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The efficiency of photocatalytic hydrogen evolution can be significantly enhanced while maintaining cost-effectiveness through the synergistic effect of defect surface engineering and multi-component heterojunctions. The structure and properties of NiCo2O4 nanorods were modified by inducing oxygen vacancies at different temperatures in this study, resulting in improved optical properties and electron adsorption capacity. The presence of oxygen vacancies leads to a reduction in the band gap of NiCo2O4, thereby enhancing electron transport efficiency through band gap engineering. Simultaneously, surface properties undergo changes, and vacancy defects serve as electron trapping centers, facilitating an increased participation of electrons in the hydrogen evolution reaction process. The dodecahedron KMP with a cavity structure is additionally introduced to form an S-scheme heterojunction with NiCo2O4. This establishes a novel mechanism for electron transport, which effectively enhances the separation of electron-hole pairs and improves the redox capacity of the photocatalytic system. The adsorption of intermediates in the hydrogen production process is enhanced through synergistic regulation of d-band centers via surface defect engineering and S-scheme heterojunction. Additionally, this approach improves the separation efficiency of electron-hole pairs and accelerates electron transfer dynamics, significantly enhancing hydrogen production efficiency.
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Designing efficient dual-functional catalysts for photocatalytic oxygen reduction to produce hydrogen peroxide (H2O2) and photodegradation of dye pollutants is challenging. In this work, we designed and fabricated an S-scheme heterojunction (g-C3N4/ZnO composite photocatalyst) via one-pot calcination of a mixture of ZIF-8 and melamine in the KCl/LiCl molten salt medium. The KCN/ZnO composite produced 4.72 mM of H2O2 within 90 min under illumination (with AM 1.5 filter), which is almost 1.3 and 7.8 times than that produced over KCN and ZnO, respectively. Simultaneously, the KCN/ZnO also showed excellent photodegradation performance for the dye pollutants (Rhodamine B, RhB), with a removal rate of 92 % within 2 h. The apparent degradation rate constant of RhB over KCN/ZnO was approximately 5-8 times that of KCN and ZnO. In the photocatalytic process, photo-generated holes and superoxide radicals are the main active species. Oxygen (O2) was mainly reduced to produce H2O2 via a two-electron (2e-) pathway with superoxide radicals as intermediates and the 2e- oxygen reduction reaction selectivity of KCN/ZnO was close to 69.82 %. Photo-generated holes are mainly responsible for the degradation of RhB. Compared with pure KCN and ZnO, the enhanced photocatalytic activity of the KCN/ZnO composite is mainly attributed to the following aspects: 1) larger specific surface area and pore volume is beneficial to expose more active sites; 2) stronger light harvesting ability and red-shifted absorption edge bestow the compound a stronger light utilization efficiency; 3) the construction of S-scheme heterostructure between KCN and ZnO improve the photogenerated electron-hole pairs separation ability and bestow photogenerated carriers a higher redox potential.
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The research in the field of photocatalysis has progressed, with the development of heterojunctions being recognized as an effective method to improve carrier separation efficiency in light-induced processes. In this particular study, CuCo2S4 particles were attached to a new cubic CdS surface to create an S-scheme heterojunction, thus successfully addressing this issue. Specifically, owing to the higher conduction band and Fermi level of CuCo2S4 compared to CdS, they serve as the foundation and driving force for the formation of an S-scheme heterojunction. Through in-situ X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis, the direction of charge transfer in the composite photocatalyst under light exposure was determined, confirming the charge transfer mechanism of the S-scheme heterojunction. By effectively constructing the S-scheme heterojunction, the d-band center of the composite photocatalyst was adjusted, reducing the energy needed for electron filling in the anti-bonding energy band, promoting the transfer of photogenerated carriers, and ultimately enhancing the photocatalytic hydrogen production. performance. After optimization, the hydrogen evolution activity of the composite photocatalyst CdS-C/CuCo2S4-3 reached 5818.9 µmol g-1h-1, which is 2.6 times higher than that of cubic CdS (2272.3 µmol g-1h-1) and 327.4 times higher than that of CuCo2S4 (17.8 µmol g-1h-1), showcasing exceptional photocatalytic activity. Electron paramagnetic resonance and in situ X-ray photoelectron spectroscopy have established a theoretical basis for designing and constructing S-scheme heterojunctions, offering a viable method for adjusting the D-band center to enhance the performance of photocatalytic hydrogen evolution.
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Photocatalysis has been proven to be an excellent technology for treating antibiotic wastewater, but the impact of each active species involved in the process on antibiotic degradation is still unclear. Therefore, the S-scheme heterojunction photocatalyst Ti3C2/g-C3N4/TiO2 was successfully synthesized using melamine and Ti3C2 as precursors by a one-step calcination method using mechanical stirring and ultrasound assistance. Its formation mechanism was studied in detail through multiple characterizations and work function calculations. The heterojunction photocatalyst not only enabled it to retain active species with strong oxidation and reduction abilities, but also significantly promoted the separation and transfer of photo-generated carriers, exhibiting an excellent degradation efficiency of 94.19 % for tetracycline (TC) within 120 min. Importantly, the priority attack sites, degradation pathways, degradation intermediates and their ecological toxicity of TC under the action of each single active species (·O2-, h+, ·OH) were first positively explored and evaluated through design experiments, Fukui function theory calculations, HPLC-MS, Escherichia coli toxicity experiments, and ECOSAR program. The results indicated that the preferred attack sites of ·O2- on TC were O20, C7, C11, O21, and N25 atoms with high f+ value. The toxicity of intermediates produced by ·O2- was also lower than those produced by h+ and ·OH.
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Tetraciclina , Tetraciclina/química , Tetraciclina/toxicidad , Catálisis , Titanio/química , Oxidación-Reducción , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/toxicidad , Aguas Residuales/química , Escherichia coli/efectos de los fármacos , Antibacterianos/química , Antibacterianos/toxicidadRESUMEN
The construction of S-scheme heterojunctions, which offers a promising approach for spatially separating photogenerated charge carriers with high redox potentials and multimolecular activation, represents a viable modification strategy in photocatalytic applications. However, the prevalent insufficient contact areas between two components result in low interface charge transfer efficiency, thereby impeding the photocatalytic performance of such heterostructures. Herein, we address this limitation by introducing a unique mCN@mPDIP molecular heterojunction through a pH-triggered molecule self-assembly eutectoid technique, enabling intimate interface contact and promoting highly efficient interfacial charge transfer following an S-scheme mechanism. Consequently, the mCN@mPDIP molecular heterojunction achieves significantly improved charge separation efficiency and higher concentration of active carriers compared to typical bCN-bPDIP bulk heterojunction and nCN/nPDIP nano heterojunction. Combined with the effective sulfide activation on mPDIP sites and O2 activation on mCN sites, the resulting mCN@mPDIP demonstrates outstanding activity in the photocatalytic aerobic oxidation of sulfides into sulfoxides without any redox mediators.
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Photocatalytic degradation of pollutants coupled with hydrogen (H2) evolution has emerged as a promising solution for environmental and energy crises. However, the fast recombination of photoexcited electrons and holes limits photocatalytic activities. Herein, an S-scheme heterojunction carbon doped-TiO2/ZnIn2S4 (C-TiO2/ZnIn2S4) was designed by substituting oxygen sites within C-TiO2 by ZnIn2S4. Under visible light irradiation, the optimal C-TiO2/ZnIn2S4 exhibits a higher degradation efficiency (88.6%) of microcystin-LR (MC-LR), compared to pristine C-TiO2 (72.9%) and ZnIn2S4 (66.8%). Furthermore, the H2 yield of the C-TiO2/ZnIn2S4 reaches 1526.9 µmol g-1 h-1, which is 3.83 times and 2.87 times that of the C-TiO2 and ZnIn2S4, respectively. Experimental and theoretical investigations reveal that an internal electric field (IEF) informed in the C-TiO2/ZnIn2S4 heterojunction, accelerates the separation of photogenerated charge pairs, thereby enhancing photocatalytic efficiency of MC-LR degradation and H2 production. This work highlights a new perspective on the development of high-performance photocatalysts for wastewater treatment and H2 generation.
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The environmental contamination caused by organophosphorus pesticides (for example, triazophos) is an escalating concern. To mitigate this issue, this study introduces a novel Al6Si2O13/WO2.72 (ASO/WO) nanocomposite photocatalyst, which markedly enhances the photocatalytic degradation of triazophos. The optimized nanocomposite material with a 60.0 % ASO loading (60-ASO/WO) achieves a degradation rate of 86.3 % for triazophos within 140.0 min, marginally exceeding 60-ASO/WO3 (72.6 %) and significantly outperforming individual ASO (65.0 %), WO (59.5 %), and WO3 (56.2 %). This catalyst retains 88.9 % of its activity after five cycles, showcasing exceptional efficiency and stability. Additionally, its electrochemical surface area (ECSA, 310.0 cm2), total organic carbon (TOC, removal rate of 73.7 %), photocurrent, and electrochemical impedance are all optimal. X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and theoretical calculations elucidate the critical role of oxygen vacancies and the S-scheme heterojunction in augmenting charge separation and photocatalytic performance, corroborating the synergistic effect of oxygen defects and the S-scheme. While individual factors can enhance photocatalytic activity, their combination results in a more pronounced effect. Liquid chromatography-mass spectrometry (LCMS) identifies the principal degradation intermediates, including 1-phenyl-3-hydroxy-1, 2, 4-triazole, diethyl thiophosphate, and 3, 5, 6-trichloro-2-pyridinol, underscoring the material's potential in environmental remediation.
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In addition to the intrinsic driving force of photocatalysis, the external thermal field from the photothermal effect can provide additional energy to the photo-catalytic system to improve the photo-catalytic hydrogen-evolution (PHE) efficiency. Herein, based on the results of density functional theory, we designed and constructed a hollow core-shell FeNi2S4@Mn0.3Cd0.7S (NFS@MCS) S-scheme heterojunction with a photothermal effect, thereby realising a significant enhancement of the PHE performance due to the thermal effect, S-scheme heterojunction and hollow core-shell morphology. As a light collector and heat source, the hollow NFS could absorb and convert photons into heat, resulting in the increased local temperature of photocatalyst particles. Moreover, the S-scheme charge path at the interface not only improved the carrier separation efficiency but also retained a higher redox potential. All these are favourable to increase the PHE activity. The PHE tests show that 0.5 %-NFS@MCS exhibits the highest PHE rate of 17.11 mmol·g-1·h-1, 7.7 times that of MCS. Moreover, through a combination of theoretical calculation and experimental evidence, the PHE mechanism of the NFS@MCS system is discussed and clarified in-depth.
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The persistent hurdles of charge rapid recombination, inefficient use of light and utilization of sacrificial reagents have plagued the field of photocatalytic hydrogen evolution (PHE). In this research, tiny MoO2 nanoparticles of 10 nm in diameter were prepared through a straightforward solvothermal approach with a specific ratio of oleylamine and oleic acid as stabilizers. The critical factor in the synthesis process was found to be the ratio of oleylamine to oleic acid. Moreover, a two-phase interface assembly method facilitated the uniform deposition of MoO2 onto CdS nanorods. Due to the localized plasmonic-thermoelectric effect on the surface of MoO2 along with its abundant oxygen vacancies, the composite catalyst exhibited outstanding photo-utilization efficiency and an abundance of active sites. The CdS-MoO2 composite displayed a unique photochemical property in transforming lactic acid into pyruvic acid and generating hydrogen simultaneously. After exposure to artificial sunlight for 4 h, significant values of 4.7 and 3.7 mmolâ g-1â h-1 were achieved for hydrogen production and pyruvic acid formation, respectively, exceeding CdS alone by 3.29 and 4.02-fold, while the selectivity of pyruvic acid was 95.68 %. Furthermore, the S-Scheme electron transport mechanism in the composites was elucidated using Electron Paramagnetic Resonance (EPR) spectroscopy, radical trapping experiments, energy band structure analysis, and the identification of critical intermediates in the process of selective oxidation. This work sheds light on the design and preparation of high-performance photocatalysts for biorefining coupled with efficient hydrogen evolution.
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The photocatalytic production of hydrogen (H2) from water is a vital avenue towards sustainable energy and addressing global environmental challenges. To maximize efficiency, harnessing the synergistic effects of multiple co-catalysts is essential, as these interactions can significantly enhance performance. In this study, we introduce a ternary heterojunction composed of a nickel-imidazole framework (Ni-MOF), graphitic carbon nitride (CN), and Ti3C2 MXene (TC), employing solvothermal and wet impregnation methods, featuring a well-designed Type II heterojunction and a noble metal-free Schottky junction for efficient hydrogen evolution. The Type II heterojunction between Ni-MOF and CN minimizes charge carrier recombination and promotes photogenerated electron generation, while TC as an electron acceptor enhances electron capture, increases participation in surface reactions, and augments active sites. Consequently, the Ni-MOF/CN/TC hybrid catalyst achieves outstanding photocatalytic hydrogen evolution under visible light, with a peak production rate of 1044.46 µmol/g over 3 hours, surpassing CN by 13 fold and Ni-MOF/CN by 50%. This work provides insights into MXene-based ternary systems, emphasizing the potential for enhanced light absorption and efficient charge separation, making it a promising platform for photocatalytic applications.
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Spatially-ordered S-scheme photocatalysts are intriguing due to their enhanced light harvesting, spatially isolated redox sites, and strong redox abilities. Nonetheless, heightening the performance of S-scheme photocatalysts via controllable defect engineering is still challenging to now. In this work, multi-armed MoSe2/CdS S-scheme heterojunction with intimate Mo-S bond coupling and adjustable Se vacancies (VSe) and Mo5+ concentrations was constructed, which consisted of few- or even single-layered MoSe2 growing on the {11-20} facets of wurtzite CdS arms. The S-scheme charge transmission mechanism of MoSe2/CdS heterojunction was validated by density functional theory calculation combined with in situ photo-irradiated X-ray photoelectron spectroscopy, surface photovoltage, and radical measurements. Moreover, the Fermi level gap between CdS and MoSe2 was enlarged by regulating the contents of donor (VSe) and acceptor (Mo5+) impurities with synthesis temperature, which strengthens the built-in electric field and carriers transfer driving force of MoSe2/CdS composites, contributing to an outstanding H2 evolution activity of 52.62 mmol·g-1·h-1 (corresponding to an apparent quantum efficiency of 34.8 % at 400 nm) under visible-light irradiation (λ > 400 nm), 25.8 times that of Pt-loaded CdS counterpart and a substantial amount of reported CdS-containing photocatalysts. Our study results are anticipated to facilitate the rational design of advanced semiconductor nanostructures for efficient solar conversion and utilization.
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The efficient separation of photogenerated charge carriers and strong oxidizing properties can improve photocatalytic performance. Here, we combine the construction of a tightly connected S-scheme heterojunction with the exposure of an active crystal plane to prepare g-C3N4/BiOBr for the degradation of high-concentration organic pollutants. This strategy effectively improves the separation efficiency of photogenerated carriers and the number of active sites. Notably, the synthesized g-C3N4/BiOBr displays excellent photocatalytic degradation activity towards various organic pollutants, including methylene blue (MB, 90.8%), congo red (CR, 99.2%), and tetracycline (TC, 89%). Furthermore, the photocatalytic degradation performance of g-C3N4/BiOBr for MB maintains 80% efficiency under natural water quality (tap water, lake water, river water), and a wide pH range (pH = 4-10). Its excellent photocatalytic activity is attributed to the tight connection between g-C3N4 and BiOBr in the S-scheme heterojunction interface, as well as the exposure of highly active (001) crystal planes. These improve the efficiency of the separation of photogenerated carriers, and maintain their strong oxidation capability. This work presents a simple approach to improving the separation of electrons and holes by tightly combining two components within a heterojunction.
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The photocatalytic conversion of solar energy to hydrogen is a promising pathway toward clean fuel production, yet it requires advancement to meet industrial-scale demands. This study demonstrates that the interface engineering of heterojunctions is a viable strategy to enhance the photocatalytic performance of CuInS2/Mo2S3. Specifically, CuInS2 nanoparticles are incorporated into Mo2S3 nanospheres via a wet impregnation technique to form an S-scheme heterojunction. This configuration facilitates directional electron transfer, optimizing electron utilization and fostering efficient photocatalytic processes. The presence of an S-scheme heterojunction in CuInS2/Mo2S3 is corroborated by in situ irradiation X-ray photoelectron spectroscopy and density functional theory analyses, which confirm the directional movement of electrons at the interface of heterojunction. Comprehensive characterization of the heterojunction photocatalyst, including phase, structural, and photoelectric property assessments, reveals a significant specific surface area and light absorption capability. These attributes augment the number of active sites available in CuInS2/Mo2S3 for proton reduction reactions. This study offers a pragmatic approach for designing metal sulfide-based photocatalysts via strategic interface engineering, potentially advancing the field toward sustainable hydrogen production.
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Integrating photocatalytic oxidation for pollutant removal with hydrogen production via photocatalysis presents a promising approach for sustainable water purification and renewable energy generation, circumventing the sluggish multi-electron transfer inherent in photocatalytic water oxidation. This study introduces novel zero-/one-dimensional (0D/1D) CuWO4/Mn0.3Cd0.7S step-scheme (S-scheme) heterojunctions that exhibit exceptional bifunctional capabilities in photocatalytic degradation and hydrogen production under full-spectrum illumination. The degradation efficiency for tetracycline (TC) using 5 %-CuWO4/Mn0.3Cd0.7S reaches 94.3 % and 94.5 % within 60 min and 6 h, respectively, under ultraviolet-visible (UV-Vis) and near-infrared (NIR) light. Notably, these 0D/1D CuWO4/Mn0.3Cd0.7S S-scheme heterojunctions demonstrate superior hydrogen production, achieving rates of 12442.03 µL g-1h-1 and 2418.54 µL g-1h-1 under UV-Vis light and NIR light irradiation, respectively-these rates are 2.3 times and 55.2 times higher than that of Mn0.3Cd0.7S alone. This performance enhancement is attributed to the intrinsic dimensional effects, transitions of transition metal d-d orbitals, and S-scheme hole/electron (h+/e-) separation characteristics. Additionally, experimental results and density functional theory (DFT) calculations have clarified the modulation of electronic configurations, band alignment, and interfacial interactions via 0D/1D S-scheme heterojunction engineering. This study sheds light on the electron transfer mechanism within S-scheme heterojunction and enhances the effectiveness, economy, and sustainability of recalcitrant pollutant removal and hydrogen production.
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Rational design of the morphology and heterojunction to accelerate the separation of electron-hole pairs has played an indispensable role in improving the photocatalytic hydrogen evolution. ZnIn2S4 (ZIS) has aroused considerable attention in solar-to-chemical energy conversion due to its remarkable photoelectrical properties and relatively negative energy band, whereas it still suffers from the severe photogenerated carrier recombination and catalyst aggregation. Herein, guided by density functional theory calculations, the constructed FeSe2@ZnIn2S4 (FS@ZIS) heterojunction model has a hydrogen Gibbs free energy closer to zero compared with pure ZIS and FS, which is beneficial for hydrogen adsorption and desorption on the photocatalyst surface. Therefore, a novel cross-like core-shell FS@ZIS Step-scheme (S-scheme) heterojunction was synthesized successfully by in-situ growing ZIS nanosheets on the surface of cross-like FS. The structure with cross-like core-shell morphology not only inhibits the agglomeration of ZIS to increase specific surface area, but also provides a tight interface with S-scheme heterojunction. Moreover, the S-scheme heterojunction with a tight interface can effectively separate electron-hole pairs, leaving photoinduced charges with higher potentials. Furthermore, FS@ZIS-20 possesses exceptional photothermal capabilities, enabling the conversion of optical energy from visible and near infrared light to heat, thereby further enhancing the photocatalysis reaction. As a result, the cross-like core-shell FS@ZIS S-scheme heterojunction exhibits an excellent photocatalytic hydrogen evolution rate (7.640 mmol g-1 h-1), which is 24 times higher than that of pure ZIS (0.319 mmol g-1 h-1) under visible and near infrared light. Furthermore, employing more in-depth density functional theory calculations further investigates the charge transfer pathway of the FS@ZIS S-scheme heterojunction. This work provides insights into the construction of S-scheme heterojunctions with core-shell structure and photothermal effect for photocatalytic evolution hydrogen.
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A novel photoelectrochemical sensor, employing an S-scheme heterojunction of phthalocyanine and TiO2 nanoparticles, has been developed to enable highly sensitive determination of glutathione. By integrating the favorable stability, environmental benignity, and electronic properties of the TiO2 matrix with the unique photoactivity of phthalocyanine species, the designed sensor presents a substantial linear dynamic range and a low detection limit for the quantification of glutathione. The sensitivity is attributed to efficient charge transfer and separation across the staggered heterojunction energy levels, which generates measurable photocurrent signals. Systematic variation of phthalocyanine content reveals an optimal composition that balances light harvesting capacity and electron-hole recombination rates. The incorporation of phosphotungstic acid (PTA) in sample preparation effectively minimizes interference from compounds like L-cysteine and others. Consequently, this leads to an improvement in accuracy through the reduction of impurity levels. Appreciable photocurrent enhancements are observed upon introduction of both oxidized and reduced glutathione at the optimized composite photoanode. Coupled with advantageous features of photoelectrochemical transduction such as simplicity, cost-effectiveness, and resistance to fouling, this sensor holds great promise for practical applications in complex biological media.
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Técnicas Electroquímicas , Glutatión , Indoles , Isoindoles , Titanio , Titanio/química , Glutatión/química , Glutatión/análisis , Indoles/química , Técnicas Electroquímicas/métodos , Técnicas Electroquímicas/instrumentación , Límite de Detección , Procesos Fotoquímicos , ElectrodosRESUMEN
Exploring low-cost visible light photocatalysts for CO2 reduction to produce proportionally adjustable syngas is of great significance for meeting the needs of green chemical industry. A S-Scheme CeO2/g-C3N4 (CeO2/CN) heterojunction was constructed by using a simple two-step calcination method. During the photocatalytic CO2 reduction process, the CeO2/CN heterojunction can present a superior photocatalytic performance, and the obtained CO/H2 ratios in syngas can be regulated from 1 : 0.16 to 1 : 3.02. In addition, the CO and H2 production rate of the optimal CeO2/CN composite can reach 1169.56 and 429.12â µmol g-1 h-1, respectively. This superior photocatalytic performance is attributed to the unique S-Scheme photogenerated charge transfer mechanism between CeO2 and CN, which facilitates rapid charge separation and migration, while retaining the excellent redox capacity of both semiconductors. Particularly, the variable valence Ce3+/Ce4+ can act as electron mediator between CeO2 and CN, which can promote electron transfer and improve the catalytic performance. This work is expected to provide a new useful reference for the rational construction of high efficiency S-Scheme heterojunction photocatalyst, and improve the efficiency of photocatalytic reduction of CO2, promoting the photocatalytic reduction of CO2 into useful fuels.
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In this study, Ag/Bi2O3/Bi5O7I with s-scheme heterostructures were successfully synthesized in situ by nano-silver modification of CUA-17 and halogenated hydrolysis.The growth rate of Bi2O3 crystals was effectively controlled by adjusting the doping amount of Ag, resulting in the formation of a facet-coupling heterojunctions. Through the investigation of the microstructure and compositional of catalysts, it has been confirmed that an intimate facet coupling between the Bi2O3 (120) facet and the Bi5O7I (312) facet, which provides robust support for charge transfer. Under visible light irradiation, the AgBOI.3 heterojunction photocatalyst exhibited an outstanding degradation rate of 98.2% for Bisphenol A (BPA) with excellent stability. Further characterization using optical, electrochemical, impedance spectroscopy, and electron spin resonance techniques revealed significantly enhanced efficiency in photogenerated charge separation and transfer, and confirming the s-scheme structure of the photocatalyst. Density functional theory calculations was employed to elucidate the mechanism of BPA degradation and the degradation pathway of BPA was investigated by LC-MS. Finally, the toxicity of the degradation intermediates was evaluated using T.E.S.T software.
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Compuestos de Bencidrilo , Bismuto , Fenoles , Plata , Fenoles/química , Compuestos de Bencidrilo/química , Bismuto/química , Catálisis , Plata/químicaRESUMEN
Photocatalytic nitrate reduction reaction (NitRR) is a promising route for environment remediation and sustainable ammonia synthesis. To design efficient photocatalysts, the recently emerged nanoarchitectonics approach holds great promise. Here, we report a nanohouse-like S-scheme heterjunction photocatalyst with high photocatalytic NitRR performance. The nano-house has a floor of plate-like metal organic framework-based photocatalyst (NH2-MIL-125), on which another photocatalyst Co(OH)2 nanosheet is grown while ZIF-8 hollow cages are also constructed as the surrounding wall/roof. Experimental and simulation results indicate that the positively charged, highly porous and hydrophobic ZIF-8 wall can modulate the environment in the nanohouse by (i) NO3 - enrichment/NH4 + discharge and (ii) suppression of the competitive hydrogen evolution reaction. In combination with the enhanced electron-hole separation and strong redox capability in the NH2-MIL-125@Co(OH)2 S-scheme heterjunction confined in the nano-house, the designed photocatalyst delivers an ammonia yield of 2454.9â µmol g-1 h-1 and an apparent quantum yield of 8.02 % at 400â nm in pure water. Our work provides new insights into the design principles of advanced photocatalytic NitRR photocatalyst.
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Charge separation driven by the internal electric field is a research hotspot in photocatalysis. However, it remains challenging to accurately control the electric field to continuously accelerate the charge transfer. Herein, a strategy of constructing a tandem electric field to continuously accelerate charge transfer in photocatalysts is proposed. The plasma electric field, interface electric field, and intramolecular electric field are integrated into the Ag/g-C3N4/urea perylene imide (Ag/PCN/UPDI) ternary heterojunction to achieve faster charge separation and longer carrier lifetime. The triple electric fields function as three accelerators on the charge transport path, promoting the separation of electron-hole pairs, accelerating charge transfer, enhancing light absorption, and increasing the concentration of energetic electrons on the catalyst. The H2 evolution rate of Ag/PCN/UPDI is 16.8 times higher than that of pristine PDI, while the degradation rate of oxytetracycline is increased by 4.5 times. This new strategy will provide a groundbreaking idea for the development of high-efficiency photocatalysts.