Internal Electric Field Research Articles

Action potential threshold variability for different electrostimulation models and its potential impact on occupational exposure limit values.

Occupational exposure limit values (ELVs) for body internal electric fields can be derived from thresholds for action potential generation. These thresholds can be calculated with electrostimulation models. The spatially extended nonlinear node model (SENN) is often used to determine such thresholds. Important parameters of these models are the membrane channel dynamics describing the ionic transmembrane currents as well as the temperature at which the models operate. This work compares action potential thresholds for five different membrane channel dynamics used with the SENN model. Furthermore, two more detailed double-cable models by Gaines et al. (MRG-Sensory and MRG-Motor) are also considered in this work. Thresholds calculated with the SENN model and the MRG models are compared for frequencies between 1 Hz and 100 kHz and temperatures at 22°C and 37°C. Results show that MRG thresholds are lower than SENN thresholds. Deriving alternative ELVs from these thresholds shows that the alternative ELVs can change significantly with different ion channel dynamics (up to a factor of 22). Using the double cable model could lead to approximately ten times lower alternative exposure limit values. On the contrary, using the SENN model with different membrane channel dynamics could also lead to higher alternative exposure limit values. Therefore, future exposure guidelines should take the influence of different electrostimulation models into account when deriving ELVs.

Cooperative S-S coupling and H2 production from photocatalytic dehydrogenation of thiols over ReSe2/ZnIn2S4 heterostructure

Photocatalytic anaerobic dehydrogenation provides a new avenue to cooperatively produce clean fuels and fine chemicals, while minimizing waste discharge and reducing environmental impact. Here, we demonstrate an efficient co-production of disulfides and H2 via photocatalytic S-S dehydrogenation of thiols using a two-dimensional (2D) heterostructure of ultrathin ZnIn2S4 (ZIS) nanosheets decorated with dispersed (1T phase) ReSe2 nanoparticles. Experimental characterizations and DFT calculations reveal that integrating ReSe2 with ZIS leads to the formation of a robust internal electric field (IEF) within the ReSe2/ZIS heterostructure. The distorted 1T phase ReSe2 with abundant active Se sites and a high Fermi level induces downward band bending of ZIS at the interface, which promotes charge separation and expedites H2 evolution. Moreover, the introduction of ReSe2 provides more adsorptive sites, increasing the concentration of reactants on the catalyst surface. This enhancement fosters surface interactions between the catalyst and p-toluenethiol (PTT), ultimately accelerating the reaction rate. The optimal H2 and S-S coupling p-tolyl disulfide (PTD) production rates of the 5 wt% ReSe2/ZIS composite reach 2275 and 2303 µmol g−1h−1, respectively, approximately 5 times greater than those of blank ZIS. Importantly, the selectivity of PTD reaches 98.4 %. This visible-light-driven dehydrogenation process aligns with the principles and objectives of green chemistry, realizing high atom economy without generating byproducts. It is anticipated to open new possibilities for sustainable and environmentally friendly routes for synthesizing high-value chemicals and producing clean energy.

Dual‐functional UiO‐66/g‐C3N4 composites for photocatalytic pesticide removal and in situ adsorption of phosphate byproducts in water

AbstractBACKGROUNDWith the increasing global demand for food, a significant amount of organophosphorus pesticides is applied to farmland, leading to pollution as they are discharged into natural water bodies with agricultural runoff. This study employed a coupling approach, utilizing a 6:4 mass ratio of zirconium‐based metal–organic framework UiO‐66 and g‐C3N4 through a grinding and annealing method to construct a Z‐type heterojunction composite material named UG 6:4.RESULTSThis material is employed for photocatalytic removal of the representative organophosphorus pesticide, dichlorvos (DDVP), from water and simultaneous in situ adsorption of its inorganic phosphorus byproducts. Results demonstrate that for initial DDVP concentrations below 5 mg L−1 (calculated as total phosphorus), both the mineralization rate under ultraviolet light irradiation with a wavelength of 365 nm and a power of 125 W and the adsorption rate of phosphorus were 100% when the pH was 6 and the UG 6:4 dosage was 0.2 g L−1. The sheet‐like g‐C3N4 tightly envelops the surface of UiO‐66, forming a Z‐scheme heterojunction. This structure imparts UG 6:4 with enhanced light absorption, faster generation and separation of photogenerated electron–hole pairs compared to individual UiO‐66 or g‐C3N4, and the establishment of an internal electric field suppresses the recombination of photogenerated charge carriers.CONCLUSIONConsequently, UG 6:4 exhibits outstanding photocatalytic pesticide removal capabilities. Furthermore, UG 6:4 demonstrates specific adsorption of inorganic phosphorus through electrostatic attraction and ligand exchange. This study indicates that UG 6:4 is a promising dual‐functional photocatalytic adsorbent with excellent application prospects. © 2024 Society of Chemical Industry (SCI).

Faraday rotation method improves the upper limit of the electron electric-dipole-moment sensitivity.

The electron electric-dipole-moment (eEDM) is a powerful tool for exploring new particles. The candidates for eEDM search are heavy atoms and their molecules, which are well known for the obvious relativistic effect. Lead atom is considered to be the most ideal relativistic atom [Park et al., Nat. Commun. 11(1), 815 (2020)]. PbH molecule is an important representative of the Pb compound and is considered a cold candidate molecule due to the high diagonal Franck-Condon factors. We systematically investigated the (eEDM) searches of PbH using a two-component approach. The parity- and time-reversal symmetry violation constants of ground and excited states, including internal effective electric field Eeff, electron-nucleon scalar-pseudoscalar interaction constant WP,T, and nuclear magnetic quadrupole moment, were obtained and compared to other molecules. In addition, we designed two experimental methods to measure the sensitivity of the eEDM, indicating that the Faraday rotation method could greatly improve its sensitivity.

Enhancing Energy Density in Aqueous Ammonium-Ion Supercapacitors via CuCo2S4@MoS2 Core@Shell Heterostructure Design.

Aqueous ammonium-ion supercapacitors (AASCs) are recognized for their rapid charge-discharge capability, long cycle life, and excellent power density. However, they still confront the challenges of low energy density. To address the above issue, this work proposes a novel strategy involving the establishment of CuCo2S4@MoS2 core@shell heterostructures to enhance the capacity of electrode material. The double electric layer energy storage mechanism of the MoS2 shell facilitates the storage and provision of a substantial ammonium source for NH4 + insertion into CuCo2S4, thereby enhancing the electrochemical performance of AASCs. The density functional theory (DFT) calculations demonstrate that the CuCo2S4@MoS2 core@shell heterostructures exhibit better affinity for NH4 + and improved conductivity. Furthermore, the internal electric field at the heterojunction accelerates NH4 + transfer, thereby enhancing the pseudocapacitive behavior of CuCo2S4. Owing to the abundant active sites and pronounced pseudo-capacitance, the CuCo2S4@MoS2 electrode achieves a specific capacity of 2045 C g-1 at 1 A g-1. With activated carbon (AC) as the negative electrode, the fabricated CuCo2S4@MoS2//AC AASC device attains a specific capacity of 591 C g-1 and an energy density of 83.23Wh kg-1. This work presents a promising new strategy for the next generation of AASCs.

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.

Facile modification of TiO2 as S-Scheme multifunctional materials for environmental protection and energy-storage applications

This paper reports a simple one-step modification of commercial TiO2 with a conducting polytrimethoxyslilypropyl aniline (PTMSPA, a polyaniline derivative having silyl networks) to have multi-functional (photocatalytic, optical, pseudocapacitive, hydrophobic, porous, antibacterial, and electromagnetic interference shielding (EMI)) properties and demonstrates associated applications. We present the S-Scheme heterojunction (SHJ) formation between TiO2 and PTMSPA through band position alignments and designate the resultant TiO2 - TiO2- based SHJ multifunctional materials as MF-TSSM. The internal electric field that is generated at the interface facilitates the transportation of the photogenerated electron transfer . The XRD pattern of MF-TSSM exhibits mainly the peaks of anatase TiO2. The TEM image of MF-TSSM indicates that the TiO2 particles are spherical in shape with sizes showing variations in diameters ranging from 60 nm to 250 nm depending on the experimental conditions of preparation and TiO2 particles are homogeneously distributed within the PTMSPA matrix. The optical energy band gap of MF-TSSM is 1.60 eV, a much lower value than PTMSPA (3.02 eV), suggesting that the composite formation between TiO2 and PTMSPA. The contact angle of MF-TSSM is significantly increased to 47.1 ° from 8.0 of TiO2, informing the increase of hydrophobic characteristics. The rate constant (k) for methylene blue photodegradation was 0.030 min-1, and 0.010 min-1 for MF-TSSM and pristine TiO2, respectively, The MF-TSSM composite exhibits a higher specific capacitance value (28.7 F/g) than TMSPA (21.1 F/g). At a frequency of 0.42 THz, MF-TSSM and PTMSPA exhibit return loss features indicating good EMI shielding performance. The MF-TSSM has been tested against two different Gram-positive and Gram-negative bacterial strains. The nanoparticles were evaluated at doses of 10, 20, 40, and 80 µg/ml. The results indicated that Klebsiella pneumoniae demonstrated a greater zone of inhibition, ranging from 9 mm at 10 µg/ml to 23 mm at 80 µg/ml, indicating increased susceptibility. Pseudomonas aeruginosa exhibited reduced inhibition zones, ranging from 10 mm at 10 µg/ml to 14 mm at 80 µg/ml, indicating increased resistance. The excellent effectiveness of MF-TSSM against various Gram-positive and Gram-negative pathogenic bacteria is explained by the interaction between reactive oxygen species and the cellular components of the bacteria as well the electrostatic interaction arising between positive charges in TMSPA and negative charges in the cell components, resulting in notable cytotoxicity and damage to the bacterial cells. The research underscores the capability of these modified TiO₂ nanoparticles in addressing bacterial infections, with efficiency differing by bacterial strain.

Construction of BaTiO3/g-C3N4 heterojunction for promoting atrazine degradation of hydraulic-driven piezocatalytic ozonation

Catalytic ozonation, as a popular water purification technology, was restrained with the dilemma of slow Me(n+m)+/Men+ redox cycle of the convention catalysts. To this end, BaTiO3/g-C3N4 (BTO/CN) piezoelectric heterojunction was designed to enhance atrazine (ATZ) degradation in piezocatalytic ozonation, utilizing the overlooked mechanical forces to activate O3 into reactive oxygen species (ROS). Characterization results demonstrated that the couple of BTO and CN successfully formed a Type-II heterojunction, enhancing the separation of piezoelectric carriers (e- and h+). Moreover, BTO/CN showed the better O3 affinity and O3 activation capability over that of BTO and CN. BTO/CN/O3 process achieved 90.1 % ATZ removal, which was 3.5 and 1.7 times over that of the BTO/O3 and CN/O3 processes, respectively. ATZ removal in BTO/CN/O3 process increased with the initial pH value. Cl-, SO42- and NO3- inhibited ATZ removal, but HCO3- enhanced ATZ removal. O3, •OH, O2- and 1O2 were all involved in ATZ degradation and •OH served as the main ROS, accounting for 79.3 % in degrading ATZ. The internal electric field along with the interfacial electric field synergistically boosted the separation and transfer of charge carriers to provide e- for O3 activation and ROS generation. This study broke through the basic need of continuous sacrifice of e- for O3 activation induced by metal redox cycle and provided a novel catalyst design strategy for piezoelectric ozonation.

0D/1D p-n heterostructured composite of bismuth ferrite perovskite clusters on sodium titanate nanotube arouse exceptional blue-light-driven photooxidation

This study describes the synthesis of a 0D/1D p-n heterostructured composite of bismuth ferrite perovskite clusters on sodium titanate nanotubes prepared using an in-situ hydrothermal method. BiFeO3/Na2Ti3O7 (BFT) nanocomposite, forming a p-n heterojunction due to the equilibrium of Fermi level, exhibits exceptional blue-light-driven photo-oxidation activity with an exceptional benzyl alcohol conversion rate of 29.64 mmolproduced BAD·g−1 h−1. The outstanding performance originates from the promotion of photogenerated charge separation and effective inhibition of charge recombination due to internal electric field of p-n heterojunction. Density functional theory calculations combined with femtosecond transient absorption spectroscopy distinctly confirms the efficient separation and transfer of photogenerated carriers to be S-scheme charge transfer mechanism over the p-n heterojunctions. Furthermore, in-situ infrared spectroscopy combined with XPS results demonstrate the strong adsorption of benzyl alcohol and weak adsorption of benzaldehyde on BFT, which facilitates the transformation of reactant and desorption of product. This study provides a simple and effective approach to enhance photocatalytic selective oxidation reactions.

Photoelectron marginalization effect in ZnO/WO3/graphene-like composites: Study of alternating strong-low photocatalytic hydrogen production performance and mechanism

ZnO/WO3/graphene-like composite photocatalysts are prepared by in-situ deposition and successfully utilized for alternating strong-low light catalytic decomposition of water to produce hydrogen. Additionally, the study details the microscopic morphology and optoelectronic properties of the ZnO/WO3/graphene-like composite. The results indicate that an internal electric field is generated between the ZnO/WO3 heterostructure and the graphene-like material. This induced electric field leads to a large amount of ordered electron transfer from ZnO/WO3 to the graphene-like material, resulting in the electron marginalization effect, which ensures the prerequisite for alternating strong-low photocatalytic splitting of water into hydrogen. When the mass fraction of the graphene-like material in the WO3/ZnO/graphene-like composite photocatalyst is 30 %, the photocatalytic hydrogen production rate reaches the maximum value of 820 times that of intrinsic ZnO. Therefore, this work provides a new perspective for alternating strong-low light catalytic water splitting to produce hydrogen.

Tribo-hygro-electric generator: Harnessing mechanical energy with liquid-infused porous cellulose for multiple sensing and DC power generation

This study introduces the Tribo-Hygro-Electric Generator (THEG), a novel device that harvests ambient mechanical and water-enabled energies for highly sensitive, self-powered multi-sensing. THEG employs a simple design using liquid-infused porous cellulose (LIPC), created by absorbing functional liquids such as water into porous cellulose, and metal contacts with distinct work functions (e.g., Al and Cu) to generate triboelectric charges through friction. It operates via a three-step process: generating triboelectric charges through sliding motion, establishing an internal electric field across Al/LIPC/Cu interfaces for charge separation, and directing charges to create unidirectional output electron transfer, producing direct current (DC) outputs. The principle behind THEG emphasizes the critical role of the single Schottky contact at the Al/LIPC interface in separating and directing charge transfer, as well as the conductive path formed by the hydrogen-bonded network of water molecules and cellulose’s functional groups. THEG can harvest DC power with a current density of up to 3.4 A/m² and 0.5 V, which can be increased to 2 V with four cells in series. THEG demonstrates impressive multiple-sensing capabilities, with robust linear relationships (correlation coefficients > 0.99) between output current density and stimuli such as pressure, velocity, water absorption, and ion concentration. Demonstrating practical utility, the generated energy powers devices like a commercial calculator. This technology advances mechanical energy harvesting and multiple sensing, reducing dependence on external power and enabling transformative IoT applications.

Construction of Z‐type heterojunction Bi4Ti3O12/g‐C3N4 with pyroelectric effect for enhanced photocatalytic performance

AbstractPhotocatalytic technology has been widely studied, discussed, and tested as a feasible wastewater degradation technology. The present study demonstrated the preparation of g‐C3N4 material using solid‐state sintering method and the construction of Bi4Ti3O12/g‐C3N4 heterostructure via hydrothermal method. This direct contact Z‐type heterojunction improves the wide bandgap of Bi4Ti3O12 monomer, enhances its photoresponsiveness, and thus improves its photocatalytic performance. During the process of photocatalytic experiments, an environment of cold and hot fluctuations were created, and the pyroelectric effect was utilized to induce self‐polarization of the material and formed an internal electric field. It improves the transport ability of electron–hole pairs and suppresses their recombination in the transport path. According to the degradation experiment results, the degradation efficiency of pyroelectric synergistic heterojunction photocatalysis reached 88.7%, which was 2.27 times that of Bi4Ti3O12. It proves that the photocatalysis by pyroelectric synergistic heterojunction has good application prospects.

A Photovoltaic Self-Powered Volatile Organic Compounds Sensor Based on Asymmetric Geometry 2D MoS2 Diodes

Transition metal dichalcogenides have gained considerable interest for vapour sensing applications due to their large surface-to-volume ratio and high sensitivity. Herein, we demonstrate a new self-powered volatile organic compounds (VOC) sensor based on asymmetric geometry multi-layer molybdenum disulfide (MoS2) diode. The asymmetric contact geometry of the MoS2 diode induces an internal built-in electric field resulting in self-powering via a photovoltaic response. While illuminated by UV-light, the sensor exhibited a high responsivity of ∼60% with a relatively fast response time of ∼10 sec to 200 ppm of acetone, without an external bias voltage. The MoS2 VOC diode sensor is a promising candidate for self-powered, fast, portable, and highly sensitive VOC sensor applications.

Broadband self-powered MoS2/PdSe2/WSe2 PSN heterojunction photodetector for high-performance optical imaging and communication

Two-dimensional (2D) semi-metal transition metal dichalcogenides (TMDs) have drawn significant attention for their distinctive physical properties. However, the inherent high dark current of these materials and the single structure of detectors hinder the further development of photodetectors with high performance. Here, we construct a PSN (p-type semiconductor/semi-metal/n-type semiconductor) architecture by sandwiching 2D semi-metal between two semiconductor layers. In this architecture, the top and bottom layers generate an internal built-in electric field, while the middle layer serves as an absorption layer for low-energy photons and facilitates the dissociation of photo-generated carriers. As a result, the heterojunction device demonstrates a wide spectrum optical response from visible to infrared light (405 nm to 1550 nm) without requiring an external voltage. Working in self-powered mode at room temperature, the device achieves a responsivity of 0.56 A/W, a detectivity of 5.63 × 1011 Jones, and a rapid response speed of 190/74 µs. Additionally, the device shows potential for applications in fast optical communication and multi-wavelength optical imaging. This work presents a novel approach for developing a new type of broadband, self-powered, high-performance miniaturized semi-metal-based photodetector.

Enhancing the Photocatalytic Performance for Norfloxacin Degradation by Fabricating S-Scheme ZnO/BiOCl Heterojunction

Construction of S-scheme heterojunctions can effectively limit the recombination of photogenerated e− and h+, thus improving photocatalytic activity. Therefore, S-scheme ZnO/BiOCl (molar ratio = 1:2) n–n heterojunctions were synthesized via a hydrothermal–hydrolysis combined method in this study. The physical and chemical properties of the ZnO/BiOCl heterojunctions were characterized by XRD, XPS, SEM, TEM, DRS, N2 adsorption–desorption and ESR. Additionally, the photoelectric performances of ZnO/BiOCl heterojunctions were investigated with TPR, M–S plot and EIS. The results show that photocatalytic degradation of NOR by ZnO/BiOCl reached to 94.4% under simulated sunlight, which was 3.7 and 1.6 times greater than that of ZnO and BiOCl, respectively. The enhanced photodegradation ability was attributed to the enhancement of the internal electric field between ZnO and BiOCl, facilitating the active separation of photogenerated electrons and holes. The radical capture experiments and ESR results illustrate that the contribution of reactive species was in descending order of ·OH > h+ > ·O2− and a possible mechanism for the photodegradation of NOR over S-scheme ZnO/BiOCl heterojunctions was proposed.

Internal Electric Fields and Structural Instabilities in Insulating Transition Metal Compounds: Influence on Optical Properties

AbstractThis work reviews new ideas developed in the last two decades which play a key role for understanding the optical properties of insulating materials containing transition metal (TM) cations. Initially, this review deals with compounds involving d4 and d9 ions where the local structure of the involved MX6 complexes (M=dn cation, X=ligand) is never cubic but distorted, a fact widely ascribed to the Jahn‐Teller (JT) effect. Nevertheless, that assumption is often wrong as the JT coupling requires an orbitally degenerate ground state in the initial geometry a condition not fulfilled even if the lattice is tetragonal. For this reason, the equilibrium geometry of d4 and d9 complexes in low symmetry lattices, is influenced by two factors: (i) The effects, usually ignored, of the internal electric field, ER, due to the rest of lattice ions on the active electrons localized in the MX6 unit. (ii) The existence of structural instabilities driven by vibronic interactions that lead to negative force constants. As first examples of these ideas, we show that the equilibrium structure, electronic ground state of KZnF3:Cu2+, K2ZnF4:Cu2+ and K2CuF4 obey to different causes and only in KZnF3:Cu2+ the JT effect takes place. These ideas also explain the local structure and optical properties of CuF2, CrF2 or KAlCuF6 compounds where the JT effect is symmetry forbidden and those of layered copper chloroperovskites where the orthorhombic instability explains the red shift of one d−d transition under pressure. In a second step, this review explores stable systems involving d3, d5 or d9 cations, where the internal electric field, ER, is responsible for some puzzling phenomena. This is the case of ruby and emerald that surprisingly exhibit a different color despite the Cr3+‐O2− distance is the same. A similar situation holds when comparing the normal (KMgF3) and the inverted (LiBaF3) perovskites doped with Mn2+ having the same Mn2+‐F distance but clearly different optical spectra. The role of ER is particularly remarkable looking for the origin of the color in the historical Egyptian Blue pigment based on CaCuSi4O10.

Construction of a In2O3/ultrathin g-C3N4 S-scheme heterojunction for sensitive photoelectrochemical aptasensing of diazinon

A single semiconductor-based photoelectrochemical (PEC) aptasensor usually faces a challenge of low sensitivity due to poor solar energy utilization and a high photogenerated carrier recombination rate. Herein, an ultra-thin carbon nitride nanosheet-coated In2O3 (In2O3/CNS) S-type heterojunction-based PEC aptasensor has been established to achieve highly sensitive detection of diazinon (DZN) pesticide in water environment. Construction of S-type heterojunction induces a band shift and an electric field effect, enhancing light utilization and accelerating directional transmission of carriers, leading to outstanding PEC performance. The creation of internal electric field at interface ensures stable carrier transport. Additionally, ultrathin CNS structure can effectively shorten the transport path of carriers. The close coating of In2O3 and CNS promotes the transfer of charge. The synergistic effects amplify the sensor’s response, ultimately enabling the effective detection of DZN residue over a wide detection range (0.98 ∼ 980.0 pg mL−1), a low detection limit (0.33 pg mL−1, S/N = 3) and excellent accuracy in practical application (RSD < 5 %). This work provides a reference for the construction of a new S-type heterojunction-based PEC sensor.

Fabrication of CoTiO3/MgIn2S4 S–scheme heterojunctions with efficient charge separation to enhance the photocatalytic activities of hydrogen generation and formaldehyde removal

The efficient separation of photoinduced charge carriers is a primary factor in the catalytic performance of photocatalysts. Constructing S-scheme heterojunctions is a prospective strategy to efficiently and spatially separate photoinduced charges while retaining strong oxidation and reduction capacities of the catalyst system. Herein, CoTiO3/MgIn2S4 (abbreviated x% CTO/MIS, where x% represents the mass ratio of CTO-to-MIS; x = 5, 10, 15, 20, and 25) heterojunctions were successfully synthesized using a hydrothermal method. These heterojunctions exhibited highly efficient and reusable visible-light photocatalytic properties for hydrogen (H2) generation and formaldehyde (HCHO) degradation. Notably, the 15 % CTO/MIS demonstrated an admirable H2 evolution activity of 631.77 μmol·g−1·h−1, with AQE = 2.25 % at λ = 420 nm, and an HCHO degradation rate of 67.18 %. The intermediate products generated during HCHO removal were identified applying in situ diffuse reflectance infrared Fourier transform spectroscopy. The exceptional catalytic performance of the synthesized materials was attributed to the boosted light absorption and utilization, rapidly separation, and transfer of photoproduced charge carriers, which resulted from the internal electric field of the S-scheme mechanism. Moreover, the S-scheme electron transfer pathway for the CTO/MIS catalyst system during the photocatalytic process was confirmed using electron spin resonance spectroscopy, free-radical capturing tests, density functional theory calculations, in situ X-ray photoelectron spectroscopy, and semiconductor energy band theory. The study offers an innovative perspective for establishing S-scheme heterojunctions with highly efficient and stable photocatalytic activity for H2 generation and HCHO removal.

Heterointerface engineering in mesoporous g-C3N4@MnFe2O4 photocatalysts for superior hydrogen (H2) evolution

Surfaces and interfaces play a pivotal role in heterostructures-based photocatalysts, which regulate the transfer, separation, and migration of photogenerated charge carriers. In this study, p-type MnFe2O4 nanoparticles (NPs) with complementary band structures were purposefully integrated with n-type porous g-C3N4 nanosheets (NSs) through precise interface engineering. The synergies in the g-C3N4@MnFe2O4 nanocomposites (NCs), leading to performance enhancement and functionalities, arise from their optimized mass fractions within the composite. The heterojunction interface formed in NCs possesses uniformly distributed mesopores (<4 nm), abundant active sites, and a high specific surface area (116 m2/g). Mesoporous heterojunctions improve photocatalytic activity by promoting the transfer of photogenerated electrons and holes to the photocatalyst surface. Notably, the optimized NCs, containing 20 wt% MnFe2O4, display the highest hydrogen evolution rate of 3.17 mmol g⁻¹ h⁻¹ (with methanol) and 5.77 mmol g⁻¹ h⁻¹ (with triethanolamine), which is many folds higher than bare MnFe2O4 and porous g-C3N4, using 1.0 wt.% of Pt as co-catalyst. The enhanced performance is corroborated by the efficient separation of photoinduced charge carriers, facilitated by an induced internal electric field arising from the Fermi level differences between the semiconductors. This study provides new insights into the advantages of designing and constructing mesoporous Z-scheme heterojunction photocatalysts for hydrogen evolution.

Tailoring carbon intercalated α,β-FePc heterophase junction to boost electron transfer for 1O2-dominated photo-Fenton reaction

Construction of 1O2-dominated photo-Fenton reaction (PFR) is of great significance to enhance the compatibility to complicated water matrices, due to the selectivity of 1O2. Herein, a carbon intercalated heterophase junction (α,β-FePc@C) is constructed through a calcination-regulated strategy. The as-synthesized α,β-FePc@C exhibited high efficiency in tetracycline degradation with catalyst-dosage-normalized kinetic rate constant of 1.39 L min-1 g-1, outperforming most previously reported works. Importantly, H2O2 activation follows h+-meditated two-step oxidation, resulting in 1O2-dominated reaction with strong anti-interference performance. Experimental and theoretical evidences reveal that dual phases of α-FePc and β-FePc are strategically retained to form heterophase junction, creating internal electric field to propel the photogenerated carrier separation. Carbon intercalation not only optimizes band structure to promote electron transition but also boosts the electron transfer for H2O2 activation. In general, this work presents a facile strategy of constructing photocatalyst for 1O2-dominated PFR and sheds light on upgrading the adaptability of PFR to complex water matrices.