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The coupling of photocatalytic hydrogen production and selective oxidation of benzylamine is a topic of significant research interest. However, enhancing the bifunctional photocatalytic activity in this context is still a major challenge. The construction of Z-scheme heterojunctions is an effective strategy to enhance the activity of bifunctional photocatalysts. Herein, a p-n type direct Z-scheme heterojunction CuS/TiO2 is constructed using metal-organic framework (MOF)-derived TiO2 as a substrate. The carrier density is measured by Mott-Schottky under photoexcitation, which confirms that the Z-scheme electron transfer mode of CuS/TiO2 is driven by the diffusion effect caused by the carrier concentration difference. Benefiting from efficient charge separation and transfer, photogenerated electrons, and holes are directedly transferred to active oxidation and reduction sites. CuS/TiO2 also exhibits excellent bifunctional photocatalytic activity without noble metal cocatalysts. Among them, the H2 evolution activity of the CuS/TiO2 is found to be 17.1 and 29.5 times higher than that of TiO2 and CuS, respectively. Additionally, the yields of N-Benzylidenebenzylamine (NBB) are 14.3 and 47.4 times higher than those of TiO2 and CuS, respectively.
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Photo-assisted uranium extraction from seawater (UES) is regarded as an efficient technique for uranium resource recovery, yet it currently faces many challenges, such as issues like biofouling resistance, low charge separation efficiency, slow carrier transfer, and a lack of active sites. Based on addressing the above challenges, a novel oxygen-deficient Co3O4-x/g-C3N4 p-n heterojunction is developed for efficient photo-assisted uranium extraction from seawater. Relying on the defect-coupling heterojunction synergistic effect, the redistribution of molecular charge density formed the built-in electric field as revealed by DFT calculations, significantly enhancing the separation efficiency of carriers and accelerating their migration rate. Notably, oxygen vacancies served as capture sites for oxygen, effectively promoting the generation of reactive oxygen species (ROS), thereby significantly improving the photo-assisted uranium extraction performance and antibacterial activity. Thus, under simulated sunlight irradiation with no sacrificial reagent added, Co3O4-x/g-C3N4 extracted a high uranium extraction amount of 1.08 mg g-1 from 25 L of natural seawater after 7 days, which is superior to most reported carbon nitride-based photocatalysts. This study elaborates on the important role of surface defects and inerface engineering strategies in enhancing photocatalytic performance, providing a new approach to the development and design of uranium extraction material from seawater.
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Organic pollutant detection has caused widespread concern regarding due to their potential environmental and human health risks. In this work, a nitrogen-doped titanium dioxide/silver oxide (N-TiO2/Ag2O) composite has been designed as a sensitive photoelectrochemical (PEC) monitoring platform of organic dyes. Sensitive determination relies on the outstanding PEC performance of N-TiO2/Ag2O. The improved PEC performance stems from the effective separation of photocarriers and the extended light response range provided by the narrowing bandgap and a p-n junction with N-TiO2/Ag2O. The N-TiO2/Ag2O electrode exhibits a photocurrent density of up to 2.2 mA/cm2, demonstrating three times increase compared with the photocurrent density observed with the pure TiO2 film. The linear detection range for rhodamine B (RhB), methylene blue (MB), and methyl orange (MO) is 0.2 ng/mL to 10 µg/mL with an ultrasensitive detection limit of 0.2 ng/mL without bias voltage. Due to the outstanding photocurrent density and sensitive response to organic pollutants, the N-TiO2/Ag2O PEC sensor provided a promising analytical method to detect environmental organic dyes.
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Morphology and structure play a crucial role in influencing the performance of gas sensors. Hollow structures, in particular, not only increase the specific surface area of the material but also enhance the collision frequency of gases within the shell, and have been studied in depth in the field of gas sensing. Taking SnO2 as an illustrative example, a dual-shell structure SnO2 (D-SnO2) was prepared. D-SnO2@Polyaniline (PANI) (DSPx, x represents D-SnO2 molar content) composites were synthesized via the in situ oxidative polymerization method, and simultaneously deposited onto a polyethylene terephthalate (PET) substrate to fabricate an electrode-free, flexible sensor. The impact of the SnO2 content on the sensing performance of the DSPx-based sensor for NH3 detection at room temperature was discussed. The results showed that the response of a 20 mol% D-SnO2@PANI (DSP20) sensor to 100 ppm NH3 at room temperature is 37.92, which is 5.1 times higher than that of a pristine PANI sensor. Moreover, the DSP20 sensor demonstrated a rapid response and recovery rate at the concentration of 10 ppm NH3, with response and recovery times of 182 s and 86 s.
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In this paper, we reported a facile and clean strategy to prepare the flake-like Ag2O/Fe2O3 bimetallic p-n heterojunction composites for photodegradation organic pollutants. The surface morphology, crystal structure, chemical composition and optical properties of Ag2O/Fe2O3 were characterized by SEM, high-resolution TEM images with EDX spectra, XRD, XPS, FT-IR and UV-vis DRS spectra respectively. The formation of Ag2O/Fe2O3 p-n heterojunction facilitated the interfacial transfer of electrons as well as the separation of charge carries. Hence, the as-synthesized Ag2O/Fe2O3-3 composites exhibited ultra-high photocatalytic activity. Under the experimental conditions of catalyst dosage of 0.4 mg mL-1 and irradiation time of 60 min, the degradation conversion rate of rhodamine B reached 96.1 %, which was 5.0 and 2.8 times of pure phase Ag2O and Fe2O3, respectively. Meanwhile, the degradation performance of Ag2O/Fe2O3-3 was not limited by pH, and it can achieve high degradation efficiency under 3-11. In addition, Ag2O/Fe2O3-3 also showed superb degradation ability for other common anionic dyes, cationic dyes and antibiotics. XPS and FT-IR spectra showed that Ag2O/Fe2O3-3 retained a carbon skeleton that facilitated electron transport and light absorption conversion. And the analyses of quenching experiment and EPR demonstrated â¢O2-, â¢OH and h+ were crucial reactive oxidant species contributing to the rapid organic pollutant degradation. This work provides new insights into obtaining p-n photocatalysts heterojunction with excellent catalytic activity for removing organic pollutants from wastewater.
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Fotólise , Catálise , Concentração de Íons de Hidrogênio , Compostos Férricos/química , Prata/química , Rodaminas/química , Poluentes Químicos da Água/químicaRESUMO
Photocatalytic CO2 reduction serves as an important technology for value-added solar fuel production; however, it is generally limited by interfacial charge transport. To address this limitation, a two-dimensional/two-dimensional (2D/2D) p-n heterojunction CuS-Bi2WO6 (CS-BWO) with highly connected and matched interfacial lattices was designed via a two-step hydrothermal tandem synthesis strategy. The integration of CuS with BWO created a robust interface electric ï¬eld and provided fast charge transfer channels due to the work function difference, as well as highly connected and matched interfacial lattices. The p-n heterojunction promoted electron transfer from the Cu to Bi sites, leading to coordination of Bi sites with high electronic density and low oxidation state. The Bi sites in BWO nanosheets facilitated the adsorption and activation of CO2, and generation of high-coverage key intermediate b-CO32-, while broad light-harvesting CuS (CS) provide abundant photoinduced electrons that were injected into the conduction band of BWO for CO2 photoreduction reaction. Remarkably, the p-n heterojunction CS-BWO exhibited CO and CH4 yields of 135.7 and 62.5 µmol g-1, respectively, which were significantly higher than those of CS, BWO, and physical mixture CS-BWO nanosheets. This work provided an innovative design strategy for developing high-activity heterojunction photocatalyst for converting CO2 into value-added solar fuels.
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Solar-driven photoelectrochemical (PEC) water splitting is a promising approach toward sustainable hydrogen (H2 ) generation. However, the design and synthesis of efficient semiconductor photocatalysts via a facile method remains a significant challenge, especially p-n heterojunctions based on composite metal oxides. Herein, a MOF-on-MOF (metal-organic framework) template is employed as the precursor to synthesize In2 O3 /CuO p-n heterojunction composite. After incorporation of small amounts of graphene nanoribbons (GNRs), the optimized PEC devices exhibited a maximum current density of 1.51 mA cm-2 (at 1.6 V vs RHE) under one sun illumination (AM 1.5G, 100 mW cm-2 ), which is approximately four times higher than that of the reference device based on only In2 O3 photoanodes. The improvement in the performance of these hybrid anodes is attributed to the presence of a p-n heterojunction that enhances the separation efficiency of photogenerated electron-hole pairs and suppresses charge recombination, as well as the presence of GNRs that can increase the conductivity by offering better path for electron transport, thus reducing the charge transfer resistance. The proposed MOF-derived In2 O3 /CuO p-n heterojunction composite is used to demonstrate a high-performance PEC device for hydrogen generation.
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Self-powered photodetectors (PDs) have been recognized as one of the developing trends of next-generation optoelectronic devices. Herein, it is shown that by introducing a thin layer of SnO film between the Si substrate and the ZnO film, the self-powered photodetector Al/Si/SnO/ZnO/ITO exhibits a stable and uniform violet sensing ability with high photoresponsivity and fast response. The SnO layer introduces a built-in electrostatic field to highly enhance the photocurrent by over 1000%. By analyzing energy diagrams of the p-n junction, the underlying physical mechanism of the self-powered violet PDs is carefully illustrated. A high photo-responsivity (R) of 93 mA W-1 accompanied by a detectivity (D*) of 3.1 × 1010 Jones are observed under self-driven conditions, when the device is exposed to 405 nm excitation laser wavelength, with a laser power density of 36 mW cm-2 and at a chopper frequency of 400 Hz. The Si/SnO/ZnO/ITO device shows an enhancement of 3067% in responsivity when compared to the Al/Si/ZnO/ITO. The photodetector holds an ultra-fast response of ≈ 2 µs, which is among the best self-powered photodetectors reported in the literature based on ZnO.
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In this study, a Z-Scheme WO3/CoO p-n heterojunction with a 0D/3D structure was designed and prepared via a simple solvothermal approach to remove the combined pollution of tetracycline and heavy metal Cr(VI) in water. The 0D WO3 nanoparticles adhered to the surface of the 3D octahedral CoO to facilitate the construction of Z-scheme p-n heterojunctions, which could avoid the deactivation of the monomeric material due to agglomeration, extend the optical response range, and separate the photogenerated electronhole pairs. The degradation efficiency of mixed pollutants after a 70 min reaction was significantly higher than that of monomeric TC and Cr(VI). Among them, a 70% WO3/CoO heterojunction had the best photocatalytic degradation effect on the mixture of TC and Cr(VI) pollutants, and the removing rate was 95.35% and 70.2%, respectively. Meanwhile, after five cycles, the removal rate of the mixed pollutants by the 70% WO3/CoO remained almost unchanged, indicating that the Z-scheme WO3/CoO p-n heterojunction has good stability. In addition, for an active component capture experiment, ESR and LC-MS were employed to reveal the possible Z-scheme pathway under the built-in electric field of the p-n heterojunction and photocatalytic removing mechanism of TC and Cr(VI). These results offer a promising idea for the treatment of the combined pollution of antibiotics and heavy metals by a Z-scheme WO3/CoO p-n heterojunction photocatalyst, and have broad application prospects: boosted tetracycline and Cr(VI) simultaneous cleanup over a Z-scheme WO3/CoO p-n heterojunction with a 0D/3D structure under visible light.
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In the current study, the photocatalytic activity of bimetallic ZnO-CuO hetero-nanocomposite was evaluated and compared with the monometallic ZnO and CuO nanoparticles using 4-nitroaniline (4-NA) and methyl orange (MO). Bimetallic ZnO-CuO hetero-nanocomposite, ZnO, and CuO nanostructure were synthesized utilizing leaf extract of Aegle marmelos and characterized by transmission electron microscopy, X-ray diffraction, and XPS. Benefiting from the p-n heterostructures formation, bimetallic ZnO-CuO hetero-nanocomposite exhibits an excellent photocatalytic activity against 4-NA as well as MO compared to pure ZnO and CuO. In particular, bimetallic ZnO-CuO hetero-nanocomposite expressed the highest photocatalytic activity by reducing 90% of 4-NA in 20 min and by degrading 96% of MO in 10 min, whereas 65% reduction of 4-NA in 30 min and 93% degradation of MO in 45 min was exhibited by CuO and 48% reduction of 4-NA in 30 min and 98% degradation of MO in 50 min was exhibited by ZnO. Moreover, bimetallic ZnO-CuO hetero-nanocomposite maintains excellent photocatalytic activity even after five cycles indicating its stability as photocatalyst and reusability. Based on the experimental findings, bimetallic ZnO-CuO hetero-nanocomposite could be used as a photocatalyst for wastewater treatment with excellent regeneration efficiency.
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Aegle , Nanocompostos , Óxido de Zinco , Compostos de Anilina , Compostos Azo , Catálise , Nanocompostos/química , Extratos Vegetais , Óxido de Zinco/químicaRESUMO
Triethylamine (TEA) exists widely in production and life and is extremely volatile, which seriously endangers human health. It is required to develop high-performance TEA sensors to protect human health. We fabricated Pt-Co3O4/WO3based on our previous work, and the performance was tested against volatile organic compounds. Compared with the previous work, its operating temperature was greatly reduced from 240 °C to 180 °C. The response value of Pt-Co3O4/WO3was increased from 1101 to 1532 for 10 ppm TEA with good selectivity. These results show a significant step toward practical use of the Pt-Co3O4/WO3sensor.
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In this work we demonstrated the process of co-deposition of copper-tin sulfide species by the atomic layer deposition (ALD) technique using all-low-cost precursors. For the deposition of tin species, the tin(IV) chloride SnCl4was used successfully for the first time in the ALD process. Moreover, we showed that the successful deposition of the tin sulfide component was conditioned by the pre-deposition of CuSxlayer. The co-deposition of copper and tin sulfides components at 150 °C resulted in the in-process formation of the film containing Cu2SnS3, Cu3SnS4andπ-SnS phases. The process involving only tin precursor and H2S did not produce the SnSxspecies. The spectroscopic characteristic of the obtained materials were confronted with the literature survey, allowing us to discuss the methodology of the determination of ternary and quaternary sulfides purity by Raman spectroscopy. Moreover, the material characterisation with respect to the morphology (SEM), phase composition (XRD), surface chemical states (XPS), optical properties (UV-vis-NIR spectroscopy) and electric (Hall measurements) properties were provided. Finally, the obtained material was used for the formation of the p-n junction revealing the rectifyingI-Vcharacteristics.
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Type II p-n heterojunction and direct Z-scheme heterojunction are identical staggered band alignments, but were reported ambiguously in many composite photocatalysts because their carriers migrate in opposite directions. In this research, metal oxides CuO, NiO and Co3O4-based heterojunctions with Na0.9Mg0.45Ti3.55O8(NMTO) were synthesized via a simple hydrothermal method. The CuO/NMTO heterojunction was demonstrated as a direct Z-scheme heterojunction, whereas the NiO/NMTO and Co3O4/NMTO heterojunctions showed type II p-n band alignment, distinguished by the direct observation of carrier migration under light illumination, and confirmed by the x-ray photoelectron spectroscopy, Mott-Schottky measurements, ultraviolet photoelectron spectra and capture experiments. These all heterojunctions enjoyed better photocatalytic performance to degrade methylene blue and antibiotics (Enrofloxacin, Metronidazole and tetracycline) than the pure NMTO, attributed to their effective separation of the photoinduced electron-hole pairs owing to the staggered band alignment. Prominently, the NiO/NMTO and Co3O4/NMTO p-n heterojunctions exhibited superior degradation ability to the CuO/NMTO Z-scheme heterojunction. The initial relative Fermi position of two semiconductors is the prerequisite to determine whether the p-n heterojunction or direct Z-scheme heterojunction is built because the electrons diffuse from one semiconductor with a higher Fermi level to another with a lower Fermi level while the holes diffuse reversely until a united Fermi level when they combine. The built-in electric field at the heterojunction interface is determined by the difference in the initial Fermi levels or work functions of two semiconductors, regulating the separation ability of photogenerated electrons and holes to affect the photocatalytic performance. Thus, the high difference in the initial Fermi levels of semiconductors is crucial in the development of heterojunctions with staggered band alignment to obtain high performance in photocatalytic reactions.
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Ag3PO4/BiPO4 heterojunction photocatalysts with an intergrowth structure composed of sphere-shaped Ag3PO4 and nanorod BiPO4 were synthesized via a facile combination of solvothermal method and in-situ deposition process. They exhibit enhanced photocatalytic activities under sunlight irradiation, and the heterojunction composite with the 10 wt% loading amounts of Ag3PO4 presented the highest photocatalytic activities against norfloxacin (NFX), ofloxacin (OFXL) and ciprofloxacin (CIP), with high degradation efficiencies of 94.7%, 95.4% and 92.1%, respectively. Additionally, the Ag3PO4/BiPO4 photocatalyst demonstrates outstanding structural and photocatalytic stability. The superior performance was attributed to the effective charge transfer across the p-n heterojunction interface and the enhancement of light absorption. This work provides a new insight into the development of novel BiPO4-based heterojunction composites and meets the remediation for contaminated aqueous environment.
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Fluoroquinolonas , Norfloxacino , Catálise , Ciprofloxacina , Luz SolarRESUMO
Constructing heterojunction is an attractive strategy for promoting photoelectrochemical (PEC) performance in water splitting and organic pollutant degradation. Herein, a novel porous BiVO4/Boron-doped Diamond (BiVO4/BDD) heterojunction photoanode containing masses of ultra-micro electrodes was successfully fabricated with an n-type BiVO4 film coated on a p-type BDD substrate by magnetron sputtering (MS). The surface structures of BiVO4 could be adjusted by changing the duration of deposition (Td). The morphologies, phase structures, electronic structures, and chemical compositions of the photoanodes were systematically characterized and analyzed. The best PEC activity with the highest current density of 1.8 mA/cm2 at 1.23 VRHE was achieved when Td was 30 min, and the sample showed the highest degradation efficiency towards tetracycline hydrochloride degradation (TCH) as well. The enhanced PEC performance was ascribed to the excellent charge transport efficiency as well as a lower carrier recombination rate, which benefited from the formation of BiVO4/BDD ultra-micro p-n heterojunction photoelectrodes and the porous structures of BiVO4. These novel photoanodes were expected to be employed in the practical PEC applications of energy regeneration and environmental management in the future.
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Bismuto , Vanadatos , Bismuto/química , Boro , Diamante , Porosidade , Vanadatos/químicaRESUMO
Simultaneous transformation of CO2 and H2 O into syngas (CO and H2 ) using solar power is desirable for industrial applications. Herein, an efficient photocatalyst based on double-shelled nanoboxes, with an outer shell of hydroxy-rich nickel cobaltite nanosheets and an inner shell of Cu2 S (Cu2 S@ROH -NiCo2 O3 ), is prepared via a multistep templating strategy. The high performance of Cu2 S@ROH -NiCo2 O3 (7.1â mmol g-1 h-1 for CO; 2.8â mmol g-1 h-1 for H2 ) is attributed to the hierarchical hollow geometry and p-n heterojunction to promote light absorption and charge separation. Spectroscopic and theoretical analyses elucidate that the ROH -NiCo2 O3 surface enhances *CO2 adsorption and lowers energy barriers for CO2 -to-CO. Therefore, modulating the hydroxy contents of ROH -NiCo2 O3 can achieve broad CO/H2 ratios from 0.51 to 1.24. This work offers in-depth insights into adjustable syngas photosynthesis and generalized concepts of selective heterogeneous CO2 photoreduction beyond cobalt-based oxides.
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Trace poisonous and harmful gases in the air have been harming and affecting people's health for a long time. At present, effective and accurate detection of ppb-level harmful gas is still a bottleneck to be overcome. Herein, we report a ppb-level triethylamine (TEA) gas sensor based on p-n heterojunction of Co3O4/WO3, which is prepared with ZIF-67 as the precursor and provides Co3O4deposited tungsten oxide flower-like structure. Due to the introduction of Co3O4and the 3D flower-like structure of WO3, the Co3O4/WO3-2 gas sensor shows excellent gas sensing performance (1101 for 10 ppm at 240 °C), superb selectivity, good long-term stability and linear response for TEA concentration. Moreover, the experimental results indicate that the Co3O4/WO3-2 gas sensor also possesses a good response to 50 ppb TEA, in fact, the theoretical limit of detection is 0.6 ppb. Co3O4not only improves the efficiency of electron separation/transport, but also accelerates the oxidation rate of TEA. This method of synthesizing p-n heterojunction with ZIF as the precursor provides a new idea and method for the preparation of low detection limit gas sensors.
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Surface enhanced Raman scattering (SERS) based on chemical mechanism (CM) attracts tremendous attention for great selectivity and stability. However, low enhancement factor (EF) limits its practical applications for trace detection. Here, a novel sponge-like Cu-doping SnO2 -NiO p-n semiconductor heterostructure (SnO2 -NiOx /Cu), was first created as a CM-based SERS substrate with a significant EF of 1.46×1010 . This remarkable EF was mainly attributed to the enhanced charge-separation efficacy of p-n heterojunction and charge transfer resonance resulted from Cu doping. Moreover, the porous structure enriched the probe molecules, resulting in further SERS signals magnification. By immobilizing CuPc as an inner-reference element, SnO2 -NiOx /Cu was developed as a SERS nose for selective recognition of multiple lung cancer related VOCs down to ppb level. The information of VOCs was recorded in a barcode, demonstrating practical potential of a desktop SERS device for biomarker screening.
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Cobre/química , Níquel/química , Compostos de Estanho/química , Compostos Orgânicos Voláteis/análise , Semicondutores , Análise Espectral RamanRESUMO
There is a need for highly efficient photocatalysts, particularly for water purification. In this study, we fabricated a mesoporous TiO2 thin film on a boron-doped diamond (BDD) layer by a surfactant-assisted sol-gel method, in which self-assembled amphiphilic surfactant micelles were used as an organic template. Scanning electron microscopy revealed uniform mesopores, approximately 20 nm in diameter, that were hexagonally packed in the TiO2 thin film. Wide-angle X-ray diffraction and Raman spectroscopy clarified that the framework crystallized in the anatase phase. Currentâ»voltage (Iâ»V) measurements showed rectification features at the TiO2/BDD heterojunction, confirming that a pâ»n hetero-interface formed. The as-synthesized mesoporous TiO2/BDD worked well as a photocatalyst, even with a small volume of TiO2 (15 mm × 15 mm × c.a. 1.5 µm in thickness). The use of deep UV light (λ = 222 nm) as a light source was necessary to enhance photocatalytic activity, due to photo-excitation occurring in both BDD and TiO2.
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Boro/química , Diamante/química , Processos Fotoquímicos , Titânio/química , Raios Ultravioleta , Catálise , PorosidadeRESUMO
The development of highly efficient and robust photocatalysts has attracted great attention for solving the global energy crisis and environmental problems. Herein, we describe the synthesis of a p-n heterostructured photocatalyst, consisting of ZnO nanorod arrays (NRAs) decorated with BiOI nanoplates (NPs), by a facile solvothermal method. The product thus obtained shows high photoelectrochemical water splitting performance and enhanced photoelectrocatalytic activity for pollutant degradation under visible light irradiation. The p-type BiOI NPs, with a narrow band gap, not only act as a sensitizer to absorb visible light and promote electron transfer to the n-type ZnO NRAs, but also increase the contact area with organic pollutants. Meanwhile, ZnO NRAs provide a fast electron-transfer channel, thus resulting in efficient separation of photoinduced electron-hole pairs. Such a p-n heterojunction nanocomposite could serve as a novel and promising catalyst in energy and environmental applications.