Sunlight-Driven Combustion Synthesis of Defective Metal Oxide Nanostructures with Enhanced Photocatalytic Activity

Synthesis of metal oxide nanostructures through combustion routes is a promising technique owing to its simplicity, rapidity, scalability, and cost-effectiveness. Herein, a sunlight-driven combustion approach is developed to synthesize pristine metal oxides and their heterostructures. Sunlight, a sustainable energy source, is used not only to initiate the combustion reaction but also to create oxygen vacancies on the metal oxide surface. ZnO nanostructures are successfully synthesized using this novel approach, and the products exhibit higher photocatalytic activity in the decomposition of methyl orange (MO) than ZnO nanostructures synthesized by the conventional methods. The higher photocatalytic activity is due to the narrower band gap, higher porosity, smaller and more uniform particle size, surface oxygen vacancies, as well as the enhanced exciton dissociation efficiency induced by the sunlight. Porous Fe3O4 nanostructures are also prepared using this environmentally benign method. Surprisingly, few-layer Bi2O3 nanosheets are successfully obtained using the sunlight-driven combustion approach. Moreover, the approach developed here is used to synthesize Bi2O3/ZnO heterostructure exhibiting a structure of few-layer Bi2O3 nanosheets decorated with ZnO nanoparticles. Bi2O3 nanosheets and Bi2O3/ZnO heterostructures synthesized by sunlight-driven combustion route exhibit higher photocatalytic activity than their counterparts synthesized by the conventional solution combustion method. This work illuminates a potential cost-effective method to synthesize defective metal oxide nanostructures at scale. Copyright - 2019 American Chemical Society.This study was supported by University Grants Commission, India, under University with Potential for Excellence (UPE) program at University of Mysore, UGC JRF (Award No. F.19-1/2013(SA-I)), and Deanship of Scientific Research (DSR) at King Fahd University of Petroleum & Minerals (KFUPM) through project no. DF181021.Scopu

Direct Z-Scheme Cs2O-Bi2O3-ZnO Heterostructures as Efficient Sunlight-Driven Photocatalysts

Limited light absorption, inefficient electron-hole separation, and unsuitable positions of conduction band bottom and/or valence band top are three major critical issues associated with high-efficiency photocatalytic water treatment. An attempt has been carried out here to address these issues through the synthesis of direct Z-scheme Cs2O-Bi2O3-ZnO heterostructures via a facile, fast, and economic method: solution combustions synthesis. The photocatalytic performances are examined by the 4-chlorophenol degradation test under simulated sunlight irradiation. UV-vis diffuse reflectance spectroscopy analysis, electrochemical impedance test, and the observed transient photocurrent responses prove not only the significant role of Cs2O in extending light absorption to visible and near-infrared regions but also its involvement in charge carrier separation. Radical-trapping experiments verify the direct Z-scheme approach followed by the charge carriers in heterostructured Cs2O-Bi2O3-ZnO photocatalysts. The Z-scheme charge carrier pathway induced by the presence of Cs2O has emerged as the reason behind the efficient charge carrier separation and high photocatalytic activity.Qatar University, Shenzhen Polytechnic, Southern University of Science and Technology, King Fahd University of Petroleum and Minerals, Excellent Young Talents Fund Program of Higher Education Institutions of Anhui Province, Ministry of Science and Technology of the People's Republic of China, National Natural Science Foundation of Chin

Direct Z-scheme Cs2O-Bi2O3-ZnO heterostructures for photocatalytic overall water splitting

In this work, a direct Z-scheme Cs2O-Bi2O3-ZnO heterostructure without any electron mediator is fabricated by a simple solution combustion route. Cs2O is chosen as a sensitizer to expand the light absorption range, and in addition, its conduction band minimum (CBM) and valence band maximum (VBM) positions are suitable to construct a direct Z-scheme system with ZnO and Bi2O3. Structural and elemental analyses show clear evidence for heterostructure formation. The Z-scheme charge carrier migration pathway in Cs2O-Bi2O3-ZnO is confirmed by high resolution XPS and ESR studies. The fabricated heterostructure exhibits a good ability to split water to H2 and O2 under simulated sunlight irradiation without any sacrificial agents or co-catalysts and has excellent photostability. The apparent quantum efficiency of the optimized Cs2O-Bi2O3-ZnO heterostructure reaches up to 0.92% at 420 nm. The excellent efficiency of this fabricated heterostructure is attributed to the efficient charge carrier separation, the high redox potential of the CBM and VBM benefiting from a direct Z-scheme charge carrier migration pathway and the extended light absorption range.Scopu

Surface Plasmonic Resonance and Z-Scheme Charge Transport Synergy in Three-Dimensional Flower-like Ag-CeO2-ZnO Heterostructures for Highly Improved Photocatalytic CO2Reduction

The design and engineering of plasmonic metal nanocomposite photocatalysts offer an operative approach for highly efficient CO2 photoreduction. Herein, the authors report a plasmonic 3D flower-like (3DF) Ag-CeO2-ZnO nanocomposite catalyst with effective charge carrier separation/transfer and CO2 adsorption capacity exhibiting a considerable enhanced performance compared to pure ZnO and CeO2 for photocatalytic CO2 reduction to CO and CH4 under UV-vis light. The apparent quantum efficiency of the optimized sample is 4.47% at 420 nm, and the CO2 to CO selectivity reaches up to 95%. The enhanced photocatalytic performance of 3DF Ag-CeO2-ZnO can be assigned to the prolonged absorption in the visible light region induced by the surface plasmon resonance (SPR) effect, the efficient separation of photogenerated charges, and the Z-scheme configuration. Furthermore, the photocatalyst displays excellent stability and reusability. The mechanism of the plasmon-mediated Z-scheme structure has been suggested in which Ag NPs act as both visible light absorber and electron mediator.Scopu

CeO2 Nanostructures Enriched with Oxygen Vacancies for Photocatalytic CO2 Reduction

Synthesizing nanomaterials at the expense of solar energy and the associated energy generation have utmost significance as far as environmental sustainability is concerned. Here, sunlight-assisted combustion synthesis of a nanoscale metal oxide (CeO2) is reported. The sunlight, as a clean renewable energy source, is used for the first time to initiate the exothermic combustion reaction and to introduce oxygen vacancies into the CeO2. The current synthesis setup controls the environmental problems of gas evolution, usually associated with the conventional method, and thus maintains the green pathway. Additionally, for comparison, CeO2 nanoparticles are also synthesized using the conventional solution combustion method (CeO2-CSC). It is found that the CeO2 synthesized using sunlight-assisted combustion (CeO2-SAC) possesses a smaller particle size, a higher concentration of oxygen vacancies, and a narrower band gap than the CeO2-CSC. Therefore, CeO2-SAC demonstrates higher photocatalytic performance in converting CO2 to CH3OH (0.702 ?mol h-1 g-1) than the CeO2-CSC (0.397 ?mol h-1 g-1), thus pointing toward environmentally benign photocatalytic CO2 reduction.Scopu

Strategies to Enhance ZnO Photocatalyst's Performance for Water Treatment: A Comprehensive Review

Despite the photocatalytic organic pollutant degradation using ZnO started in 1910?1911, many challenges are still ahead, and several critical issues have to be addressed. Large band gap, and short life-time of photogenerated electrons and holes are critical issues negatively affect the photocatalytic activity of ZnO. Various approaches have been introduced to overcome these issues including intrinsic doping, extrinsic doping, and heterostructure. This review introduces unique and deep insights into tuning of the photocatalytic activity of ZnO. It starts by description of how to tune the photocatalytic activity of pristine ZnO through tuning its morphology, surface area, exposed face, and intrinsic defects. Afterward, the review explains how the Z-scheme approach succeed to address the redox weakened issue of heterojunction approach. In general, this review provides a clear image that helps the researcher to tune the photocatalytic activity of pristine ZnO and its heterostructure.Scopu

Novel Green Biomimetic Approach for Synthesis of ZnO-Ag Nanocomposite; Antimicrobial Activity against Food-borne Pathogen, Biocompatibility and Solar Photocatalysis

10.1038/s41598-019-44309-wScientific Reports91830

Thermal, dielectric and optical studies on cellulose acetate butyrate-gold nanocomposite films prepared by laser ablation

This work employed pulsed laser ablation to produce cellulose acetate butyrate-gold (CAB-Au) nanocomposite films and the evaluation of their structural and thermal characteristics using Raman, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and Differential Scanning Calorimetry (DSC). In the frequency range 0.1–10 MHz, nanocomposite films' dielectric constant, loss, and electric modulus behavior were investigated as a function of temperature. The refractive index, finesse coefficient, Brewster coefficient, critical angles, dielectric function, and color properties of nanocomposite films were examined in the wavelength range 190–800 nm. X-ray diffraction shows a strong Au diffraction signal in all samples, confirming Au NPs. The SEM micrograph shows Au embedded in CAB. The CAB-Au nanocomposites had higher thermal stabilities (Tm) than pure CAB, and the DSC thermograms showed a fluctuating glass transition temperature due to the dynamics of organic-inorganic interactions in the nanocomposite films. Dielectric dispersion is caused by hidden dipolar polarization. The CAB (5 min) sample had the highest ac conductivity as a function of frequency at various temperatures as the Au content in the Au/CAB composite rose. The simplest quantum mechanical tunneling (QMT) model also best explains the ac conduction property. We found a relationship between the nanocomposites' refractive index and the amount (extent of incorporation) of Au in the materials, with laser irradiation time determining the various color constants. Tauc plots reveal a permitted transition with an optical energy gap of 5.1eV for the polymer film and 4.75eV after 10 and 20 min of laser irradiation