Using commercial materials for colorimetric detection of toxic cyanide (CN-) anions can greatly improve safety and benefit society. This work discusses the colorimetric sensing properties of commercially available trans-(3-nitrostyrene analogues, including trans-(3-nitrostyrene (P1), trans-4-methoxy-(3-nitrostyrene (P2), trans-4-methyl-(3-nitrostyrene (P3), trans-4-fluoro-(3-nitrostyrene (P4), trans-4-bromo-(3-nitrostyrene (P5), trans-4-chloro-(3-nitrostyrene (P6), and trans-(3-methyl-(3-nitrostyrene (P7), in dimethyl sulfoxide (DMSO) and acetonitrile (ACN). P1-P4 show strong reddish-pink and yellowish-orange colors while detecting CN-ions in DMSO and ACN, with new UV-visible peaks appearing at 515 nm/510 nm and at 490 nm/485 nm, respectively. Conversely, P5 and P6 exhibit mild color responses to CN-in DMSO and ACN, with absorbance peaks at 505 nm/510 nm and at 490 nm/430 nm, respectively. P7 shows no selectivity for CN-ions due to steric and electronic structural effects. The high selectivity of P1-P4 for CN-is confirmed through interference studies. pH values of 6 and 7 are ideal for sensory testing. The sensor response of P1-P6 to CN-is linear across a range of 0.1 to 1000 mu M (mu M = 10-6 M), with estimated detection limits (LODs) at 10-9-10-6 M. Nuclear Magnetic Resonance (NMR), mass spectra, and density functional theory (DFT) analyses validate the Michael addition as the sensing mechanism. The test strip method demonstrates the solid-state colorimetric sensing ability of P1-P3 for CN-ions. Spiked CN-ions in water samples show the real-time sensing capability of P1-P4. These results open the door for future designs using different fluorophores with nitro (-NO2) Michael acceptor.

The mechanisms for the self- and cross-reactions of anti-CH3CHOO and syn-CH3CHOO conformers have been investigated by ab initio quantum-chemical and statistical-theory calculations. The results of the study indicate that at 298 K under 5-Torr He pressure, the self-reaction of anti-CH3CHOO is the fastest with kaa = 4.90 × 10-10 cm3 molecule-1 s-1, the anti-syn cross-reaction with kas = 1.82 × 10-10 cm3 molecule-1 s-1, and the self-reaction of syn-CH3CHOO with kss = 1.28 × 10-10 cm3 molecule-1 s-1. The theoretical results, including the deactivation of internally excited dimers formed by initial bimolecular association reactions accounting for more than 50% of the predicted rates, agree with the recent experimental data within reported errors measured at 298 K and 2-10 Torr He pressure.

Photocatalytic conversion of CO2 into value-added fuels offers a viable approach to combat climate change and address global energy demands. Here, we present a fluorine-doped SnS2 thin film with sulfur vacancy (i.e., SV-SnS2:F), prepared via thermal evaporation, post-sulfurization, and fluorine ion-implantation. Substitution of sulfur with fluorine and sulfur vacancy formation changes the product selectivity from CH4 to CO with about 40-fold enhanced yield and boosted internal quantum efficiency (IQE) of 0.52%. Transient absorption, in situ near-ambient pressure X-ray photoelectron, and in situ Fourier transform infrared spectroscopies, along with first-principles density functional theory calculations, suggest that nearest-neighbor Sn to F serves as an active site and stabilizes the *COOH intermediate. Our findings shed light on how F doping activates the nearby elements and its crucial role in intermediate stabilization toward selectivity change in a heterogeneous photocatalysis process.

The use of one-step products and their applications in sensory applications has gained much importance. Herein, Schiff’s base fluorescent turn-on sensor, namely FBTS, was synthesised via a condensation reaction between 6-fluorobenzo[d]thiazol-2-amine and 2-hydroxybenzaldehyde. The probe FBTS exhibits an intense “turn-on” blue fluorescence upon binding to Al3+ ions in a dimethyl sulfoxide–water (DMSO–H2O (8:2, v/v)) medium. From photoluminescence (PL) titrations, the detection limit (LOD) for Al3+ is estimated to be 0.14 microM, and the Benesi–Hildebrand plot-based association constant (Ka) of 5.4 × 104 M−1 confirm a strong association between FBTS and Al3+. Negligible interference is observed in the presence of other metal ions. From the pH effect studies, the optimal pH range for Al3+ detection is 7–9. The recyclable reversibility of FBTS + Al3+ complex has been demonstrated via the sodium salt of ethylenediaminetetraacetic acid (Na2-EDTA) chelation. A Job’s plot and interrogations, such as high-resolution mass spectrometry (HR-MS), 1H-nuclear magnetic resonance (NMR) titration, and density functional theory (DFT), verified the 1:1 stoichiometry of binding between FBTS and Al3+. Based on multiple analyses, the binding mode and mechanism have been detailed. In addition, the practical application of FBTS for detecting Al3+ is demonstrated using the strip paper method, fish analysis, spiked real sample analysis, and cellular imaging.

To preserve the ecosystem, researchers have recommended screening for CN- ions. For the detection of CN- ions, chemodosimetric probes play a defined role by affording diverse reaction-based responses. Here, (E/Z)-9-(2-nitrovinyl)anthracene (AN) was synthesized via a one-pot reaction between anthracene-9-carboxaldehyde and nitromethane. AN possesses anticancer activity and was employed as a chemodosimeter to detect CN- ions. In the presence of CN-, the "turn-on" photoluminescence (PL) emission enhancement at 420 nm was observed due to the formation of the 1,4-addition product 'ANCN'. The maximum PL emission for 'ANCN' was achieved within one minute and was active across the pH range of 3-11. The AN-CN- detection system demonstrated linearity in the range of 0.01 to 500 µM, with a limit of detection (LOD) of 99.4 nM. The Job plot, based on the ultraviolet-visible (UV-vis) spectral investigation, revealed the 1 : 1 stoichiometric association between AN and CN-, with an association constant (K a) of 2.81 × 109 M-1. Multiple spectroscopic and density functional theory (DFT) studies confirmed the formation of 'ANCN'. The energy gap variations of AN and ANCN were derived from DFT data. The analysis of strips, cotton swabs, fish pieces, real water, and herbal extracts confirmed the analytical performance of AN. The recovery of CN- ions in real water and herbal extract was between 84.36% and 101.61%, with <5% relative standard deviation (RSD). Cytotoxicity assays in cancerous (A549 and MCF-7) and non-cancerous (WI-38 and MCF-10) cell lines defined the anticancer efficacy of AN. These findings pave the way for similar designs in the future.

Controlling spin states in earth-abundant electrocatalysts is substantial for enhancing the oxygen evolution reaction (OER). However, managing spin in pyrite-type disulfides remains challenging. In this study, a spin-tuned Co/Ni-FeS2 is synthesized via pyrolysis of molecular metal-thiolate complexes in a sulfur-rich, inert environment. This approach enables precise dopant control, atomic-scale uniformity, and scalable production that surpasses those of traditional hydrothermal or sulfidation methods, offering a versatile platform for designing multi-metal pyrites. Structural and spectroscopic analyses confirm the successful substitution of iron by cobalt and nickel, demonstrating that co-doping modifies spin and electronic states. This results in increased spin polarization, improved electron transport, and lower energy barriers for oxygen-oxygen bond formation. In situ X-ray absorption spectroscopy and post-catalytic examinations reveal controlled reconstruction into mixed-metal oxyhydroxides containing high-valence iron, cobalt, and nickel as active centers. The optimized 6% Co, 2% Ni-FeS2 shows excellent OER performance, with an overpotential of 193 mV at 10 mA cm-2, a Tafel slope of 55 mV dec-1, and high durability. Density functional theory suggests that co-doping enhances spin-selective pathways and adsorption energetics, providing a solid foundation for spin-regulated pyrite electrocatalysts in water splitting and other clean energy applications.

We report the design and fabrication of a novel hydrogenated photoactive composite, H:(Au@Cu2O/TiO2). Transmission electron microscopy (TEM) and X-ray diffraction (XRD) confirmed a well-defined core-shell architecture with a p-n heterojunction configuration. Optical and electronic band structures were systematically investigated. The localized surface plasmon resonance LSPR-induced inter-band electron transfer process from Au to Cu2O shell was elucidated from the transient absorption spectra (TAS) and in situ X-ray absorption spectroscopy (XAS). A comprehensive charge-transfer mechanism was provided; the Z-scheme configuration facilitates charge transfer and separation for improved efficiency with Cu2O shell and TiO2 NPs to complete the redox cycle. The hydrogenated heterostructure exhibited an exceptional H-2 evolution rate of 9.3 mmol g(-)(1) h(-)(1) under AM 1.5 illumination while maintaining excellent stability. This enhancement is mainly attributed to direct injection of Au LSPR, a 3.9 times improvement with respect to H:(Cu2O/TiO2) of 2.4 mmol g(-1) h(-1) which was not reported before. Apparent quantum yield (AQY) measurements reached 2.5% at 650 nm and 0.8% at 800 nm, effectively extending the photocatalytic activity into the near-infrared region. These results highlight the robust H:(Au@Cu2O/TiO2) photocatalyst as a highly promising platform for photocatalytic hydrogen evolution with methanol as an efficient hole scavenger and broader photoconversion applications.

In this study, we demonstrate vertically grown SnO2/SnS 1D/1D nanostructures for bifacially active and efficient photocatalytic CO2 conversion. Due to effective energy band engineering via the construction of 1D nanostructure, the sole nanostructured SnO2 photocatalysts are active in producing CH4 through photocatalytic CO2 conversion processes without any material modification or cocatalysts. The heterostructured SnO2/SnS 1D/1D photocatalysts demonstrate an exceptional and selective CH4 production rate of 0.33 mu mol center dot cm- 2 center dot h- 1 (= 132 mu mol center dot g- 1 center dot h- 1) and 0.365 mu mol center dot cm- 2 center dot h- 1 (= 146 mu mol center dot g- 1 center dot h- 1) from the sample-side and back side illuminations, respectively, This work presents the first demonstration of bifacially active CO2 conversion using SnO2based nanostructures as photocatalysts, without any material modification, for bifacially active photocatalytic CO2 conversion. The remarkable performance results from various factors: (1) extended active sites by the formation of the 1D/1D hetero-nanostructure, (2) light absorption enhancement to longer wavelengths of light due to the incorporation of SnS materials, (3) bifacially efficient light absorption and charge transfer by the 1D/1D nanostructure formation, (4) improved charge transfer through S-O and S-Sn-O bonds at the SnO2/SnS interface, and (5) effectively separated CO2 reduction and water oxidation reactions by activation of Z-scheme charge conduction between SnO2/SnS. This work highlights the potential of SnO2/SnS nanostructures as a highly efficient and selective photocatalyst for sustainable CO2 conversion, paving the way for practical applications in renewable energy and environmental remediation.

Photocatalytic conversion of carbon dioxide (CO2) into valuable chemical and fuel products is a potentially effective pathway to mitigate the continuous increment of CO2 concentrations in the atmosphere. Nevertheless, the insufficient conversion efficiency and product selectivity of the photocatalytic reaction remain serious obstacles that restrict its future and practical commercialization. Herein, a borate-functionalized In2S3 nanosheet catalyst is successfully synthesized for the first time via a boric acid (BA)-assisted solvothermal method and demonstrated to exhibit highly efficient and selective photocatalytic CO2 conversion. This synthetic approach not only decorated the catalyst surface with borate functional groups but also engineered the energy band structure of In2S3, overcoming the limitations of In2S3-based materials in photocatalysis. Accordingly, the optimum photocatalyst (i.e., BIS-3) has exceptional CO2 conversion efficiency (28 & micro;mol g-1 h-1 and 0.8 & micro;mol g-1 h-1 for CO and CH4, respectively) with 89.2% selectivity toward CO production, which is the highest record among reported phase-pure In2S3 and metal sulfide photocatalysts without the utilization of sacrificial agents. Moreover, the fabricated catalyst achieved high stability and excellent recyclability. This remarkable performance is attributed to the enhanced charge carrier generation/separation, as well as the optimal redox efficiency provided by the borate functionalization-induced energy band structure engineering. In addition, theoretical simulations demonstrated that the borate-rich surface is favorable for excellent CO2 adsorption and facile CO desorption. This work offers a facile method for rationally functionalizing photocatalysts and electronically engineering the band structure, opening avenues for developing the efficiency, selectivity, and stability of metal sulfides in the light-driven CO2 conversion field.

Two-dimensional (2D) PdCu bimetallene (PdCu) exhibits unique structural and electronic properties, enhancing surface reactivity for crucial electrochemical reactions in energy conversion and storage. The one-pot synthesis, followed by dealloying (DA) to form DA PdCu, further enhances surface reactivity by altering the electronic structure. This process induces geometrical effects, significantly impacting surface strain and influencing selectivity and performance for (oxygen reduction reaction) ORR and (methanol oxidation reaction) MOR in an alkaline medium. The heterogeneous surface of DA PdCu with crystalline and amorphous regions and abundant surface defects, enhances active sites for improved ORR and MOR kinetics. During ORR, the DA PdCu exhibits superior mass activity (MA) of 0.62 mA mu g-1 and extended stability with a positive shift (10 mV) in half-wave potential after 20,000 cycles. Additionally, it exhibits excellent MOR-MA (3335.9 mA mg-1) with 62.3% retention after 10,000 cycles, effectively competing with reported catalysts. Theoretical studies clarify the electronic strain transformation and its influence on adsorption energies of reaction intermediates on PdCu and DA PdCu during ORR and MOR, crucially correlating with experimental findings. The alloying-dealloying process in 2D-layered PdCu is a promising strategy to enhance the structure-activity relationship for improved multifunctional electrocatalysis with greater endurance.

Lithium iron sulfide (Li2FeS2) exhibits unique characteristics, including multielectron redox behavior and abundant valence states, making it a promising candidate for electrode material in lithium-ion batteries. However, the sluggish charge transfer kinetics, low stability, and slow rate performance hamper its practical application. Herein, we propose a strategy to boost the electrochemical performance of Li2FeS2 by substituting F dopants with S sites through a two-step solid-state process. The effects of F dopants on material characteristics and electrochemical behaviors are investigated. Experimental results show that F dopants significantly enhance diffusion kinetics and rate performance, indicating improved interfacial activity in Li2FeS2−xFx. Theoretical calculations confirm that F substitution occurs at the S site, enhancing charge mobility. After 100 cycles, the optimized Li2FeS2-xFx cathode exhibits a specific capacity of 250 mAh g−1, higher than pristine Li2FeS2. The improved electrochemical properties, diffusion kinetics, capacity, and rate performance are attributed to the enhanced structural stability from a stronger metal–fluorine bond compared to metal–sulfur, and increased Li+ ion diffusion due to a greater electronegativity difference. Lithium iron sulfide is a promising electrode material in lithium-ion batteries but suffers from sluggish charge transfer kinetics and low stability. Here, the electrochemical performance of lithium iron sulfide was improved by substituting F dopants with S sites through a two-step solid-state process

Pristine biochar typically exhibits limited capacity for heavy metal adsorption due to its inadequate pore development and insufficient surface functionality. This study introduces an innovative chemical strategy to enhance the surface of sawdust biochar with sulfur-based functional groups (C=S, C-S, S-S, S2-, S-H,-SO32-,-SO42-) to significantly improve cadmium (Cd) adsorption. Sulfur-doping using H2SO4, Na2S, and Na2S2O3 markedly increased the sulfur content from 0.11% (pristine) to 2.81% (H2SO4), 0.57% (Na2S), and 13.27% (Na2S2O3). Characterization techniques such as SEM-EDS, FTIR, and XPS confirmed the successful incorporation of sulfur moieties and additional oxygen-containing groups, improving surface functionality. The Cd adsorption capacity of S-modified biochar increased by 4.8-9.0 times compared to pristine biochar, with peak values of 39.38, 20.84, and 34.14 mg g- 1 for H2SO4, Na2S, and Na2S2O3-modified biochar, respectively. The equilibrium time was significantly reduced from 4 h (pristine) to 5-10 min (S-modified). The enhanced Cd adsorption was attributed to the synergistic interplay of electrostatic attraction, cadmium-it electron interactions, complexation, and ion exchange mechanisms, facilitated by the presence of oxygen and sulfur functional groups. Density Functional Theory (DFT) calculations showed that sulfur doping modulated the electronic properties of the biochar-Cd systems, narrowing the band gap and enhancing the Cd-O bonds, thereby improving the Cd adsorption performance. Additionally, the binding energies of the S-modified biochar-Cd complex were found to be more stable compared to those before Cd adsorption. This study demonstrates that both oxygen and sulfur-functionalized sawdust biochar is an effective and eco-friendly adsorbent for Cd removal, highlighting the significance of tailored surface modifications to augment biochar's reactivity and affinity towards specific contaminants. The developed material offers a sustainable and scalable solution for Cd removal from aqueous environments, contributing to advanced water treatment technologies and environmental remediation strategies.

This study reports on the rational design of hydroxyl-functionalized covalent organic framework nanofibers (HO-COFs: PyTA-2,3-NA(OH)2 and PyTA-2,6-NA(OH)2) by a scalable solvothermal method. The resulting PyTA-2,3-NA(OH)2 HO-COF is more hydrophilic than the PyTA-2,6-NA(OH)2 HO-COF, which can effectively enhance the sensitivity of the sensor toward basic ethylenediamine (EDA). The fabricated HO-COF nanofiber-based quartz crystal microbalance sensor exhibits a rapid sensing response and a distinguished selectivity toward EDA vapor, arising from the strong hydrogen bonding interactions with the NH2 groups of EDA, as investigated by a wide variety of chemical analysis techniques and density functional theory calculations. The presence of exposed neighboring hydroxyl groups that face the same direction in the PyTA-2,3-NA(OH)2 HO-COF and the NH2 groups present in EDA exhibited efficient interactions. The PyTA-2,3-NA(OH)2 nanofiber with neighboring hydroxyl groups exhibits 1.6 times higher sensitivity to 100 ppm (ppm) EDA than PyTA-2,6-NA(OH)2 with hydroxyl groups in opposite directions, with a low limit of detection of 2.9 ppm. The PyTA-2,3-NA(OH)2 nanofiber structure has abundant active neighboring hydroxyl groups facing the same direction, making them favorable active sites for binding EDA molecules through strong hydrogen bond interactions. The color of the HO-COF changed after exposure to EDA vapor, as investigated by colorimetric assessment and naked-eye detection. These HO-COF nanofibers exhibit remarkable selectivity for EDA in the presence of other interfering chemical vapors and show high stability with only a 6.4% drop in sensitivity after 6 months. The adsorption of EDA on PyTA-2,3-NA(OH)2 nanofibers follows a pseudo-first-order kinetic model, with an adsorption rate about 8.0 times faster than PyTA-2,6-NA(OH)2 nanofibers. The findings of this study highlight the potential use of COFs, particularly those nanofibers with close neighboring hydroxyl groups, as effective sensing materials for the selective detection of harmful EDA.

Solar-driven CO2 reduction holds great promise for sustainable energy, yet the role of atomic active sites in governing intermediate formation and conversion remains poorly understood. Herein, a synergistic strategy using Ni single atoms (SAs) and surface oxygen vacancies (Ov) is reported to regulate the CO2 reduction pathway on the Bi2WO6 photocatalyst. Combining in-situ techniques and theoretical modeling, the reaction mechanism and the structure-activity relationship is elucidated. In-situ X-ray absorption spectroscopy identifies Bi and Ni as active sites, and in-situ diffuse reflectance infrared Fourier transform spectroscopy demonstrates that adsorption of H2O and CO2 readily forms CO32- species on the Ov-rich catalyst. Optimally balancing Ni SAs and Ov lowers the energy barrier for the formation and dehydration of a key COOH intermediate, leading to favorable CO formation and desorption. Consequently, a superior CO production efficiency of 53.49 mu mol g-1 is achieved, surpassing previous reports on Bi2WO6-based catalysts for gas-phase CO2 photoreduction.

The stereo-specific production of syn- and anti-CH3CHOO conformers from the CH3CHI + O2 reaction has been investigated by ab initio quantum-chemical and statistical theory studies. The results of the studies clearly indicate that the [syn]:[anti] product ratio depends on both temperature and pressure of the reaction system, and is kinetically, rather than thermodynamically, controlled. Most experimental data measured near room temperature at 2–10 Torr He pressure agree with the predicted results in terms of either the absolute rate constants for syn- and anti-CH3CHOO production and/or the [syn]:[anti] product ratio. If the stereo-specificity of syn- and anti-CH3CHOO formation were controlled thermodynamically, one would predict [syn]:[anti] = 241:1 independent of pressure at 298 K, instead of (80 ± 10):(20 ± 10) measured experimentally or 86:14 predicted theoretically at 5-Torr He pressure. All calculations were performed using Gaussian 16 software. Geometry, frequency, and IRC analysis calculations were conducted at the B3LYP/Aug-cc-PVTZ level of theory. The potential energy surface of the system was computed at the CCSD(T)/Aug-cc-PVTZ//B3LYP/Aug-cc-PVTZ level. The rate constants for individual product channels in the reaction, including the direct production of IO + CH3CHO and the collisional deactivation of the excited CH3CHIO2* intermediate formed by the association of CH3CHI with O2, were predicted by statistical theory calculations using the Variflex code.

Herein, for the first time, asymmetric zinc coordination sites (Zn-N1S3) were confined in ZnIn2S4 monolayer (NZISV) via N,N-Dimethylformamide/ethylene glycol (DMF/EG)-assisted hydrothermal method, overcoming the limitation of symmetric metal coordination in intrinsic ZnIn2S4. Through growing an NZISV on ultra-thin benzene-functionalized crystalline g-C3N4 nanosheets (CBCN), a delicately designed heterojunction was constructed with chemically bonded channels (In-N) and dislocation-induced tensile strain at the heterointerface. Consequently, the optimum catalyst achieves a superior CO2-to-CO conversion efficiency of 166.5 mu mol center dot g-1 center dot h-1 with an apparent quantum yield of 5.4 % at 420 nm, outperforming the CO2-to-CO conversion among all reported g-C3N4-and ZnIn2S4-based photocatalysts. The experimental techniques and theoretical simulations confirm that the modulated Z-scheme catalyst has maximum interfacial charge transfer efficiency. Furthermore, in situ-based characterization and computational calculations confirmed the highly activated/adsorbed CO2 molecules and intermediates via the uniquely designed heterostructured catalyst. Also, Zn-N1S3 centers reduce the energy barrier formation of the key intermediate (*COOH) and CO desorption via modulating the d-band center of the zinc atoms. This work underscores the crucial role of asymmetric active-site design in precisely modulated Zscheme heterostructured materials for CO2 conversion.

Simultaneous detection of multiple hazards like cesium (Cs+), hydroxide ions (OH-), and picric acid (PA) using a fluorescent probe has not been reported before. To address this, a perylene derivative called PDIDE was synthesized and effectively used to detect Cs+, OH-, and PA with minimal interference. UV-visible and photoluminescence (PL) spectral analyses, along with colorimetric and fluorometric images, clearly demonstrate the sensor's selectivity for PDIDE. The PL linear response ranges of PDIDE for Cs+, OH-, and PA are set between 0.2-500, 0.3-1000, and 0.1-100 mu M, with detection limits (LODs) of 180, 233, and 71 nM, respectively. Job's plots indicate 1:2 (for Cs+ and OH-) and 2:1 (for PA) stoichiometries. Association constants (K-a) for PDIDE with Cs+, OH-, and PA are estimated at 8.261 x 10(-)(5) M--(2), 5.628 x 10(-)(4) M--(2), and 5.375 x 10(-)(6) M--(2), respectively. Binding modes, bandgap changes, and mechanisms are analyzed using nuclear magnetic resonance (NMR), mass spectrometry, Fourier-transform infrared spectroscopy (FTIR), density functional theory (DFT), and time-resolved photoluminescence (TRPL). Biocompatibility and sensor applicability are demonstrated through sulforhodamine B (SRB) assays, paper strips, cotton buds, fish, and cellular imaging studies. Spiked interrogations of tap water, Radix Hedysari extract, Nelumbinis Stamen extract, corroded iron rod extract, and soil water extract at various concentrations lead to 63 data points, showing > 93 % recoveries with relative standard deviation (RSD) values of < 5 %, confirming the sensor's practical utility.

Light-driven conversion of CO2 into small energy-rich molecules effectively addresses both energy demands and reduction in carbon dioxide emissions. However, due to the low efficiency of light absorption and charge carrier separation/transfer, most semiconducting materials have a low conversion activity and poor conversion product selectivity. Herein, ZnIn2S4 nanosheets are introduced to oxygen vacancy-rich ZnO microrod films for CO2 conversion. This heterostructure forms an atomically disordered heterointerface that can play an important role in strengthening the contact between the two crystalline materials and providing an efficient charge transfer pathway. The resulting ZnIn2S4/ZnO film photocatalyst exhibits superior performance compared to other ZnO-film-based photocatalysts (0.84 and 0.34 μmol·cm-2·h-1 for CH4 and CO, respectively) with ∼90.8% selectivity toward CH4 production. The formation of the ZnIn2S4/ZnO heterojunction film contributes to strengthening the charge carrier generation, separation, and migration through a defect-engineered Z-scheme mechanism. This work highlights the role of disorder-engineered heterointerfaces in film-based heterostructured photocatalysts for optimizing the CO2 conversion efficiency.