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Designing of a visible-light-driven semiconductor-based heterojunction with suitable band alignment and well-defined interfacial contact is considered to be an effective strategy for the transformation of solar-to-chemical energy and environmental remediation. In this context, MXenes have received tremendous attention in the research community due to their merits of abundant derivatives, elemental composition, excellent metallic conductivity, and surface termination groups. Meanwhile, a facile synthetic strategy for MXene-derived TiO2 nanocomposites with stable framework and higher photocatalytic activity under visible-light irradiation still remains a challenge for researchers. Herein, we report a novel synthetic strategy of preparing a two-dimensional Ti3C2@TiO2 nanohybrid by a facile reflux method under acidic conditions. In this oxidation reaction, protonation of the hydroxyl terminal group of MXene creates Ti more electrophilic and susceptible to an oxidative nucleophilic addition reaction with the presence of both water and oxygen. The physicochemical properties of the nanohybrid Ti3C2@TiO2 were verified by varieties of characterization techniques. High-resolution transmission electron microscopy and X-ray photoelectron spectroscopy analysis specifically elucidated the intimate interfacial interaction between Ti3C2 and TiO2. The optimized Ti3C2@TiO2-48 h photocatalyst exhibited the highest tetracycline hydrochloride (TCH, 90% in 90 min) degradation efficiency in comparison to pristine TiO2 with a rate constant (k) of 0.02463 min-1. The major contribution of •O2- and •OH radicals throughout photocatalytic TCH degradation was confirmed by the trapping experiment. Moreover, the photocatalyst showed the highest hydrogen generation rate of 140.8 µmol h-1 along with an apparent conversion efficiency of 2.2%. The excellent photocatalytic activity of Ti3C2@TiO2 originated from the superior electrical conductivity of cocatalyst Ti3C2, which facilitated spatial photogenerated e-/h+ separation and transfer at the Ti3C2 MXene@TiO2 interface. Overall, this research work will describe a promising protocol of designing MXene-derived photocatalysts toward efficient environmental remediation and wastewater treatment applications.

RESUMEN

In the present work, we report the preparatory strategy of MgCr-layered double hydroxide (LDH) nanosheets with 90% degree of delamination by employing a formamide-assisted co-precipitation and mild hydrothermal route for the degradation of methylene blue (MB) under solar light exposure. The as-synthesized MgCr-LDH nanosheets were characterized by assorted characterization techniques such as powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), Raman, thermogravimetric analysis (TGA), N2 adsorption-desorption measurement, X-ray photoelectron spectroscopy (XPS) and UV-Visible diffused reflectance spectroscopy (UV-DRS). The XRD pattern of MgCr-LDH nanosheets quantified the strain (ε) and dislocation density (δ) of 1.371 lines-2 m-4 and 0.5723 lines m-2 related to the (110) plane with d-spacing value of 1.6169 Ȧ. With a minimum band gap of ∼2.63 eV, the as-synthesized MgCr-LDH nanosheets displayed 90.6% MB photodegradation under the experimental protocols such as catalyst dosage of 30 mg/L, initial MB concentrations of 20 ppm, pH of 7 and time duration of 2 h under solar light exposure. Further, the recyclability test of the photocatalyst signifies material stability up to four successive cycles with 90% retention of MB degradation under sunlight exposure. The superior catalytic performances of the MgCr-LDH nanosheets could be ascertained to the suppression of excitonic recombination and effective light harvestation properties, synergistically contributed by the porous structural aspects via association of uni/multi-lamellar nanosheets, surface defect sites and photoactive Cr3+ cations. Additionally, the surface -OH groups of LDH contributed towards the generation of •OH radicals for triggering the catalytic performances. This type of work advances the novel ideas for establishing highly potent photocatalysts via synergizing structural and surface properties, paving towards effective wastewater treatment.

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RESUMEN

In the present work, we report the synthesis of single system three-dimensional (3D) open porous structure of MgCr-LDH nanoparticles in a substrate-free path by using one-step formamide assisted hydrothermal reaction followed by visible light irradiation for significant photoelectrochemical (PEC) properties that manifest towards photocatalytic H2 and O2 production. The as-prepared nanostructured materials were characterized by various physico-chemical characterization techniques. Moreover, this unique synthetic approach produces 3D open porous network structure of MgCr-LDH nanoparticles, which were formed by stacking of numerous 2D nanosheets, for effective light harvestation, easy electronic channelization and unveil superlative PEC properties, including high current density (6.9 mA/cm2), small Tafel slope of 82 mV/decade, smallest arc of the Nyquist plot (59.1 Ω cm-2) and photostability of 6000 s for boosting water splitting activity. In addition, such perfectly self-stacked 2D nanosheets in 3D MgCr-LDH possess more surface active defect sites as enriched 50% oxygen vacancy resulting a good contact surface within the structure for effective light absorption along with easy electron and hole separation, which facilitates the adsorption of protons and intermediate for water oxidation. Additionally, the Cr3+ as dopant pull up the electrons from water oxidation intermediates, thereby displaying superior photocatalytic H2 and O2 production activity of 1315 µmol/h and 579 µmol/h, respectively. Therefore, the open 3D morphological aspects of MgCr-LDH nanoparticles with porous network structure and high surface area possess more surface defect sites for electron channelization and identified as distinct novel features of this kind of materials for triggering significant PEC properties, along with robustly enhance the photocatalytic water splitting performances.

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The charge separation and transfer are the major issues dominating the under-laying energy conversion mechanism for photocatalytic system. Construction of semiconductor-based heterojunction system considered to be viable option for boosting the spatial charge separation and transfer in the photocatalytic water splitting system. Here, we design a ternary heterojunction of Ti3C2/N, S-TiO2/g-C3N4 by thermal annealing and ultrasonic assisted impregnation method having a well-designed n-n heterojunction and noble metal free Schottky junction for adequate hydrogen evolution. The optimal content of 4 wt% Ti3C2 on N, S-TiO2/g-C3N4 (4-TC/NST/CN) exhibit the highest rate of hydrogen generation 495.06µ mol h-1 which is 3.1, 4.1 and 1.6 fold higher than the pristine N, S doped-TiO2, g-C3N4 and binary hybrid (N, S doped-TiO2/g-C3N4) respectively, with 7% apparent conversion efficiency (ACE). The increment in the activity is described to the robust photogenerated carrier separation and double charge transfer channels because of the formation of dual heterojunction (n-n heterojunction and Schottky junction). XRD and Raman results revealed the occupancy of Ti3C2 in the heterojunction due to the strong interaction between Ti3C2, with N, S doped-TiO2 and g-C3N4. The HRTEM analysis confirmed the formation of close interfacial junction between the Ti3C2, N, S doped-TiO2 and g-C3N4. Moreover, the higher photocurrent, low PL intensity and lower impedance arc suggested the lower charge carrier recombination rate in 4-TC/NST/CN heterojunction. This work represents a significant development to establish a sound foundation for future design of MXene-based ternary hybrid system towards significant charge carrier separation and transfer for H2 production activity.

RESUMEN

Photocatalytic (PC) and photoelectrochemical (PEC) water splitting is a plethora of green technological process, which transforms copiously available photon energy into valuable chemical energy. With the augmentation of modern civilization, developmental process of novel semiconductor photocatalysts proceeded at a sweltering rate, but the overall energy conversion efficiency of semiconductor photocatalysts in PC/PEC is moderately poor owing to the instability ariseing from the photocorrosion and messy charge configuration. Particularly, layered double hydroxides (LDHs) as reassuring multifunctional photocatalysts, turned out to be intensively investigated owing to the lamellar structure and exceptional physico-chemical properties. However, major drawbacks of LDHs material are its low conductivity, sluggish mass transfer and structural instability in acidic media, which hinder their applicability and stability. To surmount these obstacles, the formation of LDH@graphene and analogus heterostructures could proficiently amalgamate multi-functionalities, compensate distinct shortcomings, and endow novel properties, which ensure effective charge separation to result in stability and superior catalytic activities. Herein, we aim to summarize the currently updated synthetic strategies used to design heterostructures of 2D LDHs with 2D/3D graphene and graphene analogus material as graphitic carbon nitride (g-C3 N4 ), and MoS2 as mediator, or interlayer support, or co-catalyst or vice versa for superior PC/PEC water splitting activities along with long-term stabilities. Furthermore, latest characterization technique measuring the stability along with variant interface mode for imparting charge separation in LDH@graphene and graphene analogus heterostructure has been identified in this field of research with understanding the intrinsic structural features and activities.

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Antibiotic contaminants have received much attention due to the increasing serious environmental concerns. In this work, for the first time, we have fabricated a series of significant type-II p-n heterostructure with Z-scheme charge transfer between p-type B-doped g-C3N4 with different proportion of n-type BN through a simple in-situ growth process. PXRD, FTIR, UV-Vis, FESEM, HRTEM and EIS analysis were applied for the detailed characterization of the as-prepared composites to study the crystal phase, structural features, optical and electrical properties. The photocatalytic behaviour of BN/BCN photocatalyst was investigated by the degradation of tetracycline hydrochloride under solar light illumination. Experimental results revealed that about 88.1% of TCH was degraded by the BN/BCN composite containing 4 wt% BN in the BN/BCN matrix, in 60 min of solar light irradiation. Reduction in recombination rate of photo generated electron-hole pair's and enhanced visible light absorption ability is credited to the enhanced photocatalytic performance of BN/BCN composite. Trapping experiment for the scavenging agents has confirmed that superoxide (O2¯) and hydroxyl (OH) radicals are the main reactive species during the TCH degradation process. The high stability shown by the BN/BCN composite opens a new path for designing of significant BN based Z-scheme photocatalyst for prevention of environmental issues.

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Designing of an efficient heterostructure photocatalyst for photocatalytic organic pollutant removal and H2 production has been a subject of rigorous research intended to solve the related environmental aggravation and enormous energy crises. Z-scheme-based charge-transfer dynamics in a p-n heterostructure could significantly replicate the inherent power of natural photosynthesis, which is the key point to affect the transportation of photoinduced exciton pairs. In this finding, a series of p-type MoS2 loaded with n-type NiFe-layered double hydroxide (LDH) forming a heterostructure MoS2/NiFe LDH were designed by electrostatic self-assembled chemistry and an in situ hydrothermal strategy for photocatalytic rhodamine B (RhB) dye degradation and H2 production. The creation of p-n heterojunctions of type-II and Z-scheme mode of charge transfer modified the optical and electronic property of the as-synthesized MSLDH3, thereafter promoting the generation, separation, and migration of photoinduced electron-hole pairs. The as-synthesized MSLDH3 showed superior photocatalytic activities in degradation of RhB with H2 evolution, which was enhanced by 3- and 4.5-fold and 10.9 and 19.2 times higher than that of NiFe LDH and MoS2, respectively. Last but not the least, heterostructure MSLDH3 possesses practical stability for its resultant enhanced photocatalytic activity with recyclability for everyday life.

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A series of heterostructure NiFe LDH/N-rGO/g-C3N4 nanocomposite were fabricated by combining calcinations-electrostatic self-assembly and hydrothermal steps. In this method, negatively charged N-rGO was electrostaticaly bonded to the self-assembled interface of n-n type g-C3N4/NiFe LDH hybrid. XRD and AFM results revealed successful formation of heterostructure nanocomposite due to the coupling effect of exfoliated NiFe LDH nanosheets with N-rGO and g-C3N4. Among the as synthesized heterostructure, CNNG3LDH performed superior photocatalytic activities towards 95 and 72% mineralization of RhB and phenol. Furthermore, CNNG3LDH could achieve the highest photocatalytic H2 evolution rate of 2508 µmolg-12h-1 and O2 evolution rate of 1280 µmolg-12h-1 under visible light irradiation. The CNNG3LDH possess lowest PL intensity, reduced arc of the Nyquist plot (43.8 Ώ) and highest photocurrent density (-0.97 mA cm-2) which revealed effective charge separation for superior photocatalytic activities. TRPL spectral results reveal the synergistic effect of layered component in CNNG3LDH for achievable higher life time of excitons of ~16.52 ns. In addition, N-rGO mediator based Z-scheme charge transfer mechanisms in CNNG3LDH were verified by the ESR and TA-PL studies. Enriched oxygen vacancy type defects in NiFe LDH and N-rGO mediated Z-scheme charge transfer mechanistic path strongly manifest the superior photocatalytic activities of the heterostructure materials.

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The hybrid structure of nanoparticles (NPs) with nanosheets has the advantage of both anisotropic properties of NPs and large specific surface areas of nanosheets, which is desirable for many technological applications. In this study, MgCr2O4 spinel NPs decorated on highly porous MgO nanosheets forming MgO/MgCr2 O4( x) nanocomposites were synthesized by a one pot coprecipitation method followed by a heat treatment process of the solvated wet gel of MgCr-LDH with polar solvent N, N-dimethylformamide (DMF) at 400 °C. This novel synthetic methodology generates materials consisting of porous metal oxides nanosheets adhered with spinel phase NPs due to the slow generation of gases such as H2O, CO2, and NH3 under moderate temperature during the heat treatment process. The synergistic effect of much wider band gap MgO nanosheets and narrow band gap MgCr2O4 NPs added increased stability due to the stronger bonding coordination of MgCr2O4 NPs with MgO nanosheets. The obtained MgO/MgCr2 O4( x) nanocomposites possess large specific surface areas, highly porous structure, and excellent interface between MgCr2O4 NPs and MgO nanosheets, which proved from N2 sorption isotherm, TEM, HR-TEM study. With metallic ratio of MgCr3:1, MgO/MgCr2O4(MgCr3:1) nanocomposites exhibit highest H2 evolution rate of 840 µmolg-12h-1, which was 2 times higher than that of pure MgCr2O4(420 µmolg-12h-1). The LSV measurement study of MgO/MgCr2O4 (MgCr3:1) nanocomposite shows an enhancement of light current density of 0.22 µA/cm2 at potential bias of -1.1 V. The Mott-Schottky analysis suggested the band edge positions of the n-type constituents and formation of n-n type heterojunctions in MgO/MgCr2O4 (MgCr3:1) nanocomposite, which facilitates the flow of charge carriers. The EIS and Bode phase plot of MgO/MgCr2O4 (MgCr3:1) nanocomposite signifies the lower interfacial charge transfer resistance and higher lifetime of electrons (2.7 ms) for enhanced H2 production. Lastly, the enhanced photocatalytic H2 production activity and long-term stability of MgO/MgCr2O4(MgCr3:1) could be attributed to maximum specific surface area, porous structure, close intimacy contact angle between two cubic phases of MgCr2O4 NPs and MgO nanosheets, abundant oxygen vacancies sites, reduced charge transfer resistance and suitable band edge potential to drive the thermodynamic energy for H2 production. This work highlighted an effective strategy for the synthesis of cost-effective 2D porous heterojunctions nanocomposite photocatalyst for promising applications in the field of clean H2 production utilizing abundant solar energy.

RESUMEN

Photocatalytic generation of H2 and O2 by water splitting remains a great challenge for clean and sustainable energy. Taking into the consideration promising heterojunction photocatalysts, analogous energy issues have been mitigated to a meaningful extent. Herein, we have architectured a highly efficient bifunctional heterojunction material, i.e., p-type Co(OH)2 platelets with an n-type ZnCr layered double hydroxide (LDH) by an ultrasonication method. Primarily, the Mott-Schottky measurements confirmed the n- and p-type semiconductive properties of LDH and CH material, respectively, with the construction of a p-n heterojunction. The high resolution transmission electron microscopy results suggest that surface modification of ZnCr LDH by Co(OH)2 hexagonal platelets could form a fabulous p-n interfacial region that significantly decreases the energy barrier for O2 and H2 production by effectively separating and transporting photoinduced charge carriers, leading to enhanced photoreactivity. A deep investigation into the mechanism shows that a 30 wt % Co(OH)2-modified ZnCr LDH sample liberates maximum H2 and O2 production in 2 h, i.e., 1115 and 560 µmol, with apparent conversion efficiencies of H2 and O2 evolution of 13.12% and 6.25%, respectively. Remarkable photocatalytic activity with energetic charge pair transfer capability was illustrated by electrochemical impedance spectroscopy, linear sweep voltammetry, and photoluminescence spectra. The present study clearly suggests that low-cost Co(OH)2 platelets are the most crucial semiconductors to provide a new p-n heterojunction photocatalyst for photocatalytic H2 and O2 production on the platform of ZnCr LDH.

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In this work, a series of heterostructure Ag@Ag3PO4/g-C3N4/NiFe layered double hydroxide (LDH) nanocomposites were prepared by a combination of an electrostatic self-assembly and in situ photoreduction method. In this method, positively charged p-type Ag3PO4 was electrostatically bonded to the self-assembled negatively charged surface of the n-n-type g-C3N4/NiFe (CNLDH) LDH hybrid material with partial reduction of Ag+ to metallic Ag nanoparticles (NPs) by the photogenerated electrons and available surface -OH groups of LDH under visible light irradiation. The presence of Ag3PO4 as a p-type semiconductor, the surface plasmon resonance (SPR) effect of metallic Ag NPs, and oxygen vacancies as Ov-type defects in NiFe LDH could greatly achieve the quasi-type-II p-n/n-n dual heterojunctions, which was revealed by the shifted conduction band and valence band potentials in Mott-Schottky (M-S) analysis. Among all the optimized heterostructures, CNLDHAgP4 could achieve the highest photocatalytic Cr(VI) reduction rate of 97% and phenol oxidation rate of 90% in 2 h. The heterostructure CNLDHAgP4 photocatalyst possesses a unique morphology consisting of cubic phases of both Ag NPs and Ag3PO4, which adhered to the thin and curvy layers of the CNLDH hybrid for smooth electronic and ionic charge transport. Furthermore, the intimate Schottky barriers formed at the interface of quasi-type-II p-n/n-n dual heterojunctions were verified by the photoluminescence, linear sweep voltammetry, M-S, electrochemical impedance study, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy studies. The SPR effect of Ag NPs and oxygen vacancies as Ov-type defect in NiFe LDH can effectively accelerate the threshold of charge separation and be the main reason for the enhanced activity achieved by the as-fabricated heterostructure photocatalyst.