Interfacial Chemical Bonds Research Articles

Interfacial Bi-O-C bonds and rich oxygen vacancies synergistically endow carbon quantum dot/Bi2MoO6 with prominent photocatalytic CO2 reduction into CO

Developing the photocatalysts with the low charge-transfer resistance and fast charge kinetics is crucial to photocatalytic CO2 reduction into hydrocarbon fuels. Herein, we depict the interfacial Bi-O-C bond-bridged carbon quantum dot (CD)/oxygen vacancy-rich Bi2MoO6 (VOR-BMO) Ohmic junction photocatalysts. They were constructed by in-situ anchoring carbon quantum dots (CDs) onto the VOR-BMO hierarchical petal-like structures (HPs), which are self-assembled from numerous nanosheet subunits. Experimental analysis together with density functional theory (DFT) calculations indicate that the Bi-O-C bonds can provide the atomic-level interfacial channels, and introducing rich oxygen vacancies (VOs) into the BMO HPs can induce the enhanced built-in electric field (IEF) of the Ohmic heterojunction formed between VOR-BMO HPs and CDs, synergistically contributing the eminent charge transfer kinetics, so as to sharply boost the separation and transfer of the photoinduced electrons of VOR-BMO HPs into CDs with a near-zero resistance; Besides, the CD/VOR-BMO heterostructures can not only change the endoergic rate-determining step of VO-poor (VOP)-BMO HPs (i.e., CO* desorption to form CO) to an exoergic reaction process, thus promoting the CO* desorption from the photocatalyst surface, but also decrease the overall activation energy barrier. Consequently, in the presence of H2O vapor with no sacrificial agent, the optimum photocatalyst (CD/VOR-BMO-1.2) exhibits the fantabulous performances of CO2 photoreduction into CO with the production rate and selectivity of 60.00 μmol·g−1·h−1 and near 100 %, respectively. Such performances are comparable with the most recently reported photocatalysts for CO2 conversion. The study offers a valid strategy that harnesses the synergistic effect of the interfacial chemical bonds and Vo-induced enhanced IEF to design the high-efficiency photocatalysts for both energy and environmental applications.

An Electron Bridge of Shared Atoms Mediated Cs3Bi2Br9/Bi2WO6 Z‐Scheme Heterojunction for Photocatalytic CO2 Reduction

AbstractConverting clean solar energy into chemical energy through artificial photosynthesis is an effective solution to solve the energy and environmental issues. Here, we report a Cs3Bi2Br9/Bi2WO6 (CBB/BWO) Z‐scheme heterojunction constructed via electrostatic self‐assembly, which facilitates efficient separation of photogenerated carriers and ensures the corresponding redox capacity of both components. By sharing Bi atoms, a Br−Bi−O bond is established between CBB and BWO, serving as an “electron bridge”. The electrons generated by BWO are efficiently channeled to CBB through the heterojunction‐formed “electron bridge”, thereby achieving effective photocatalytic CO2 reduction. Under simulated sunlight conditions, it exhibits the highest CO yield of 72.52 μmol g−1 (without the addition of any precious metal, photosensitizers or sacrifices), which is approximately 7‐fold and 18‐fold greater than that of pure CBB and BWO, respectively. This work provides a more profound comprehension of the regulation of electron transfer through interfacial chemical bonds, thereby proposing a promising strategy for the development of efficient heterojunction photocatalysts for CO2 photoreduction.

Enhancing Built‐In Electric Field via Defect‐Mediated Interfacial Chemical Bond Construction in Chalcogenide Heterojunction for Alcohol Photooxidation Coupled with H2 Production

AbstractRationally designing nanostructures based on an adequate understanding of structure‐performance relationships is key for directional charge transfer regulation in heterojunction photocatalysts. A general strategy is developed for synthesizing bifunctional Sv‐chalcogenide/Ti3C2 Schottky junctions (Sv = sulfur vacancies, chalcogenides containing CdS, CdIn2S4, ZnIn2S4, ZnS, CuInS2) featuring a giant built‐in electric field (BIEF) via defect‐mediated heterocomponent anchorage, which consists of sulfur vacancy modulation of chalcogenides and Ti3C2 nanoparticle anchoring at defects via interfacial Metal─Oxygen (M─O) bonds. These heterojunctions have the distinctive interface structure of semicoherent phase boundaries and a directionally aligned BIEF pointing from chalcogenides to Ti3C2. The enhanced BIEF creates an asymmetrical charge distribution, which not only governs the charge migration behavior by enabling charge carrier localization and delocalized electron transport continuity but also regulates the molecular catalytic behavior by optimizing pivotal intermediate adsorption/activation (*Ar‐CH(R2)‐OH in dehydrogenation and H* in H2 evolution) in selective alcohol photooxidation coupled with H2 generation. Encouragingly, Sv‐chalcogenide/Ti3C2 exhibits unprecedented performance (up to 13.34‐fold higher efficiency than unmodulated chalcogenides) and good substrate compatibility for various alcohols. This work demonstrates the synergistic effects of surface electron density control and interfacial interaction modulation in regulating BIEFs, elucidating the substantial impact of reinforced BIEF on carrier transport properties and molecular catalytic behavior.

Interfacial chemical bonds and sulfur vacancies synergistically modulated charge transfer in ZnIn2S4/MoO2-C Ohmic-junction photocatalyst for efficient hydrogen evolution

The construction of an Ohmic contact with a strong built-in electric field is crucial for the photocatalytic hydrogen evolution performance. However, consciously modulating Ohmic contacts to facilitate charge transfer remains very difficult. Herein, a sulfur vacancies-rich ZnIn2S4/MoO2-C Ohmic contact structure was synthesized by solvothermal method. Experimental results and DFT calculations indicated that the structure of MoO2-C changes under high temperature and pressure conditions, leading to the formation of interfacial Mo-S bonds with sulfur-vacancy-rich ZnIn2S4 in close contact. Importantly, the electronic structure of the Ohmic junction was synergistically modulated by interfacial chemical bonds and sulfur vacancies, creating a strong built-in electric field that effectively facilitated charge transfer and exciton dissociation at the interface. The optimized ZnIn2S4/MoO2-C composite exhibited a photocatalytic hydrogen evolution rate of 59.9 µmol h−1, which was 12 times and 4.7 times higher than that of ZnIn2S4 without sulfur vacancies and with sulfur vacancies, respectively. This work presented a novel method of synergistically modulating charge transfer in Ohmic junctions, promising improved photocatalytic performance.

Monolithic Integration of Full-Color Microdisplay Screen with Sub-5µm Quantum-Dot Pixels.

Monolithic integration of color-conversion materials onto blue-backlight micro-light-emitting-diodes (micro-LEDs) has emerged as a promising strategy for achieving full-color microdisplay devices. However, this approach still encounters challenges such as the blue-backlight leakage and the poor fabrication yield rate due to unsatisfied quantum dot (QD) material and fabrication process. Here, the monolithic integration of 0.39-inch micro-display screens displaying colorful pictures and videos are demonstrated, which are enabled by creating interfacial chemical bonds for wafer-scale adhesion of sub-5 µm QD-pixels on blue-backlight micro-LED wafer. The ligand molecule with chlorosulfonyl and silane groups is selected as the synthesis ligand and surface treatment material, facilitating the preparation of high-efficiency QD photoresist and the formation of robust chemical bonds for pixel integration. This is a leading record in micro-display devices achieving the highest brightness larger than 400 thousand nits, the ultrahigh resolution of 3300 PPI, the wide color gamut of 130.4% NTSC, and the ultimate performance of service life exceeding 1000h. These results extend the mature integrated circuit technique into the manufacture of micro-display device, which also lead the road of industrialization process of full-color micro-LEDs.

Interfacial Sb[sbnd]O[sbnd]C bond and structural confinement synergistically boosting the reaction kinetics and reversibility of Sb2Se3/NC nanorods anode for sodium storage

Antimony selenide (Sb2Se3) has been considered as a prospective material for sodium-ion batteries (SIBs) because of its large theoretical capacity. Whereas, grievous volume expansion caused by the conversion-alloying reaction leads to fast capacity decay and inferior cycle stability. Herein, the confined Sb2Se3 nanorods in nitrogen-doped carbon (Sb2Se3/NC) with interfacial chemical bond is designed to further enhance sodium storage properties of Sb2Se3. The robust enhancing effect of interfacial SbOC bonds can significantly promote electron transfer, Na+ ions diffusion kinetics and alloying reaction reversibility, combining the synergistic effect of the unique confinement structure of N-doped carbon shells can efficiently alleviate the volume change to ensure the structural integrity. Moreover, in-situ X-ray diffraction reveals intercalation/de-intercalation, conversion/reversed conversion reaction and alloying/de-alloying reaction mechanisms, and the kinetics analysis demonstrates the diffusion-controlled to contribute high capacity. As a result, Sb2Se3/NC anode delivers a high reversible capacity of 612.6 mAh/g at 0.1 A/g with a retentive specific capacity of 471.4 mAh/g after 1000 cycles, and long-cycle durability of over 2000 cycle with the reversible capacities of 371.1 and 297.3 mAh/g at 1 and 2 A/g are achieved, respectively, and an good rate capability. This distinctive interfacial chemical bonds and confinement effect design shows potential applications in the improved conversion/alloying-type materials for SIBs.

Modulating Ti t2g Orbital Bonding in Dual‐Channeled TiO2/rGO Hybrid Architecture for Stable Photocatalytic Methanol to Hydrogen

AbstractCarbon materials are commonly integrated with TiO2 to achieve high carrier mobility and excellent photocatalytic performance, and the chemical bond between TiO2 − C is considered as a significant strategy to enhance efficiency. Nevertheless, few analyses have elucidated the formation mechanism of Ti3 + − C bonds and the underlying reasons for the performance enhancement. To address these issues, this study conducts an in‐depth investigation into the electronic structure of TiO2 − C and demonstrates that the charge in the nonbonding molecular orbital t2g of Ti3 + is transferred to the unoccupied 2p energy level of C through the formation of 1π and 2π bonds, i.e., (Ti 3dxz ‐ C 2py) and (Ti 3dxy ‐ C 2px). The hybridization of t2g‐2p orbitals endows the Ti3 + − C bond with higher carrier mobility and a stronger binding force, thereby contributing to stable photocatalytic H2 production. Inspired by this scenario, the NSTiO2/rGO hybrid architecture, featuring the {101}/{001} surface heterojunction and the Ti3 + − C interfacial chemical bond, has been constructed. As a result, the hybrid catalyst exhibited excellent photocatalytic cycling stability of and an H2 evolution rate of 33.4 mmolh−1g−1. This work proposes a strategy for designing efficient photocatalyst by regulating orbitals to achieve high‐performance photocatalytic methanol splitting.

Construction of multi-functional S-Vacancy-Zn3In2S6/Bi-MOF S-scheme heterojunction containing interfacial chemical bonds for the efficient photocatalytic production of H2O2 and excellent photocatalytic degradation of OTC and TC

Designing outstanding S-scheme heterojunction photocatalysts for eliminating pharmaceutical pollution and energy dilemmas is an effective strategy for tackling the issue of global environmental pollution. Herein, the Zn3In2S6/Bi-MOF S-scheme heterojunction was prepared through a facile in-situ hydrothermal method. The Bi-S bonds were introduced into the interface of an S-vacancy-containing Zn3In2S6/Bi-MOF S-scheme heterojunction, which profoundly boosts migration and separation of photogenerated carriers as the highway for electron transfer. The practical significance of Zn3In2S6/Bi-MOF composites for environmental pollution control was assessed using oxytetracycline (OTC) and tetracycline (TC) as representative pharmaceutical pollutants. Simultaneously, the production performance of H2O2 as a new energy carrier was also evaluated to determine the multi-functionality of the Zn3In2S6/Bi-MOF composite. The H2O2 production rate of optimal proportion photocatalyst reaches 3689.94 μmol/g/h without using the sacrificial agent. In addition, it exhibited a photocatalytic degradation of OTC and TC efficiency of 88.1 % and 65.2 % within 60 min, respectively. The Zn3In2S6/Bi-MOF photocatalytic not only exhibits excellent cyclic stability but also has exceptional anti-interference properties-systematic elucidation of the effects of catalyst dosage, pH, and co-existing substances. The efficient photocatalytic production of H2O2 and the degradation of OTC/TC through Bi-S bonds and VS-modificatory S-scheme charge transfer offer valuable new perspectives for designing photocatalysts.

Activation of Bi2MoO6/Zn0.5Cd0.5S charge transfer through interface chemical bonds and surface defects for photothermal catalytic CO2 reduction

The photocatalytic reduction of CO2 to high-value fuels has been proposed as a solution to the energy crisis caused by the depletion of energy resources. Despite significant advancements in photocatalytic CO2 reduction catalyst development, there are still limitations such as poor CO2 adsorption/activation and low charge transfer efficiency. In this study, we employed a defect-induced heterojunction strategy to construct atomic-level interface Cd-O bonds and form Bi2MoO6/Zn0.5Cd0.5S heterojunctions. The sulfur vacancies (VS) formed in Bi2MoO6/Zn0.5Cd0.5S acted as activation sites for CO2 adsorption. While the interfacial stability provided by the Cd-O bonds served as an electron transfer channel that facilitated the movement of electrons from the interface to the catalytic site. The VS and Cd-O bonds simultaneously influence the distribution of charge, inducing the creation of an interface electric field that facilitates the upward displacement of the center of the d-band. This enhances the adsorption of reaction intermediates. The optimized Bi2MoO6/Zn0.5Cd0.5S heterostructure exhibited high selectivity and stability of photoelectrochemical properties for CO, generating 42.97 μmol⋅g−1⋅h−1 of CO, which was 16.65-fold higher than Zn0.5Cd0.5S under visible light drive. This research provides valuable insights for designing photocatalyst interfaces with improved CO2 adsorption conversion efficiency.

Insight into interfacial engineering for enhancing the synergistic effect of piezo-photocatalytic hydrogen peroxide production

Constructing heterojunctions represents a prevalent approach for enhancing piezo-photocatalytic performance. However, it remains challenging due to contradictory charge polarity and a poor active site. In this study, we employed an in situ hydrothermal method to fabricate a ZnIn2S4-BiOCl compact heterojunction with interfacial chemical bonding. Experimental and theoretical calculations demonstrate that the interfacial chemical bond (Bi-S bond) creates a strong interfacial electronic effect between the heterojunctions, acting as strain centers and charge transfer channels to enhance coordinated piezoelectric and photoelectric fields, thereby facilitating charge transfer. Additionally, interfacial bonding induces dynamic surface reconstruction and redistribution of electron density, improving reactant activation and charge exchange while reducing reaction barriers. Consequently, ZB-4 catalyst exhibits exceptional piezoelectric photocatalytic performance for pure water to H2O2 conversion (1987.33 μmol g-1·h-1), which is 5.85 times than that of pure BiOCl. This study presents a valuable strategy for enhancing positive coordination between heterojunctions and the photocatalytic piezoelectric effect.

Boosted charge separation in porphyrin-based MOFs/CdS photocatalyst via interfacial −N−Cd− bridge bond construction

The high interfacial charge transfer barrier has been a main thermodynamic obstacle for improving the catalytic efficiency of heterojunction materials. Optimizing the interfacial environment is an effective strategy to achieve high catalytic efficiency. Herein, the coordinate bond (−N−Cd−) is designed to connect the hafnium porphyrin−metal organic framework (HT) and CdS nanoparticles, which is systematically analyzed by the 1H NMR, FTIR, Raman and DRS, respectively. The optimized 15HT1.5 H/CdS6 composite featuring interfacial bridge bonds, exhibits an H2 production up to 11.9 mmol·g−1·h−1, which is 28.5, 52.8 and 7 times greater than pure CdS, HTH, and mechanically mixed sample without interfacial chemical bonds connected, respectively. Mechanistic study suggests that the coordination bonds between HT and CdS serve as the directional carrier transfer bridges, significantly improving interfacial charge separation and chemical stability. Moreover, the formed Z-scheme charge transfer mechanism also endows the composite with high redox ability. This strategic construction of interfacial chemical bonds within heterojunction provides an effective pathway for improving interfacial charge transfer in the heterojunction photocatalysts.

Molecular investigation on interfacial toughening between silane coupling agent treated glass fiber and cement

Silane coupling agents (SCAs) are widely used as adhesion promoters to tightly bond glass fiber (GF) and cement matrix (CM) for developing sustainable and high-performance glass fiber-reinforced cementitious (GFRC) composites. This study uses molecular dynamics (MD) simulation to examine the effect of 3-aminopropyltriethoxysilane (APS) on CM/GF interfacial properties. Pure cement and nine cement models bonded to APS-modified GF with APS concentrations of 0.00%, 12.50%, 25.00%, 37.50%, 50.00%, 62.50%, 75.00%, 87.50%, and 100.00% are constructed. It is shown that pure CSH system experiences interfacial delamination. With increasing APS from 0.00% to 37.50%, the failure mode transits from interfacial delamination to CSH delamination, and with increasing APS to 100.00%, it transits to interfacial delamination. Meanwhile, it is measured that with increasing APS from 0.00% to 37.50%, the tensile strength increases from 0.48 to 0.58 GPa and the adhesion energy increases from 0.71 to 0.90 J⋅m−2. Comparatively, with increasing APS to 100.00%, the tensile strength decreases to 0.26 GPa, and the adhesion energy decreases to 0.23 J⋅m−2. Moreover, the interfacial structure and chemical bond analysis demonstrate that with increasing APS from 0.00% to 37.50%, the peak of H2O molecules decreases, which denotes stronger interfacial bonding. With increasing APS from 37.50% to 100.00%, the peak of the H2O molecules increases, which induces low interfacial bonding. These findings provide a basis for optimizing APS concentrations for specific performance enhancements of GFRC materials.

Construction of a Composite Sn‐DLC Artificial Protective Layer with Hierarchical Interfacial Coupling Based on Gradient Coating Technology Toward Robust Anodes for Zn Metal Batteries

AbstractDeveloping a robust zinc (Zn) anode, free from Zn dendrites and unwanted side reactions, relies on designing a durable and efficient interfacial protection layer. In this study, gradient coating technology is employed to construct a hierarchically structured composite of Sn with diamond‐like carbon (DLC/Sn‐DLC) as an artificial protective layer. The DLC framework endows DLC/Sn‐DLC layer with high stability and adaptability, achieving long‐term stability of the anode–electrolyte interface. The gradual‐composite Sn, with its Sn─O─C interface chemical bonds, facilitates rapid charge transfer and offers ample zincophilic sites at the base, promoting uniform Zn2+ reduction reaction and deposition. Additionally, the DLC/Sn‐DLC composite exhibits a “lotus effect” and favorable hydrophobic properties, preventing water‐reduced side reactions. Leveraging this structural design and the synergistic cooperation of DLC and Sn, the DLC/Sn‐DLC@Zn electrode demonstrates remarkable Zn plating/stripping reversibility, eliminating Zn dendrites and side reactions. Notably, under a high current density of 10 mA cm−2, the DLC/Sn‐DLC@Zn anode‐based symmetrical cell exhibits stable operation for over 1550 h, with a low nucleation overpotential of 101 mV. The DLC/Sn‐DLC@Zn||Mn3O4‐CNTs full battery delivers a high capacity of 109.8 mAh cm−2 after 5800 cycles at 2 A g−1, and the pouch cell shows potential for energy storage applications.

Constructing interfacial chemical interaction of dual-carbon protected cobalt diselenide anode for sodium storage

Transition metal selenides are attracting enormous attention due to their high theoretical capacity and appropriate working potential for sodium storage, while their intrinsic low electronic conductivity and large volume expansion during the cycling processes inevitably result in inadequate rate performance and inferior cycling stability. Herein, cobalt diselenide-based hollow sugarloaf-like self-supporting fiber membranes with strong interfacial chemical (Co-C) bonds have been reported for sodium-ion batteries (SIBs) via the dual-carbon protection strategy. Based on X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) combined with density functional theory (DFT), A built-in electric field is generated at the interface between CoSe2/C and CNFs, which provides a strong driving force for electron transfer and ion migration, making the optimal CoSe2/C−0.3@CNFs anode over 67.8 % of capacity retention from 0.1 to 5 A/g and maintained about 269.5 mAh/g of discharge capacity at 5 A/g. The strong interfacial Co-C bonds in CoSe2/C@CNFs enhance the interfacial affinity between CoSe2/C and CNFs, making it easier for CoSe2/C to trap sodium ions and effectively resist the volume expansion during cycling, thus showing excellent cyclic stability with a reversible capacity of 247.6 mA h g−1 at 1.0 A/g after 2600 cycles. The sodium storage mechanism of CoSe2/C−0.3@CNFs electrode in SIBs is systematically analyzed via in-situ XRD and in-situ Raman spectra. This study provides an effective approach to constructing heterostructured composites with strong chemical bonds and built-in electric field characteristics for high-rate capability and long-cycle stability SIBs. Moreover, the sodium ion diffusion kinetics in the CoSe2/C−0.3@CNFs anode is also revealed.

Accelerated Charge Transfer through Interface Chemical Bonds in MoS2/TiO2 for Photocatalytic Conversion of Lignocellulosic Biomass to H2.

Solar photocatalytic H2 production from lignocellulosic biomass has attracted great interest, but it suffers from low photocatalytic efficiency owing to the absence of highly efficient photocatalysts. Herein, we designed and constructed ultrathin MoS2-modified porous TiO2 microspheres (MT) with abundant interface Ti-S bonds as photocatalysts for photocatalytic H2 generation from lignocellulosic biomass. Owing to the accelerated charge transfer related to Ti-S bonds, as well as the abundant active sites for both H2 and ●OH generation, respectively, related to the high exposed edge of MoS2 and the large specific surface area of TiO2, MT photocatalysts demonstrate good performance in the photocatalytic conversion of α-cellulose and lignocellulosic biomass to H2. The highest H2 generation rate of 849 μmol·g-1·h-1 and apparent quantum yield of 4.45% at 380 nm was achieved in α-cellulose aqueous solution for the optimized MT photocatalyst. More importantly, lignocellulosic biomass of corncob, rice hull, bamboo, polar wood chip, and wheat straw were successfully converted to H2 over MT photocatalysts with H2 generation rate of 10, 19, 36, 29, and 8 μmol·g-1·h-1, respectively. This work provides a guiding design approach to develop highly active photocatalysts via interface engineering for solar H2 production from lignocellulosic biomass.

Mn-S chemical bond mediated Z-scheme photocatalyst boosting efficient H2 evolution with apparent quantum yield exceeding 32% under visible light

Developing a highly effective solar-to-H2 conversion system is a promising strategy for carbon neutrality. Here, we report a chemically bonded Z-scheme photocatalyst by specifically linking the conduction band site of ZnIn2S4 with the valence band site of Mn0.3Cd0.7S1-x. Deviates from the typical van der Waals interactions between two semiconductors, the in-built robust binding force (Mn-S bond) and charge transfer channel facilitates the electron mobility, minimizes detrimental deep charge trapping, and prolongs the active charge lifetime from 983 ps to 4250 ps. The sulfur vacancies in Mn0.3Cd0.7S1-x are partially refilled by atoms of the same element in ZnIn2S4 during the in-situ formation of heterojunctions, which promotes and solidates the establishment of interfacial chemical bonds. The optimal photocatalyst achieves a high quantum efficiency of 32.71 % at 420 nm. This study offers a new insight into the development of Z-Scheme heterojunctions via a synergistic approach involving doping, vacancy filling and strong interfacial chemical bonds.

Constructing Robust Interfacial Chemical Bond Enhanced Charge Transfer in S‐Scheme 3D/2D Heterojunction for CO2 Photoreduction

AbstractA stable ZnTe@Cs3Sb2I9 catalyst with 3D/2D‐hollow‐composite structure is constructed for CO2 photocatalytic reduction via the in situ growth of Cs3Sb2I9 nanosheets on hollow ZnTe microspheres using lattice matching. The formed Tellurium‐Antimony (Te─Sb) bonds improved the poor contact at the heterojunction interface, effectively promoted charge separation, and successfully suppressed photocorrosion. The unique core‐shell structure not only strengthens light absorption but also improves CO2 adsorption capacity. Consequently, the S‐scheme heterojunction with the synergistic effect of chemical bonds and 3D/2D‐hollow‐composite structure significantly enhances photocatalytic performance. The ZnTe@Cs3Sb2I9 photocatalyst offers a CO selectivity of 90.5%, which is higher than that of pure ZnTe (22.9%) and Cs3Sb2I9 (56.9%). This structure holds great promise for practical applications in CO2 photocatalytic reduction.

Constructing interface chemical coupling S-scheme heterojunction MoO3-x@PPy for enhancing photocatalytic oxidative desulfurization performance: Adjusting LSPR effect via oxygen vacancy engineering

Construction of photocatalyst that combines excellent electron transfer and photoresponse capabilities to enhance photocatalytic performance remains a challenging task. In this work, interfacial Mo-N bonds and vacancy engineering collaborative modified MoO3-x@polypyrrole (MP) S-scheme heterojunction is rational designed for efficient photocatalytic oxidative desulfurization. The addition of polypyrrole introduces rich defects which inducing the localized surface plasmon resonance (LSPR) effect and enhancing light absorption. Furthermore, the combination facilitates the formation of Mo-N bonds. The modifications amplify the built-in electric field and conduct the efficacious separation of photogenerated carriers. With the synergism of LSPR effect and interfacial chemical Mo-N bonds, the optimal MP photocatalyst displays attractive desulfurization rate of 100% for dibenzothiophene (DBT) in 60 min under illumination, touching the objective of ultra-deep desulfurization. The study extends a novel understanding of the impact of LSPR effect and heterojunction interface charge transfer on the photocatalytic desulfurization ability.

Construction of La2O3/AgCl S-scheme heterojunction with interfacial chemical bond for efficient photocatalytic degradation of bisphenol A

The formation of interfacial chemical bonds in S-scheme heterostructure is a crucial factor to realize efficient interfacial charge transfer. High-energy mechanical ball-milling is an effective method to form interfacial chemical bonds. In this work, an S-scheme La2O3/AgCl heterojunction catalyst was designed and prepared by ball-milling method. XPS, FTIR and Raman measurements showed that La-Cl chemical bond was formed at the interface of La2O3 and AgCl and an S-scheme charge transfer path mechanism existed in the La2O3/AgCl composite. The results of electrochemistry, photo-electrochemistry, capture experiments, free radical measurement and EPR verified that the S-scheme heterojunction and the interfacial La-Cl bond significantly accelerated the charge transfer rate between La2O3 and AgCl, and enhanced the photocatalytic capability of the composite catalysts. The degradation rate of bisphenol A by La2O3/AgCl heterojunction composite (LA50) reached 99 % in 20 min, and it also had excellent anti-interference ability and cycling stability. The toxicity of the degradation intermediates of bisphenol A was much less than itself, as calculated by TEST simulation. This work provided a promising strategy for improving the performance of S-scheme heterojunction catalysts by introducing interfacial chemical bonds as charge transfer channels.

Preparation of TiO2–SiO2–CaCO3 composite opacifier by hydrophobic agglomeration and mechanism of inhibiting glaze yellowing

This study investigates the preparation of TiO2–SiO2–CaCO3 composite opacifier (Ti–Si–Ca) and its application in sanitary ceramic glazes. This approach involved hydrophobic agglomeration through surface-induced hydrophobic modification of TiO2, SiO2 and CaCO3 particles, along with the interactions between the hydrophobic carbon chains of modifiers. The Ti–Si–Ca formed a uniform coating with well-dispersed TiO2 and SiO2 particles on the CaCO3 surface and strong bonds formed among TiO2, SiO2 and CaCO3 through interpenetration of the organic carbon chains on the surface. The Ti–Si–Ca was added to the basic glazes of sanitary ceramics at a proportion of 15.5 % and fired at 1125 °C for 4 h. The resulting white ceramic glazes had chromaticity values of L*, a*, and b* at 93.76, −0.73, and 3.89, respectively, demonstrating superior glaze opacity and whiteness compared to glazes made with a ZrSiO4 opacifier (L* 90.30, b* 4.50). Glass and titanite phase make up the majority of the Ti–Si–Ca ceramic glazing layer of, with titanite serving as the opacified phase. Elimination of organic groups in Ti–Si–Ca during glaze firing formed interfacial chemical bonds among TiO2, SiO2 and CaCO3, which facilitated the synthesis of titanite from the three components at high temperatures. The Ti–Si–Ca was a highly opaque glaze without yellowing because the organic groups of Ti–Si–Ca were removed and interfacial chemical bonds formed among the TiO2, SiO2 and CaCO3 in the low-temperature stage of glaze firing. This transformed the three phases into titanite at high temperature and eliminated free TiO2. The formation of rutile TiO2, which has a yellow hue, at high temperatures was inhibited. This study provides a novel approach for low-energy preparation of TiO2–SiO2–CaCO3 composite opacifiers and addresses the challenge of replacing ZrSiO4 with TiO2 in ceramic opacifiers.