One-step synthesis of three-dimensional mesoporous Co_(3)O_(4)@Al_(2)O_(3)nanocomposites with deep eutectic solvent:An efficient and stable peroxymonosulfate activator for organic pollutant degradations

The effective,stable,and secure catalysts are essential for sulfate radical(SO_(4)·−)-based advanced oxidation processes(SR-AOPs)to the degradation of organic contaminants in water.Heterogeneous supported cobalt-based catalysts are commonly used to activate peroxymonosulfate(PMS)to achieve the degradation.In this work,we synthesized Co_(3)O_(4)@Al_(2)O_(3)three-dimensional(3D)mesoporous nanocomposite(denoted as Co_(3)O_(4)@Al_(2)O_(33)DPNC)in just one step by calcining cheap and green deep eutectic solvent(DES)solution containing Co salt.Co_(3)O_(4)@Al_(2)O_(33)DPNC with the high specific surface area(93.246 m^(2)/g),uniform pore distribution(3.829 nm)and rich porosity(0.255 cm^(3)/g)were attained in a beautiful hierarchical structure which exhibited the open 3D propeller-like microstructure,two-dimensional lamellar substructure with rich folds,as well as the decoration of highly dispersed Co_(3)O_(4)nanoparticles on mesoporous amorphous Al_(2)O_(3).The excellent chemical and thermal stability of Al_(2)O_(3)ensures the high stability of the catalyst,and the formation of the complex hierarchical structure makes the active Co_(3)O_(4)be homogenously dispersed for effective catalysis.The catalyst demonstrated outstanding performance for catalytic degradations of organic pollutants(acetaminophen,oxytetracycline,5-sulfosalicylic acid,orange G and Rhodamine B)by generated SO_(4)·−,·OH and^(1)O_(2).With a very low cobalt content(equal to 28.2 mg/L of Co),the catalyst exhibited very high stability and excellent reusability in the recycling usages,while the leaching of the cobalt element(<0.145 mg/L)was also at a low level.Our catalyst achieved effective degradations of acetaminophen in cycles without losing its stable hierarchical nanostructure.

BiVO_4 Photoanode with Exposed(040) Facets for Enhanced Photoelectrochemical Performance

A BiVO_4 photoanode with exposed(040) facets was prepared to enhance its photoelectrochemical performance.The exposure of the(040) crystal planes of the BiVO_4 film was induced by adding NaCl to the precursor solution. The asprepared BiVO_4 photoanode exhibits higher solar-light absorption and charge-separation efficiency compared to those of an anode prepared without adding Na Cl. To our knowledge,the photocurrent density(1.26 m A cm^(-2) at 1.23 V vs. RHE) of as-prepared BiVO_4 photoanode is the highest according to the reports for bare BiVO_4 films under simulated AM1.5 G solar light, and the incident photon-to-current conversion efficiency is above 35% at 400 nm. The photoelectrochemical(PEC)water-splitting performance was also dramatically improvedwith a hydrogen evolution rate of 9.11 lmol cm^(-2) h^(-1), which is five times compared with the BiVO_4 photoanode prepared without NaCl(1.82 lmol cm^(-2) h^(-1)). Intensity-modulated photocurrent spectroscopy and transient photocurrent measurements show a higher charge-carrier-transfer rate for this photoanode. These results demonstrate a promising approach for the development of high-performance BiVO_4 photoanodes which can be used for efficient PEC water splitting and degradation of organic pollutants.

Bandgap engineering of tetragonal phase CuFeS_(2)quantum dots via mixed-valence single-atomic Ag decoration for synergistic Cr(VI)reduction and RhB degradation

Bandgap engineering through single-atom site binding on semiconducting photocatalyst can boost the intrinsic activity,selectivity,carrier separation,and electron transport.Here,we report a mixed-valence Ag(0)and Ag(I)single atoms co-decorated semiconducting chalcopyrite quantum dots(Ag/CuFeS_(2)QDs)photocatalyst.It demonstrates efficient photocatalytic performances for specific organic dye(rhodamine B,denoted as RhB)as well as inorganic dye(Cr(VI))removal in water under natural sunlight irradiation.The RhB degradation and Cr(VI)removal efficiencies by Ag/CuFeS_(2)QDs were 3.55 and 6.75 times higher than those of the naked CuFeS_(2)QDs at their optimal pH conditions,respectively.Besides,in a mixture of RhB and Cr(VI)solution under neutral condition,the removal ratio has been elevated from 30.2%to 79.4%for Cr(VI),and from 95.2%to 97.3%for RhB degradation by using Ag/CuFeS_(2)QDs after 2 h sunlight illumination.The intrinsic mechanism for the photocatalytic performance improvement is attributed to the narrow bandgap of the single-atomic Ag(I)anchored CuFeS_(2)QDs,which engineers the electronic structure as well as expands the optical light response range.Significantly,the highly active Ag(0)/CuFeS_(2)and Ag(I)/CuFeS_(2)effectively improve the separation efficiency of the carriers,thus enhancing the photocatalytic performances.This work presents a highly efficient single atom/QDs photocatalyst,constructed through bandgap engineering via mixed-valence single noble metal atoms binding on semiconducting QDs.It paves the way for developing high-efficiency single-atom photocatalysts for complex pollutions removal in dyeing wastewater environment.

Recent Progress on Visible Light Responsive Heterojunctions for Photocatalytic Applications

Photocatalysis has attracted much attention in recent years due to its potential in solving energy and environmental issues. Even though numerous achievements have been made, the photocatalytic systems developed to date are still far from practical applications due to the low efficiency and poor durability. Efficient light absorption and charge separation are two of the key factors for the exploration of high performance photocatalytic systems, which is generally difficult to be obtained in a single photocata- lyst. The combination of various materials to form heterojunctions provides an effective way to better harvest solar energy and to facilitate charge separation and transfer, thus enhancing the photocatalytic activity and stability. This review concisely summarizes the recent development of visible light respon- sive heterojunctions, including the preparation and performances of semiconductor/semiconductor junctions, semiconductor/cocatalyst junctions, semiconductor/metal junctions, semiconductor/non- metal junctions, and surface heterojunctions, and their mechanism for enhanced light harvesting and charge separation/transfer.

Fluorinated inverse opal carbon nitride combined with vanadium pentoxide as a Z-scheme photocatalyst with enhanced photocatalytic activity

In this work,Z-scheme V_(2)O_(5) loaded fluorinated inverse opal carbon nitride(IO F-CN/V_(2)O_(5)) was synthesized as a product of ternary collaborative modification with heterostructure construction,element doping and inverse opal structure.The catalyst presented the highest photocatalytic activity and rate constant for degradation of typical organic pollutants Rhodamine B(RhB)and was also used for the efficient removal of antibiotics,represented by norfloxacin(NOR),sulfadiazine(SD)and levofloxacin(LVX).Characterizations confirmed its increased specific surface area,narrowed bandgap,and enhanced visible light utilization capacity.Further mechanism study including band structure study and electron paramagnetic resonance(EPR)proved the successful construction of Z-scheme heterojunction,which improved photogenerated charge carrier migration and provide sufficient free radicals for the degradation process.The combination of different modifications contributed to the synergetic improvement of removal efficiency towards different organic pollutants.

Large-sized nano-TiO2/SiO2 mesoporous nanofilm-constructed macroporous photocatalysts with excellent photocatalytic performance

Novel large-sized mesoporous nanofilm-constructed macroporous SiO2(LMNCMS)with two sets of well-defined 3D continuous pass-through macropores(pore size of 0.5-1.0 um,wall thickness of 40-50 nm)was prepared through a dual-templating approach,and used as an advanced support for TiO2 nanocrystalline photocatalyst.The structural and optical properties of the as-prepared materials were investigated by various characterization techniques in order to explore the connections between catalysts'features and catalytic performance.The photocatalytic activities were evaluated by degradations of methylene blue(MB)and phenol under the simulated sunlight irradiation.To gain insight into the impact of preparation and operation conditions on photocatalytic degradation processes,experiments were conducted at wide ranges of the TiO2 loading content,calcination temperature,solution pH,and photocatalyst dosage.Nano-TiO2/LMNCMS exhibited high photocatalytic activity and stability.Rapid matter transport,good access ibility of pollutants to TiO2 and high light harvesting could mainly account for the superior photocatalytic performance.The trapping experiments were performed to identify the main reactive species in the catalytic reactions.