Well-designed ZnIn2S4/TiO2 Z-type heterojunction for efficient photocatalytic reduction of Cr(VI)

ZnIn₂S₄/TiO₂ photocatalyst was obtained by a facile hydrothermal method. Various techniques were used to characterize the ZnIn₂S₄/TiO₂, crystal structure and optical properties of ZnIn₂S₄/TiO₂. Cr (Ⅵ) as highly-toxic pollutant was used as the target reduction product to evaluate the catalytic performance of ZnIn₂S₄/TiO₂ under visible light irradiation. According to the experiment results, the reduction rate of Cr(VI) in the presence of ZnIn₂S₄/TiO₂ reaches 99% within 60 min, which is much better than ZnIn₂S₄ and TiO₂, respectively. At the same time, ZnIn₂S₄/TiO₂ also performs good stability for reduction rate hardly changes after 5 recycling experiments.     

Alkali-free synthesis of a novel heterostructured CeO2-TiO2 nanocomposite with high performance to reduce Cr(VI) under visible light

In this study, a novel CeO₂-TiO₂ nanocomposite denoted as CeO₂-3TiO₂ was successfully synthesized via a facile one pot hydro-thermal method without alkali. It exhibits high photocatalytic reduction reactivity toward Cr(VI) under visible light. The photocatalytic reactivity of CeO₂-3TiO₂ is 18 times higher than that of pure CeO₂, 28 times higher than pure TiO₂, 15 times higher than the sample of simply mixed CeO₂ and TiO₂. The solution with Cr(VI) initial concentration of 2780 ppb can be fast photoreduced by CeO₂-3TiO₂ in 60 min under visible light to meet the criterion of U.S. Environmental protection Agency. Characterization results indicate CeO₂-3TiO₂ has the good crystal form of heterojunction structure, narrow pore size distribution, narrow energy gap and high photogenerated electron-hole separation efficiency. Based on the experimental results, a speculated photocatalytic mechanism was proposed.     

The enhanced performance of Cr(VI) photoreduction and antibiotic removal on 2D/3D TiO2/ZnIn2S4 nanostructures

In this study, 2D/3D TiO₂/ZnIn₂S₄ nanostructures with TiO₂ sheet cluster embedded into ZnIn₂S₄ micro flowers were fabricated via hydrothermal method. The matched band structure, the enlarged surface area and the efficient photo-induced charge transfer offered by effective heterostructures formed between the two components endowed the TiO₂/ZnIn₂S₄ nanoarchitecture with excellent photocatalytic Cr(VI) reduction and tetracycline hydrochloride (TC) degradation performance. Especially, the Cr(VI) photoreduction efficiency of 50% TiO₂/ZnIn₂S₄ was 8.8 times higher compared to pure ZnIn₂S₄. The enhanced separation efficiency of photo-excited charge carriers was induced by the matched band structure, the enlarged surface area and the strong interaction between TiO₂ and ZnIn₂S₄. The key roles of ·O₂^? was confirmed via trapping experiments. Otherwise, the pathway of TC degradation was investigated. The proposed mechanism during photocatalysis process was also discussed according to the photocatalytic and characterization results.     

Nanorod-pillared mesoporous rGO/ZnO/Au hybrids for photocatalytic Cr (VI) reduction: Enhanced Cr(VI) adsorption and solar energy harvest

Herein, we fabricated mesoporous ternary hybrids composed of Au-functionalized ZnO nanorods grown on rGO nanosheets. The ZnO nanorods distributed on the rGO nanosheets can act as a pillaring layer to avoid the agglomeration of rGO, leading to the formation of abundant mesopores within the hybrids. The high-surface-area, mesoporous hybrids can offer sufficient active sites and transport channels for efficient adsorption and diffusion of Cr(VI), which was favorable for its photocatalytic reduction due to the adsorption enrichment effects. Moreover, the plasmonic-induced visible-light absorption of Au nanoparticles and efficient charge separation by rGO synergistically contributed to the significantly improved solar-light-driven photocatalytic Cr(VI) reduction properties of the ternary hybrids.     

NiO_x修饰TiO_2纳米管光催化还原Cr(Ⅵ)离子研究

以TiO2纳米粒子(Degussa P25)为原料,经水热处理制得钛酸盐纳米管,通过离子交换将Ni2+插入钛酸盐纳米管,然后通过焙烧及氢气还原处理得到NiOx修饰TiO2纳米管,并考察了该纳米管在紫外光下还原Cr(Ⅵ)的性能。结果表明:经氢气还原处理后,NiOx的修饰能够显著提高TiO2纳米管的光催化还原Cr(Ⅵ)的活性,而未经还原处理的NiO对电子的转移起到了抑制作用。     

nZVI/PANI/ATP纳米纤维复合材料制备及对Cr(VI)的去除性能

采用原位聚合法合成了硝酸掺杂的纳米零价铁/聚苯胺/凹凸棒黏土(nZVI/PANI/ATP)纳米纤维复合材料,用于去除废水中的Cr(VI)。考察了投料质量、吸附时间和p H值对其吸附性能的影响,对吸附过程进行了动力学和热力学分析。结果表明,PANI/ATP表面负载纳米零价铁(nZVI),解决了nZVI颗粒的团聚及在处理Cr(Ⅵ)时容易被腐蚀和钝化的问题。复合材料制备过程中Fe、An和ATP的质量比为0.74∶1∶4时,所制备的材料吸附容量达到87.95 mg/g,nZVI/PANI/ATP复合材料对Cr(Ⅵ)的吸附符合准二级动力学模型,吸附为化学吸附。     

Adsorption performance and physicochemical mechanism of MnO2-polyethylenimine-tannic acid composites for the removal of Cu(II) and Cr(VI) from aqueous solution

In this work, an adsorbent, which we call MnPT, was prepared by combining MnO₂, polyethylenimine and tannic acid, and exhibited efficient performance for Cu(II) and Cr(VI) removal from aqueous solution. The oxygen/nitrogen-containing functional groups on the surface of MnPT might increase the enrichment of metal ions by complexation. The maximum adsorption capacities of MnPT for Cu(II) and Cr(VI) were 121.5 and 790.2 mg·g⁻¹, respectively. The surface complexation formation model was used to elucidate the physicochemical interplay in the process of Cu(II) and Cr(VI) co-adsorption on MnPT. Electrostatic force, solvation action, adsorbate–adsorbate lateral interaction, and complexation were involved in the spontaneous adsorption process. Physical electrostatic action was dominant in the initial stage, whereas chemical action was the driving force leading to adsorption equilibrium. It should be noted that after adsorption on the surface of MnPT, Cr(VI) reacted with some reducing functional groups (hydroxylamine-NH₂) and was converted into Cr(III). The adsorption capacity declined by 12% after recycling five times. Understanding the adsorption mechanism might provide a technical basis for the procedural design of heavy metal adsorbents. This MnPT nanocomposite has been proven to be a low-cost, efficient, and promising adsorbent for removing heavy metal ions from wastewater.     

Removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound

ABSTRACT

Cu(II) is an important and typical heavy metal ion in the wastewater containing Cr(VI), and its removal during Cr(VI) reduction by zero valent iron (ZVI) may make it separately be recovered as a kind of copper resource. In this study, the removal behavior of Cu(II) during Cr(VI) reduction by cast iron powder in absence and presence of ultrasound was investigated by atomic absorption spectrometry (AAS), X-ray powder diffractometer (XRD), scanning electron microscope-energy dispersion spectrum (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The AAS tests indicated that the ultrasound could not only obviously enhance the removal of Cu(II) but also improve the reduction rate of Cr(VI). The XRD and SEM-EDS analyses showed that Cu(II) in the solution was reduced to metallic copper and then was deposited at the surface of ZVI. The ultrasound could remove the Fe-Cr oxides and hydroxides at the ZVI surfaces, resulting in the active surfaces of iron increased. The XPS analyses demonstrated that the surface of metallic copper would be transformed into the film of copper oxide (CuO) in the ultrasound system. The obtained metallic copper and copper oxide could be recovered alone by traditional method of the acid pickling.     

Selective removal of Cr (VI) from hydrometallurgical effluent using modified cellulose nanocrystals (CNCs) with succinic anhydride and ethylenediaminetetraacetic acid: Isotherm,kinetics, and thermodynamic studies

Biological sources are renewable basic resources that may be used for several purposes, including the development of green materials for the removal of heavy metal ions. Cellulose nanocrystals (CNCs) extracted from waste papers via acid hydrolysis were modified and utilized as adsorbents to remove Cr (VI) ions from metallurgical effluent in this work. X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis, and zeta potentiometer were used to characterize the CNCs. The CNCs treated with succinic anhydride and ethylenediaminetetraacetic acid tetrasodium salt have thin particle sizes and are porous. The carboxylate functional group is primarily engaged in the coordination and selective removal of metal ions (–COO²⁻) and thermal degradation of 85%, observed at temperatures between 250–380°C. On the surface of the modified CNCs, the zeta potential data showed a decrease in negative value. The results revealed that the modified CNCs had a maximum adsorption capacity of 387.25 ± 0.88 mg L⁻¹ at pH 5, at CNCs doses of 25 and 400 mg L⁻¹ as starting concentrations. The adsorption equilibrium period was 300 min and the temperature was 313 K. The equilibrium results fit the Langmuir isotherm model with an R² of 0.993 and a qmax of 340 ± 0.97. The Chi-square (X²) and Marquardt's percent standard deviation tests confirmed that the adsorption process was pseudo-second-order with an R² of 0.998, and the Elovich model revealed that Cr (VI) complexed with the adsorbent's functional groups. The reaction was endothermic due to positive ΔH and spontaneous due to negative ΔG. The positive ΔS indicates that the adsorption process enhances the unpredictability of the solid/liquid interface, according to thermodynamic analysis. After acid treatment, the CNCs may be effectively reused for six cycles with an adsorption capacity of 220 ± 0.78 mg g⁻¹.     

Optimizing the structural and photocatalytic performance of Ag-decorated ZnO/Zn(OH)2 nanoparticles for RhB degradation

In this study, as-prepared and Ag-decorated ZnO/Zn(OH)₂ composite nanoparticles (NPs) were obtained using the sol–gel technique. First, the effect of aging on the structural, optical, and morphological features was examined. Ag NPs can interact with the electronic structure of ZnO/Zn(OH)₂ NPs, resulting in changes in their energy levels. It was found that the composite NPs obtained after 6 h solution aging increased in full width at half maximum and good crystallinity of the structures from the X-ray diffraction (XRD) measurements. The Raman spectrum supports the experimental data obtained from XRD and Fourier transform infrared, a material containing a mixture of ZnO and Zn(OH)₂. From the morphological study, Ag NPs were successfully decorated on the ZnO/Zn(OH)₂ surface, and composite NPs did not change the morphological appearance of the structure. Second, the photocatalytic performance of the samples was investigated. In the experimental setting, ultra-violet A light was employed as the irradiation source, whereas rhodamine B (RhB) was used as the dyestuff. The photo-degradation of the RhB dyestuff on composite NPs was observed to be 98.5% and 92.5% for 6 and 2 h aged samples, respectively. On Ag NPs, the catalytic performance of the sample was increased up to 95% after 180 min.     

Synthesis, structure and photocatalytic properties of Fe(III)-doped TiO2 prepared from TiCl3

Iron(III)-doped titanium dioxide photocatalysts were prepared from aqueous titanium(III) chloride solution in the presence of dissolved FeCl₃ (0–10.0 at.% relative to TiCl₃) by co-precipitation method. The precipitate was completely oxidized in the aerated suspension, hydrothermally treated, washed and calcinated. The structure of the powders was characterized by thermoanalysis (TG-DTA), diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), nitrogen adsorption and transmission electron microscopy (TEM). The light absorption of the iron-containing powders is red shifted relative to the bare sample. The particle size and anatase content were found to significantly decrease at iron contents ≥6.0 at.% which is accompanied with the increase of their specific surface area. XANES measurements showed that the local structure of iron systematically changes with the variation of the dopant concentrations: at higher Fe-contents, hematite- or goethite-like environments were observed, consistent with the formation of separate X-ray amorphous Fe(III)-containing phases. The local structure of iron gradually transformed with decreasing dopant concentrations, possibly due to substitution of Fe(III) in the titania (TiO₂) crystal lattice. Energy dispersive X-ray analysis (EDX) and chemical analysis was used to characterize the iron content of the samples in the bulk and X-ray photoelectron spectroscopy (XPS) in the surface layer of the particles. The photocatalytic performance of the prepared photocatalysts was compared with the activity of Aldrich anatase under UV–vis and VIS irradiation in two different photoreactors. Maximum photocatalytic performance was found at 3.0 at.% iron concentration for UV–vis and at 1.2 at.% for VIS irradiation. Doping with iron(III) ions increased the photodegradation rate of phenol by a factor of three for UV–vis irradiation and by a factor of two for VIS irradiation, relative to the bare photocatalyst.     

Potassium ferrate(VI) and decomposed K2FeO4 assisted methanol electro-oxidation in alkaline media

The cyclic voltammograms (CVs) and current-time curves of methanol electro-oxidation, assisted by K₂FeO₄, decomposed K₂FeO₄ and Fe(NO₃)₃ added in strong alkaline solution, were investigated on a Pt electrode. The results show that Fe(NO₃)₃ and K₂FeO₄, especially decomposed K₂FeO₄, can promote the activity and poisoning tolerance of a Pt electrocatalyst for methanol oxidation in alkaline solution. We propose that iron(III)-containing compounds such as Fe(OH)₃ and FeOOH in a strong alkaline solution tend to encourage the formation of OH adsorption (OH_ads) species, which are necessary for the promotion of the CO-like intermediates of oxidation on the Pt electrode.     

Evaluation of humic acid, chromium (VI) and TiO2 ternary system in relation to adsorptive interactions

Batch adsorption studies were carried out for the assessment of the adsorptive interactions of the system composed of humic acid, Cr(VI) and TiO₂. These were preceded by a thorough investigation of the effect of the chromium ion concentration on the adsorption of humic acid onto TiO₂. The adsorption equilibrium of total chromium, humic acid, and titanium dioxide in water were examined separately and in all combinations in order to distinguish the effects based on the interaction of the components. The adsorption data for the binary system as well as the ternary system were modeled with a simple Freundlich model and the model parameters were compared in terms of Cr(VI) and humic acid as expressed by Color₄₃₆ (color forming moieties) and UV₂₅₄ (UV absorbing centers) parameters.

In binary systems composed of Cr(VI) and TiO₂ no direct relationship could be assessed between adsorption capacity values (K_F) and changes in chromium ion concentration. Chromium ion and humic acid interactions were followed by UV-Vis spectra. A minor change irrespective of added chromium ion concentration was observed for Color₄₃₆ and UV₂₅₄ parameters of humic acid (<5%). However, a significant alteration was observed at 365 nm wavelength indicating the formation of chromate esters. In ternary systems comprising humic acid, Cr(VI) and TiO₂, increasing Cr(VI) concentration five-fold did not cause drastic changes in the adsorption capacity values in terms of Cr(VI) concentration. On the other hand, the adsorption capacity values for color forming moieties as well as for UV absorbing centers of humic acid exhibited a decreasing trend with respect to increasing chromium ion concentration.     

Construction of defect-containing UiO-66/MoSe2 heterojunctions with superior photocatalytic performance for wastewater treatment and mechanism insight

Metal–organic frameworks are recognized as promising multifunctional materials, especially metal–organic framework-based photocatalysts, which are considered to be ideal photocatalytic materials. Herein, a new type of UiO-66/MoSe₂ composite was prepared using the solvothermal method. The optimum composite was selected by adjusting the mass ratio of UiO-66 and MoSe₂. X-ray diffraction analysis showed that the mass ratio influenced the crystal plane exposure rate of the composite, which may have affected its photocatalytic performance. The composite is composed of ultra-thin flower-like MoSe₂ that wrapped around cubic UiO-66, a structure that increases the abundance of active sites for reactions and is more conducive to the separation of carriers. The photocatalytic properties of the composite were evaluated by measuring the degradation rate of Rhodamine B and the catalyst’s ability to reduce Cr(VI)-containing wastewater under visible light irradiation. Rhodamine B was decolorized completely in 120 min, and most of the Cr(VI) was reduced within 150 min. The photochemical mechanism of the complex was studied in detail. The existence of Mo⁶⁺ and oxygen vacancies, in addition to the Z-type heterojunction promote the separation of electrons and holes, which enhances the photocatalytic effect.     

Construction of Bi2Fe4O9/red phosphorus heterojunction for rapid and efficient photo-reduction of Cr(VI)

Construction of heterojunctions with matching energy band structures between two semiconductors displays great potential in promoting the separation and transfer of photogenerated charge carriers and is one of the effective strategies for obtaining high active photocatalysts. In this study, a type-II heterojunction photocatalyst was designed and prepared using Bi₂Fe₄O₉ (BFO) nanoparticles and hydrothermal-treated red phosphorus (HRP). The photocatalytic performance test exhibited that the 3%BFO/HRP composite photocatalyst with 3% mass fraction of BFO rapidly and efficiently photoreduced Cr(VI), and the reduction was completed within 25 min, with a rate constant of 0.15 min⁻¹, which was 15 times higher than that of pure HRP. Further mechanistic investigation revealed that the photocatalytic activity was enhanced due to the tight heterojunction between BFO and HRP, thereby effectively promoting carrier transfer, destroying the carrier recombination, and reducing the charge-transfer resistance of composite catalyst. Mott–Schottky diagrams and UV-vis diffuse reflectance spectroscopy data indicated the theoretical feasibility of establishing a close contact between BFO and HRP. X-ray photoelectron spectroscopy provided evidence for the way in which interfacial charges were transferred. This work provides a new possibility to construct heterojunction photocatalysts for the rapid and efficient reduction of Cr(VI).     

The influence of Fe(III) speciation on supported TiO2 efficiency: example of monuron photocatalytic degradation

The degradation of herbicide monuron (initial concentration 5×10⁻⁵ M) in plate photoreactor with laminar flow of the solution using heterogeneous (TiO₂) and/or homogeneous photocatalyst (Fe(ClO₄)₃) was investigated. For the rate of photoinduced degradation with Fe(III) aquacomplexes, the initial concentration of monomer Fe(OH)²⁺, which is the most photocatalytically active form of Fe(III), is crucial. The degradation rate for combination of both photocatalysts is higher than the sum of the rates for separately taken single catalysts. This is caused not only by the addition of the two effects but also by the fact that Fe(III) acts as scavanger of electrons photogenerated in TiO₂ particles thus let down hole–electron recombination. Fe(OH)²⁺ appears to be the most photoactive trap for electrons.     

胺功能化MIL-101(Cr)@SiO_2@Fe_3O_4催化剂及其Knoevenagel反应性能

采用溶剂热法在纳米SiO_2@Fe_3O_4磁性颗粒表面原位合成MIL-101(Cr),制备磁性MIL-101(Cr)@SiO_2@Fe_3O_4催化剂。采用甲胺、乙二胺和丁二胺对制备的磁性催化剂进行功能化,得到胺功能化NH2-MIL-101(Cr)@SiO_2@Fe_3O_4催化剂。利用XRD、FT-IR、BET、SEM、TEM和VSM等对催化剂结构进行表征,评价胺功能化NH2-MIL-101(Cr)@SiO_2@Fe_3O_4催化剂对糠醛和氰乙酸乙酯Knoevenagel缩合反应性能和重复使用性能,考察反应条件与催化性能的关系。结果表明,制备的新型胺功能化NH2-MIL-101(Cr)@SiO_2@Fe_3O_4催化剂具有MIL-101(Cr)的结构特征和良好的超顺磁性能,对糠醛和氰乙酸乙酯Knoevenagel缩合反应表现出很好的催化性能,其中,乙二胺功能化30%MIL-101(Cr)@SiO_2@Fe_3O_4催化剂对Knoevenagel缩合反应的性能最佳,在反应温度40℃和反应时间1 h条件下,氰乙酸乙酯转化率为97. 0%,产物选择性接近100%。反应后磁性催化剂可以通过外磁场容易进行分离,重复使用5次,氰乙酸乙酯转化率仍大于93%。     

Electrocatalytic reduction of chromium by poly(aniline-co-o-aminophenol): An efficient and recyclable way to remove Cr(VI) in wastewater

Poly(aniline-co-o-aminophenol) (PANOA)-modified glassy carbon electrode (GCE) was first used to investigate the electrocatalytic reduction of dichromate in a NaCl solution of pH 5.0. The results of cyclic voltammograms and UV–vis spectra demonstrated that the reduction of Cr(VI) occurred at PANOA-modified GCE. The FT-IR, ESR and XPS results showed that the Cr(VI) can be doped in the PANOA films and can convert to less-toxic Cr(III). The doping level Cr/N was 78.2% and trace amount of Cl (0.42%) was detected in the doped PANOA, which indicated that the doping process is effective and PANOA had rather good ion selectivity in the 0.10 M NaCl supporting electrolyte. The factors influenced the reduction were also considered. Various initial concentrations of Cr(VI) had different removal rates. The maximum removal rate of Cr(VI) at 20 mg L⁻¹ (32.3%) was better than that of at 5 mg L⁻¹ (22.9%). The solution pH had little effect on Cr(VI) reduction and doping process of the PANOA because PANOA had good electrochemical activity and stability in a wide range of pHs (from pH 4 to pH 8).