Novel Two-Dimensional AgInS2/SnS2/RGO Dual Heterojunctions: High Spatial Charge and Toxicity Evaluation.

A single semiconductor employed into photo(electro)catalysis is not sufficient for charge carrier separation. Designing a multiple heterojunction system is a practical method for photo(electro)catalysis. Herein, novel two-dimensional AgInS2/SnS2/RGO (AISR) photocatalysts with multiple junctions were prepared by a simple hydrothermal method. The synthesized AISR heterojunctions showed superior photoelectrochemical performance and photocatalytic degradation of norfloxacin, with a high degradation rate reaching 95%. More importantly, the toxicity of photocatalytic products decreased within the reaction process. High spatial separation efficiency of photogenerated electron-hole pairs was evidenced by optical and photoelectrochemical characterizations. Furthermore, a laser flash photolysis technique was carried on investigating the lifetime of the charge carrier of the fabricated dual heterostructures. In addition, sulfur and oxygen vacancies existed in AISR heterojunctions could largely constrain the recombination of electron-hole pairs. Density functional theory calculations were carried out to analyze the mechanism of photoinduced interfacial redox reactions, showing that reduced graphene oxide and AgInS2 act as electron and hole trappers in the photocatalytic reaction, respectively. Due to the interfacial electric field formed from AISR dual heterojunctions, the effective spatial charge separation and transfer contributed to the boosting photo(electro)catalytic performance.

Double Active Sites in Co-Nx-C@Co Electrocatalysts for Simultaneous Production of Hydrogen and Carbon Monoxide.

The hydrogen evolution reaction (HER) by electrocatalytic water splitting is a prospective and economical route. However, the approach is severely hindered by the sluggish anodic OER, poor reactivity of electrocatalysts, and low-value-added byproducts at the anode. Herein, formaldehyde was added as an anode sacrificial agent, and a bifunctional Co-Nx-C@Co catalyst containing abundant Co-N4 sites and Co nanoparticles was successfully fabricated and evaluated as both a cathodic and an anodic material for the HER and formaldehyde selective oxidation reaction (FSOR), respectively. Co-Nx-C@Co displayed a remarkable electrocatalytic performance simultaneously for both HER and FSOR with high hydrogen (H2) and carbon monoxide (CO) selectivity. Density functional theory calculations combined with experiments identified that Co-N4 and Co nanoparticles were dominating active sites for CO and H2 generation, respectively. The coupling tactic of FSOR at the anode not only expedites the reaction rate of HER but also offers a high-efficiency and energy-saving means for the generation of valuable H2/CO syngas.

Boosting interfacial charge transfer and electricity generation for levofloxacin elimination in a self-driven bio-driven photoelectrocatalytic system.

Recently, molybdenum disulfide (MoS2) has stimulated significant research interest as a promising electrode candidate in solar cells and energy conservation fields. Unfortunately, the short lower electron/hole migration lifetimes and easy agglomeration hamper its wide practical applications to some extent. Herein, interface engineering coupled with a bio-assisted photoelectrochemical (PEC) strategy is presented to construct a 0D MoS2 quantum dot (QD)/1D TiO2 nanotube electrode for pollutant elimination. Aimed at accelerating charge transfer over the 0D/1D composite interface, three types of coupling PEC models were developed to optimize the catalytic performance. The single chamber microbial fuel cell (SCMFC)-PEC integrated system was found to be the best alternative for levofloxacin (LEV) elimination (0.029 min-1), and the sequential SCMFC-PEC further realized the whole system self-running independently. In addition, the interfacial electron migration and LEV degradation pathways were thoroughly investigated by LC/TOF/MS coupled with density functional theory (DFT) calculations to clearly elucidate the electron transfer paths, LEV-attacked sites and mineralization pathways in a joint sequential SCMFC-PEC system. As such, the constructed self-recycling system provides a new platform for bio-photo-electrochemical utilization, which could exhibit promising potential in environmental purification.

Synergetic Effect of Facet Junction and Specific Facet Activation of ZnFe2O4 Nanoparticles on Photocatalytic Activity Improvement.

Crystal facet engineering has been proved as a versatile approach in modulating the photocatalytic activity of semiconductors. However, the facet-dependent properties and underlying mechanisms of spinel ZnFe2O4 in photocatalysis still have rarely been explored. Herein, ZnFe2O4 nanoparticles with different {001} and {111} facets exposed were successfully synthesized via a facile hydrothermal method. Facet-dependent photocatalytic degradation performance toward gaseous toluene under visible light irradiation was observed, where truncated octahedral ZnFe2O4 (ZFO(T)) nanoparticles with both {001} and {111} facets exposed exhibited a superior performance than the others. The formed surface facet junction between {010} and {100} facets was responsible for the improved activity by separating photogenerated e-/h+ pairs efficiently to reduce their recombination rate. Photogenerated electrons and holes were demonstrated to be immigrated onto {001} and {111} facets, separately. Intriguingly, electron paramagnetic resonance trapping results indicated that both •O2- and •OH were abundantly present in the ZFO(T) sample under visible light irradiation as major reactive oxygen species involved in the photocatalytic degradation process. Additionally, further investigation revealed that {001} facets played a predominant role in activating photogenerated transient species H2O2 into •OH, beneficially boosting the intrinsic photocatalytic activity. This work has not only presented a promising strategy in regulating photocatalytic performance through the synergetic effect of facet junction and specific facet activation but also broadened the application of facet engineering with multiple effects simultaneously cooperating.

Facile tailoring of Co-based spinel hierarchical hollow microspheres for highly efficient catalytic conversion of CO2.

High-performance and low-cost photocatalysts are of significance to artificial photosynthetic systems for converting of CO2 into CO and other value-added products. In this work, we developed a controllable and scalable self-templated approach to fabricate hierarchical Co-base spinel hollow microspheres for visible light-driven CO2 reduction with a Ru-based sensitizer. The hollow microspheres are assembled by ultrathin nanosheets using Ni-Co-hydroxides as the morphology-conserved precursor. A series of characterization techniques were conducted to investigate structural features of the prepared Co-base spinel hollow spheres. Owing to the integration of the specific microstructure, functional Ni/Co species and oxygen vacancies, Co-base spinel hollow spheres possess enhanced CO2 adsorption ability, more active sites, and efficient transfer and separation of photoexcited electrons. The high CO-evolving rate (27.7 µmol h-1) and selectivity (84.4%) manifest desirable performance of Co-base spinel hollow spheres for CO2 photocatalytic reduction. The findings suggest that such spinel-structured bimetallic oxides hierarchical hollow spheres, facilely synthesized via the proposed self-templated method, are efficient for photocatalytic CO2 reduction.

In situ construction of yolk-shell zinc ferrite with carbon and nitrogen co-doping for highly efficient solar light harvesting and improved catalytic performance.

In this work, carbon and nitrogen co-doped yolk-shell ZnFe2O4 nanostructures (CN-ZnFe2O4) were successfully synthesized through a facile self-templated method with in situ doping strategy. A series of characterizations were processed to present a comprehensive properties of the as-prepared photocatalyst samples. Doping amount could be moderated by the addition mass of dopamine, which was regarded as both the carbon and nitrogen source. And the void space between yolk and shell could be adjusted by heating rates in the calcination process of precursors. With an excellent separation efficiency of photogenerated electron-hole pairs and transfer efficiency of photogenerated electrons, the obtained CN-ZnFe2O4 sample exhibited an enhanced visible light response than ZnFe2O4. And their photocatalytic performances towards gaseous 1, 2-dichlorobenzene (o-DCB) was also systematically studied. The results demonstrated that the CN-ZnFe2O4 sample with 100 mg dopamine addition and 20 °C/min calcination heating rate exhibited the best o-DCB degradation efficiency. In situ Fourier Transform infrared (FTIR) spectroscopy was also recorded to give a detailed information of intermediate products and reveal the mechanism of photocatalytic degradation towards o-DCB. Particularly, density functional theory (DFT) calculation was used to further study the electronic structure of prepared samples to support the experimental results and especially explain the mechanism of enhanced photocatalytic activity through a proposed lattice junction. Additionally, electron paramagnetic resonance (EPR) technique was carried out to prove the reactive oxygen species involved in the photodegradation process. This work not only presents a promising strategy in photocatalyst fabrication but also provides a new sight of enhanced photocatalysis mechanism.

Oxygen Vacancy-rich Porous Co3O4 Nanosheets toward Boosted NO Reduction by CO and CO Oxidation: Insights into the Structure-Activity Relationship and Performance Enhancement Mechanism.

Oxygen vacancy-rich porous Co3O4 nanosheets (OV-Co3O4) with diverse surface oxygen vacancy contents were synthesized via facile surface reduction and applied to NO reduction by CO and CO oxidation. The structure-activity relationship between surface oxygen vacancies and catalytic performance was systematically investigated. By combining Raman, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and O2-temperature programmed desorption, it was found that the efficient surface reduction leads to the presence of more surface oxygen vacancies and thus distinctly enhance the surface oxygen amount and mobility of OV-Co3O4. The electron transfer towards Co sites was promoted by surface oxygen vacancies with higher content. Compared with the pristine porous Co3O4 nanosheets, the presence of more surface oxygen vacancies is beneficial for the catalytic performance enhancement for NO reduction by CO and CO oxidation. The OV-Co3O4 obtained in 0.05 mol L-1 NaBH4 solution (Co3O4-0.05) exhibited the best catalytic activity, achieving 100% NO conversion at 175 °C in NO reduction by CO and 100% CO conversion at 100 °C in CO oxidation, respectively. Co3O4-0.05 exhibited outstanding catalytic stability and resistance to high gas hour space velocity in both reactions. Combining in situ DRIFTS results, the enhanced performance of OV-Co3O4 for NO reduction by CO should be attributed to the promoted formation and transformation of dinitrosyl species and -NCO species at lower and higher temperatures. The enhanced performance of OV-Co3O4 for CO oxidation is due to the promotion of oxygen activation ability, surface oxygen mobility, as well as the enhanced CO2 desorption ability. The results indicate that the direct regulation of surface oxygen vacancies could be an efficient way to evidently enhance the catalytic performance for NO reduction by CO and CO oxidation.

Relationships Between Crystal, Internal Microstructures, and Physicochemical Properties of Copper-Zinc-Iron Multinary Spinel Hierarchical Nano-microspheres.

Rational design and fabrication of high quality complex multicomponent spinel ferrite with specific microstructures and solar light harvestings toward CO2 reduction and antibiotic degradation to future energetic and catalytic applications are highly desirable. In this study, novel copper-zinc-iron multinary spinel hierarchical nano-microspheres (MSHMs) with different internal structures (solid nano-microspheres, yolk-shell hollow nano-microspheres, and double-shelled hollow nano-microspheres) have been successfully developed by a facile self-templated solvothermal strategy. The morphology and structure, optical, as well as photoinduced redox reactions including interfacial charge carrier behaviors and the intrinsic relationship of structure-property between intrinsic nano-microstructures and physicochemical performance of copper-zinc-iron ferrite MSHMs composites were systematically investigated with the assistance of various on- and/or off- line physical-chemical means and deeply elucidated in terms of the research outcomes. It is demonstrated that the modification of the interior microstructures can be applied to tune the catalytic properties of multinary spinel by tailoring the temperature programming to fine control the two opposite forces of contraction (Fc) and adhesion (Fa). Among various internal microstructures, the obtained double-shelled copper-zinc-iron MSHMs exhibited the superior catalytic performance toward 8.8 and 38 µmol for H2 and CO productions as well as 80.4% removal of sulfamethoxazole antibiotics. As evidenced from primary characterizations, for example, combined steady-state PL, ns-TAS, and Mössbauer and sequential investigations, the remarkable improvements in the catalytic activity can be primarily attributed to several crucial factors, for example, the more effective e--h+ spatial separations and interfacial transfers, multiple internal light scattering, higher photonic energy harvesting and effective reactive oxygen species generation with long radical lifetimes. The current research provides new insights into the molecular design of novel copper-zinc-iron multinary spinels and the intrinsic relationship of structure-property between interior structures (e.g., different crystal texture, morphologies structures) and the physicochemical performance of the aforementioned multinary spinels.

Improvement of catalytic activity over Mn-modified CeZrOx catalysts for the selective catalytic reduction of NO with NH3.

A series of MnCeZrOx mixed oxide catalysts were facilely synthesized using the impregnation-NH3·H2O coprecipitation method and tested for selective catalytic reduction (SCR) of NO with NH3. Doping manganese significantly improved the catalytic activity and the best performing SCR catalyst, Mn0.25Ce0.5Zr0.25Ox, was shown to achieve NO conversion > 80% in the temperature range (60-350 °C), with the denitration effect up to 50% at room temperature (conditions: [NO] = [NH3] = 500 ppm, [O2] = 5 vol%, He as balance, flow rate  =  100 mL/min, GHSV  =  40, 000 h-1). Characterization of the catalyst using BET, XRD, XPS, H2-TPR, and in-situ FTIR proved that the improved SCR activity may be attributed to the large surface area, great reduction ability and increased amount of surface adsorbed oxygen afforded by the introduction of manganese. The SCR reaction mechanisms were also investigated by analyzing in-situ FTIR spectra and the SCR reaction pathway over the Mn0.25Ce0.5Zr0.25Ox catalyst was shown to mostly follow the E-R mechanism.

Rational design and synthesis of highly oriented copper-zinc ferrite QDs/titania NAE nano-heterojunction composites with novel photoelectrochemical and photoelectrocatalytic behaviors.

This work reported that novel highly oriented and vertically aligned stoichiometric copper- and zinc-based ferrites, i.e., Cu0.5Zn0.5Fe2O4 quantum dots (QDs) anchored with TiO2 nanotube array electrode (NAE) composites, with n-n nano-heterojunctions and highly effective simulated solar light harvesting could be successfully achieved via electrochemical anodization followed by a vacuum-assisted impregnation strategy. It has been observed that Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAE composites exhibit distinctly enhanced visible light photoelectrocatalytic (PEC) performance toward the degradation of typical pollutants including sulfamethoxazole (SMX) and methylene blue (MB) as compared to that of pristine TiO2 NAEs, which can be attributed to the synergistic effect of heterostructures with strong interfacial interaction and abundant 1D nanotube array structures to facilitate efficient spatial charge separation and interfacial transfers. The cocatalyst-anchoring of ternary oxides with derived spinel crystal structures onto nanotube arrays forming novel nanocomposites have obviously achieved remarkably enhanced photoelectrochemical (PE) conversion efficiencies, up to a dedicated value of 3.75%, under visible light irradiation as compared to that of 0.88% for aligned standalone TiO2 NAEs. Transient absorption spectroscopy quantitatively indicated long-lived photo-holes with lifetimes exceeding 72.23 µs generated among Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAE nanocomposites. Electron spinning resonance (ESR) demonstrated that more ˙O2- species derived from molecular uptake played the predominant role in the PEC oxidations of SMX and MB species. Moreover, the binding energy of the onset edge (Evf) and Fermi level (Ef) of Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAEs indicated that Cu0.5Zn0.5Fe2O4 QDs modification could considerably enhance the visible light harvesting and adsorption properties of TiO2 NTs. Furthermore, Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAEs achieved up to 50% PEC degradation efficiency and 52.4% COD removal with regard to practical textile wastewater when irradiated by simulated sunlight. This work has provided new insights into the molecular tailing and coupling of multiple spinels with TiO2 NTs possessing remarkable visible light harvesting and sensitization characteristics, which would offer a prospective strategy toward designing highly efficient and easily recyclable photocatalytic materials for environmental remediation and solar energy utilizations and conversions both simultaneously and standalone.

Rational design of cobalt and nitrogen co-doped carbon hollow frameworks for efficient photocatalytic degradation of gaseous toluene.

In this work, the hollow Co/N co-doped carbon frameworks (Co/N-C) were successfully constructed by in situ transformation of zeolitic imidazolate frameworks (ZIF-67) through polycondensation of dopamine. The hollow and porous structure of Co/N-C was demonstrated by transmission electron microscopy (TEM). The doping and Co-N-C active sites were verified by X-ray photoelectron spectroscopy (XPS). The UV-vis diffusion reflectance spectra (UV-vis DRS) of hollow Co/N-C nanoparticles reflected a significant enhancement of optical absorption in the range of 300-800 nm. With hollow porous structure, strong optical absorption and rich Co-N-C active sites, the Co/N-C exhibited a high photocatalytic performance by using gaseous toluene as a model pollutant, and the degradation efficiency of gaseous toluene was found to be around 78.2% under mild conditions (i.e., Temperature = 273 K, Pressure = 1 atom, λ ≥ 420 nm, t = 6 h). The photocatalytic degradation process and mechanism of toluene were further investigated by in situ Fourier transform infrared (FTIR) spectroscopy, which indicated that multiple hydroxylation and benzen ring opening are both involved in the catalytic elimination processes, and the initial intermediate species including benzaldehyde and benzoic acid were firstly derived from the hydroxylation due to the hydroxyl radical followed by further oxidation into carbon dioxide and water.