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).     

Synthesis of S-rich flower-like Fe2O3-MoS2 for Cr(VI) removal

A novel Fe₂O₃-MoS₂ nanocomposite was synthesized directly via the solvothermal method. Scanning electron microscopy (SEM) results showed the as-prepared Fe₂O₃-MoS₂ had a uniform 3D blooming flower-like nanostructure with a MoS₂ substrate. The high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) confirmed the Fe₂O₃ nanostructures were well-dispersed on the surface of the layered MoS₂. The elemental mapping results revealed Fe, O, Mo and S elements coexisted in the Fe₂O₃-MoS₂ nanocomposite. X-ray photoelectron spectroscopy (XPS) results displayed an S-rich MoS₂ structure had been formed in the Fe₂O₃-MoS₂ nanocomposite. As expected, the S-rich Fe₂O₃-MoS₂ nanocomposite had better photocatalytic performance on Cr(VI) reduction than that of bare Fe₂O₃, MoS₂ and TiO₂ P25.     

Generation of hydrogen under visible light irradiation with enhanced photocatalytic activity of Bi2WO6/Cu1.8Se for organic pollutants under Vis‐NIR light reign

To make better use of solar light, a new Bi₂WO₆/Cu_1.8Se photocatalyst active to visible and near‐infrared light has been synthesized by a facile hydrothermal method. The composites were characterized by X‐ray diffractometry (XRD), scanning electron microscopy (SEM), UV‐vis diffuse reflectance spectroscopy (DRS), and photoluminescene (PL). The photocatalytic activities of Bi₂WO₆/Cu_1.8Se are evaluated by degrading Congo red solution and hydrogen generation from water. It was found that the molar percentage of Cu_1.8Se had great effects on the morphology and photocatalytic property of the Bi₂WO₆/Cu_1.8Se heterojunctions, and the composite with suitable molar amount of Cu_1.8Se exhibits much enhanced photocatalytic activity for Congo red degradation under visible and near‐infrared light irradiation and for hydrogen generation under visible light compared to Bi₂WO₆. The significant improvement photocatalytic activity of the composite could be attributed to its good light absorption, suitable band gap structure, and effective separation of photogenerated electron‐hole pairs of Bi₂WO₆/Cu_1.8Se heterojunction. This work presents an efficient multifunction photocatalyst owning the activity both for water splitting under visible light and for organic contaminants decomposition under visible‐near‐infrared light.     

微波辐射下Al_2(SO_4)_3·nH_2O催化合成α-萘乙酸甲酯

以固体A l2(SO4)3.nH2O为催化剂,在微波辐射下,以α-萘乙酸和甲醇为原料合成了α-萘乙酸甲酯。考察了催化剂的用量、微波功率、微波辐射时间、醇酸比对酯产率的影响。实验结果表明,最佳实验条件为:催化剂用量6%,微波功率600 W,微波辐射时间28 m in,醇酸摩尔比12∶1,酯产率72.45%。     

Bi2O2CO3/Fe3O4磁性复合物在环境污染治理领域中的应用

以Fe₃O₄纳米粒子和Bi₂O₂CO₃为原料,采用溶剂热法制备Bi₂O₂CO₃/Fe₃O₄磁性复合物,并通过对印染废水中染料的去除、剩余污泥厌氧消化过程中产甲烷潜力的影响两方面探讨其在环境污染治理中的应用。借助X射线衍射（XRD）、扫描电镜（SEM）、傅里叶红外光谱（FTIR）和比表面积及孔径分析对Bi₂O₂CO₃/Fe₃O₄复合物进行表征分析,SEM分析结果表明复合物表面较粗糙,BET结果显示复合物的比表面积为9.2294m²/g,Fe₃O₄的引入大幅度增加了Bi₂O₂CO₃的比表面积,使其具有明显的介孔结构。一方面,以甲基橙（MO）为目标污染物,研究了不同实验条件下该材料对染料的去除效果,结果表明,最大吸附量可达14.373mg/g,且该吸附反应过程符合拟二级动力学和Langmuir吸附等温模型,趋于单分子层吸附;另一方面,评估了复合物对污泥厌氧消化产甲烷潜力的影响,结果表明,复合物的引入对污泥厌氧消化产甲烷过程有一定的促进作用,累积产甲烷量相比于对照组提高了10%。分别用一级动力学模型和修正Gompertz模型模拟厌氧消化过程,模拟结果显示一级动力学模型可以更好地描述引入Bi₂O₂CO₃/Fe₃O₄磁性复合物的污泥厌氧消化过程。     

Graphene‐supported nickel ferrite: A magnetically separable photocatalyst with high activity under visible light

A straightforward strategy is designed for the fabrication of a magnetically separable NiFe₂O₄‐graphene photocatalyst with different graphene content. It is very interesting that the combination of NiFe₂O₄ nanoparticles with graphene sheets results in a dramatic conversion of the inert NiFe₂O₄ into a highly active catalyst for the degradation of methylene blue (MB) under visible light irradiation. The significant enhancement in photoactivity under visible light irradiation can be ascribed to the reduction of GO, because the photogenerated electrons of NiFe₂O₄ can transfer easily from the conduction band to the reduced GO, effectively preventing a direct recombination of electrons and holes. The results of the kinetic study indicated that the rate‐determining stage is the adsorption process of MB molecules. NiFe₂O₄ nanoparticles themselves have a strong magnetic property, which can be used for magnetic separation in a suspension system, and, therefore, the introduction of additional magnetic supports is no longer necessary. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Anthranilic acid assisted preparation of Fe3O4–poly(aniline‐co‐o‐anthranilic acid) nanoparticles

Magnetic Fe₃O₄–poly(aniline‐co‐o‐anthranilic acid) nanoparticles were prepared by a novel and simple method: anthranilic acid assisted polymerization. The synthetic strategy involved two steps. First, Fe₃O₄ nanoparticles capped by anthranilic acid were obtained by a chemical precipitation method, and then the aniline and oxidant were added to the modified Fe₃O₄ nanoparticles to prepare well‐dispersed Fe₃O₄–poly(aniline‐co‐o‐anthranilic acid) nanoparticles. Fe₃O₄–poly(aniline‐co‐o‐anthranilic acid) nanoparticles exhibited a superparamagnetic behavior (i.e., no hysteresis loop) and high‐saturated magnetization (M_s = 21.5 emu/g). The structure of the composite was characterized by Fourier‐transform infrared spectra, X‐ray powder diffraction patterns, and transmission electron microscopy, which proved that the Fe₃O₄–poly(aniline‐co‐o‐anthranilic acid) nanoparticles were about 20 nm. Moreover, the thermal properties of the composite were evaluated by thermogravimetric analysis, and it showed excellent thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1666–1671, 2006     

Simultaneous degradation of RhB and reduction of Cr(VI) by MIL-53(Fe)/Polyaniline (PANI) with the mediation of organic acid

MIL-53(Fe)/polyaniline (PANI) composite was prepared by in situ depositing PANI on the surface of MIL-53(Fe) and their catalytic performances on the simultaneous removal of RhB and Cr(VI) were investigated. The elimination efficiency of both RhB and Cr(VI) reached more than 98% under pH=2 where hydrochloric acid and citric acid were used to adjust the pH. The results indicated that MIL-53(Fe)/PANI revealed an obvious pH response to the degradation of RhB, while citric acid promoted the Cr(VI) photoreduction. UV-Vis spectra, EIS, and photocurrent response experiments showed that MIL-53(Fe)/PANI had a better light response and carrier migration ability than MIL-53(Fe). The transient absorption spectra also exhibited that the lifetimes of photo-generated carriers were prolonged after the conductive polymer deposition on the MIL-53(Fe) surface. Scavenger experiments demonstrated that the main active species were ·O₂^- and OH. Combined with activity evaluation results, and the possible photocatalytic mechanism of MIL-53(Fe)/PANI on RhB oxidation and Cr(VI) reduction was proposed. The addition of conductive polymer can effectively improve the light response of the catalyst under acidic conditions, and meanwhile citric acid also provided a new mediation for the synergistic degradation of multiple pollutants. Good activity and stability of the catalysts made the scale-up purification of acid water feasible under UV-Vis light.     

A vibrational study of phase transitions in Fe2P2O7 and Cr2P2O7 under high‐pressures

The vibrational properties of synthetic iron diphosphate (Fe₂P₂O₇) and chromium diphosphate (Cr₂P₂O₇) are studied under high‐pressure conditions between ~22 and ~30 GPa, respectively. Each compound's structural response to pressure and pressure‐induced phase transitions are characterized. The chromium‐bearing sample shows coalescence of infrared bands occurring near 6 and 17 GPa: these may be associated with increases in the local symmetry of the P₂O₇ group. The iron sample undergoes a first‐order phase transition near ~9 GPa, and a possible phase transition near 5.5 GPa. At 9 GPa, the initially single, strong symmetric PO₄ stretching mode splits into four modes, and the sole asymmetric PO₄ stretching mode splits into two bands. These changes indicate the presence of multiple tetrahedral environments within a larger volume unit cell, and the relative frequencies of the split vibrations indicate a P₂O₇ environment with a markedly narrowed P–O–P angle. The difference between the behavior of the iron and chromium compounds is probably generated by the smaller iron ion producing a discontinuous decrease in the P–O–P angle at lower pressures than in the analogous chromium compound. Our results demonstrate that the dimerized P₂O₇ group remains stable under compression to over 20‐30 GPa at 300 K.     

Magnetite (Fe3O4) Nanoparticles‐Catalyzed Sonogashira– Hagihara Reactions in Ethylene Glycol under Ligand‐Free Conditions

A novel application of nanoparticles of paramagnetic magnetite (Fe₃O₄) as an efficient catalyst for carbon‐carbon bond formation via the Sonogashira–Hagihara reaction under heterogeneous ligand‐free conditions in ethylene glycol (EG) is described. By using this catalyst, arylalkynes are produced from the reaction of aryl iodides and activated heteroaryl bromides with alkynes. The results are reproducible using the catalyst, which was prepared from different sources. The catalyst is easily separated by an external magnetic field from the reaction mixture. The separated catalyst can be recycled for several consecutive runs without appreciable loss of its catalytic activity.     

Synthesis and swelling characteristics of poly(4‐vinylpyridine) gels crosslinked by irradiation

The effect of irradiation under vacuum on thermal properties and swelling behavior on poly(4‐vinylpyridine) (P4VP) was investigated. The gel percentage in the irradiated P4VP films was determined by Soxhlet extraction. UV spectroscopy was also used to determine sol percentage, which decreased as the radiation dose increased. The changes in thermal properties, such as glass‐transition temperature (T_g), were followed by differential scanning calorimetry before and after Soxhlet extraction. The gels prepared after irradiation were characterized with respect to their swelling properties and network structures. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2609–2614, 2001     

Effect of pre‐treatments on the biosorption of Chromium (VI) ions by the dead biomass of Rhizopus arrhizus

BACKGROUND: This work fulfils the need to develop an eco‐friendly biosorbent, elucidating the mechanism of biosorption. Removal of Cr(VI) by Rhizopus arrhizus was investigated in batch mode. Enhancement in the performance of the biosorbent was attempted by pre‐treating the biomass with inorganic and organic acids, chelating agent, cross‐linker and an organic solvent followed by autoclaving. The surface characterization of the biomass was carried out by potentiometric titration, surface area analysis, infrared spectroscopy, chemical modification of the biomass and scanning electron microscopy. RESULTS: All the physico‐chemical treatments of the biosorbent improved Cr(VI) uptake compared with the native biomass (21.72 mg g^?1). The highest biosorption capacity (31.52 mg g^?1) was achieved after pre‐treating the biomass with 0.5 mol L^?1 HNO₃ followed by autoclaving. Surface characterization of the biomass using pH_zpc, potentiometry and Fourier transform infrared (FTIR) analysis revealed the role of amino and carboxyl groups in Cr(VI) removal by electrostatic attraction. Chemical modification of amino and carboxyl groups significantly decreased Cr(VI) uptake capacity confirming their role in biosorption. SEM analysis showed adsorption of Cr(VI) on the biosorbent surface. CONCLUSION: Rhizopus arrhizus biomass proved to be an effective and low cost alternative biosorbent for removal of Cr(VI) from aqueous solutions. Copyright © 2011 Society of Chemical Industry     

Structural elucidation and iron oxidation states in situ formed β‐Ca3(PO4)2/α‐Fe2O3 composites

A detailed structural analysis on the in situ synthesized β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites is demonstrated. Compositional ratios, the influence and occupancy of iron at the β‐Ca₃(PO₄)₂ lattice, oxidation state of iron in the composites are derived from analytical techniques involving XRD, FT‐IR, Raman, refinement of the powder X‐ray diffraction and X‐ray photoelectron spectroscopy. Iron exists in the Fe³⁺ state throughout the investigated systems and favors its occupancy at the Ca²⁺(5) site of β‐Ca₃(PO₄)₂ until critical limit, and thereafter crystallizes as α‐Fe₂O₃ at ambient conditions. Fe³⁺ occupancy at the β‐Ca₃(PO₄)₂ lattice yields a Ca₉Fe(PO₄)₇ structure that is isostructural with its counterpart. A strong rise in the soft ferromagnetic behavior of β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites is obvious that depends on the content of α‐Fe₂O₃ in the composites. Overall, the diverse level of iron inclusions at the calcium phosphate system with a Ca/P ratio of 1.5 yields a structurally stable β‐Ca₃(PO₄)₂/α‐Fe₂O₃ composites with assorted compositional ratios.     

MnO2/NH4NaY 催化剂上的NO低温选择性催化还原（SCR）

研究了NO在新型MnO₂/NH₄NaY催化剂上的低温转化行为，并对MnO₂/NH₄NaY的再生及稳态操作进行了考察。结果表明，以MnO₂/NaY为母体，用硫酸铵溶液离子交换制备的新型MnO₂/NH₄⁺NaY分子筛催化剂具有良好的低温活性，120 ℃时，NO转化率近100％。但催化剂不能在高于150 ℃的反应温度下操作，防止NH₄⁺挥发解吸。离子交换过程中，NH₄⁺的交换度可达40%，在120 ℃、氧体积分数6%、空速3 000h^-1和水体积分数7%和无外加还原剂条件下，MnO₂/NH₄NaY可保证入口浓度为1 000×10^-6的NOx在连续7 h内达到完全转化。在高空速（12 000 h^-1）有稳定氨源下，于MnO₂/NH₄NaY上进行的SCR稳态实验充分证明，存在于MnO₂/NH₄NaY的NH₄⁺对催化反应明显有利。 它可使NH₃与NOx物质的量比从以往的1.2降至1，大大减少由于NH₃泄露而造成的二次污染。     

Graft copolymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto carboxymethylcellulose (sodium salt) by H2O2/Fe+2 redox pair

The effect of the reaction conditions on the grafting parameters during grafting of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto sodium carboxymethylcellulose using H₂O₂/Fe⁺² redox pair are studied at 30°C. The grafting ratio, add on, and conversion initially increase with the H₂O₂ concentration in the range of (10.0–15.0) × 10^?2 mol dm^?3. Thereafter, these parameters decrease with the H₂O₂ concentration. The grafting ratio, add on, and conversion increase when increasing the ferrous ion concentration from (0.5 to 4.0) × 10^?2 mol dm^?3 and decrease with a further increase in the concentration. It is observed that the grafting ratio and add on increase with the monomer concentration, whereas the conversion decrease. The hydrogen ions seem to be facilitating the grafting reaction up to a certain concentration and after this concentration seem to be retarding the process. The grafting ratio, add on, and conversion decrease with the sodium carboxymethylcellulose concentration. When increasing the time period from 60 to 90 min, the grafting parameters increase but decrease thereafter. Similarly, when increasing the temperature from 25 to 30°C, the grafting parameters increase and decrease thereafter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4819–4825, 2006