. Detailed photocatalytic mechanism studies revealed that both photoexcited electrons and holes were the main active species involved in the photocatalytic Suzuki coupling reaction process. In particular, the diphenyl yield over Au@CeO2–Pd catalyst was ~1.7 times higher than that of core–shell–satellite Au@SiO2–Pd, where a 19‐nm‐thick SiO2 shell was introduced to prevent the migration of hot electrons. This distinctly certified that the hot electrons transfer in the core–shell–satellite Au@CeO2–Pd under illumination played an important role to drive Suzuki reaction. Overall, this design of core–shell–satellite Au@CeO2–Pd plasmonic photocatalyst has the potential in the field of photo‐driven organic transformations.

Bright Nanocomposites based on Quantum Dot‐Initiated Photocatalysis

AbstractIntegrating quantum dots (QDs) into polymer matrix to form nanocomposites without compromising the QD photoluminescence (PL) is crucial to emerging QD light‐emitting and solar energy conversion fields. However, the most widely‐used bulk polymerization technique, where monomers serve as the QD solvent, usually leads to QD PL quenching caused by radical initiators. Here we demonstrate high‐brightness nanocomposites with near‐unity PL quantum yield (QY), through a novel QDs‐catalyzed (‐initiated) bulk polymerization without using any radical initiators. Different from previous reports where QDs were designed as photo‐sensitizers/catalysts (always with cocatalysts) and hence non‐emissive in catalytic conditions, our QDs combine high brightness with highly effective catalysis, a combination that was previously considered to be hardly possible. In our case, apart from emitting light (at a large probability), the photoexcited QDs act as ‘overall reaction’ catalysts by simultaneously employing photoexcited electrons and holes to produce active radicals without the need of any sacrificial agents. These active radicals, though with a small amount, are sufficient to initiate effective chain reaction‐dominated bulk polymerization, eliminating the requirement of extra radical initiators. This study provides new insights for understanding and development of QDs for energy applications.

Bright Nanocomposites based on Quantum Dot-Initiated Photocatalysis.

Integrating quantum dots (QDs) into polymer matrix to form nanocomposites without compromising the QD photoluminescence (PL) is crucial to emerging QD light-emitting and solar energy conversion fields. However, the most widely-used bulk polymerization technique, where monomers serve as the QD solvent, usually leads to QD PL quenching caused by radical initiators. Here we demonstrate high-brightness nanocomposites with near-unity PL quantum yield (QY), through a novel QDs-catalyzed (-initiated) bulk polymerization without using any radical initiators. Different from previous reports where QDs were designed as photo-sensitizers/catalysts (always with cocatalysts) and hence non-emissive in catalytic conditions, our QDs combine high brightness with highly effective catalysis, a combination that was previously considered to be hardly possible. In our case, apart from emitting light (at a large probability), the photoexcited QDs act as 'overall reaction' catalysts by simultaneously employing photoexcited electrons and holes to produce active radicals without the need of any sacrificial agents. These active radicals, though with a small amount, are sufficient to initiate effective chain reaction-dominated bulk polymerization, eliminating the requirement of extra radical initiators. This study provides new insights for understanding and development of QDs for energy applications.

Solar‐Driven Methanogenesis through Microbial Ecosystem Engineering on Carbon Nitride

AbstractSemi‐biological photosynthesis combines synthetic photosensitizers with microbial catalysts to produce sustainable fuels and chemicals from CO2. However, the inefficient transfer of photoexcited electrons to microbes leads to limited CO2 utilization, restricting the catalytic performance of such biohybrid assemblies. Here, we introduce a biological engineering solution to address the inherently sluggish electron uptake mechanism of a methanogen, Methanosarcina barkeri (M. barkeri), by coculturing it with an electron transport specialist, Geobacter sulfurreducens KN400 (KN400), an adapted strain rich with multiheme c‐type cytochromes (c‐Cyts) and electrically conductive protein filaments (e‐PFs) made of polymerized c‐Cyts with enhanced capacity for extracellular electron transfer (EET). Integration of this M. barkeri‐KN400 co‐culture with a synthetic photosensitizer, carbon nitride, demonstrates that c‐Cyts and e‐PFs, emanating from live KN400, transport photoexcited electrons efficiently from the carbon nitride to M. barkeri for methanogenesis with remarkable long‐term stability and selectivity. The demonstrated cooperative interaction between two microbes via direct interspecies electron transfer (DIET) and the photosensitizer to assemble a semi‐biological photocatalyst introduces an ecosystem engineering strategy in solar chemistry to drive sustainable chemical reactions.

Solar-Driven Methanogenesis through Microbial Ecosystem Engineering on Carbon Nitride.

Semi-biological photosynthesis combines synthetic photosensitizers with microbial catalysts to produce sustainable fuels and chemicals from CO2. However, the inefficient transfer of photoexcited electrons to microbes leads to limited CO2 utilization, restricting the catalytic performance of such biohybrid assemblies. Here, we introduce a biological engineering solution to address the inherently sluggish electron uptake mechanism of a methanogen, Methanosarcina barkeri (M. barkeri), by coculturing it with an electron transport specialist, Geobacter sulfurreducens KN400 (KN400), an adapted strain rich with multiheme c-type cytochromes (c-Cyts) and electrically conductive protein filaments (e-PFs) made of polymerized c-Cyts with enhanced capacity for extracellular electron transfer (EET). Integration of this M. barkeri-KN400 co-culture with a synthetic photosensitizer, carbon nitride, demonstrates that c-Cyts and e-PFs, emanating from live KN400, transport photoexcited electrons efficiently from the carbon nitride to M. barkeri for methanogenesis with remarkable long-term stability and selectivity. The demonstrated cooperative interaction between two microbes via direct interspecies electron transfer (DIET) and the photosensitizer to assemble a semi-biological photocatalyst introduces an ecosystem engineering strategy in solar chemistry to drive sustainable chemical reactions.

Highly efficient magnesium ferrite/graphene nano-heterostructure for visible-light photocatalytic applications: Experimental and first-principles DFT studies

In this research study, the electronic structure of magnesium ferrite/graphene (MFO/Gr) nano-heterostructure for photocatalytic application was studied. The MFO nanoparticles with a median size of 85 nm were composited with Gr sheets using a photo-assisted reduction process. The XRD and SAED results, respectively, showed the spinal crystalline structure of MFO and the hexagonal structure of Gr in MFO/Gr nanocomposite. The XPS results revealed that the orbitals of MFO and Gr atoms interacted with each other, implying a Van der Waals heterojunction nanocomposite. The optical characteristics using UV–Vis diffuse reflectance spectrophotometry (UV–Vis DRS) and photoluminescence (PL) spectra demonstrated a lowering of MFO band gap from 2.05 to 1.84 eV by incorporation of Gr. Furthermore, the photoelectrocatalytic and photocatalytic dye degradation examinations showed a substantial impact of Gr on the photocatalytic activity of MFO nanoparticles: a 28-fold increase in the photocurrent and an 8-fold increase in the dye-degradation rate. The density functional theory (DFT) studies on MFO/Gr heterojunction revealed a considerable hybridization between Gr atoms orbitals (2p orbitals) and MFO atoms orbitals (Mg 3 s and Fe 3d orbitals) in the conduction band, which facilitate the transfer of photo-excited electrons from MFO to Gr. Also, the charge density difference at the MFO/Gr interface led to a polarized field at the interface, which is desirable for hindering photogenerated electron-hole recombination in the MFO/Gr nanocomposite. Along with the experimental results, the DFT results also revealed that the MFO/Gr nano-heterostructure is an excellent candidate for photocatalytic applications such as water splitting using sunlight to produce green hydrogen fuel.

Fabrication of heterostructure multilayer devices through the optimization of Bi-metal sulfides for high-performance quantum dot-sensitized solar cells.

In this work, a titanium dioxide and lead sulfide (TiO2/PbS) nano-size heterostructure with tin sulfide was fabricated and coated via a two-step direct deposition process. Its microstructure, morphology, elemental composition, optical absorption, and photochemical activity were investigated. Linear sweep voltammetry and cyclic voltammetry curves substantiated its catalytic activity, indicating quantum dot effects of a well-developed space charge domain on the surface of the hybrid structure. These give rise to electron-hole recombination suppression and a high charge mobility rate. Moreover, direct stabilization was identified in current density, corresponding to the hybrid structures limiting the diffusion current process. Higher J SC values observed were substantiated by the role of quantum dot-size effects and enhanced crystalline structures, leading to a reduction in series resistance and an improved conversion efficiency of 10.05%. Overall, theoretical analyses and empirical findings indicated that the seamless migration of photoexcited electrons across the interfaces of SnS and PbS is linked to quantum dot effect synergy. This is facilitated by the space charge region, which serves as a conduit for efficient electron transfer between the respective materials.

Strong Built-In Electric Field-Assisted ZnO/ZnIn2S4 S-Scheme Heterostructure to Promote Photocatalytic Hydrogen Production.

Photocatalysis is an eco-friendly and significant perspective for generating hydrogen. Our study investigated the ZnO/ZnIn2S4 heterojunction photocatalytic system prepared through hydrothermal technique. Accordingly, the ZnIn2S4 nanofibers loaded with 11 mol % ZnO exhibited the hydrogen evolution rate of about 1998 μmol g-1 h-1, which was 2.6 times higher than the pristine ZnIn2S4. In situ electron paramagnetic resonance results proved the S-scheme photocarrier transport route, and in situ KPFM further characterized the internal electric field between ZnO and ZnIn2S4. The development of S-scheme heterojunctions allows for the spatial segregation and transport of charges by preserving photoexcited holes and electrons with a tremendous redox potential. Furthermore, the photoelectrochemical analysis demonstrated that the S-scheme heterojunction could also be employed for the separation of photoexcited species.

Nd3+ induces three-dimensional hierarchical rosette-shaped Bi3O4Br to generate abundant oxygen vacancies for enhanced photocatalytic activity

Three-dimensional hierarchical rosette-shaped Bi3O4Br has been successfully prepared by a one-step hydrothermal method for the first time, in which the doping of Nd3+ into the matrix of Bi3O4Br induces abundant oxygen vacancies and triggers energy-band hybridization to produce new dopant levels, which can efficiently receive photo-excited electrons and inhibit the complexation of photogenerated carriers. Impressively, the doped energy levels act as “springboards” for photogenerated electron jumps, exacerbating the inhomogeneity of charge distribution and accelerating charge separation. In addition, the fine-tuning of Nd3+ improves the band structure and photocatalytic performance of Nd/Bi3O4Br. Notably, the unique 3D rosette-like Bi3O4Br could enhance the adsorption capacity of the catalyst and provide more opportunities for the introduction of Nd3+ to induce the generation of abundant oxygen vacancies. Both experimental and density functional theory (DFT) results reveal the synergistic effect of energy band hybridization and oxygen vacancies. In addition, comparative experiments showed that Nd/Bi3O4Br enhanced the maximum removal efficiency of heavy metal mercury by 29.66 % relative to Bi3O4Br under visible light. The present work reveals the reaction mechanism of photocatalytic oxidation for mercury removal, which provides a new direction for realizing energy conversion and environmental purification in the future.