Molybdenum imidazole citrate and bipyridine homocitrate in different oxidation states – balance between coordinated α-hydroxy and α-alkoxy groups

Oxo and thiomolybdenum(iv/vi) imidazole hydrocitrates K₂{Mo^IV₃O₄(im)₃[Mo^VIO₃(Hcit)]₂}·3im·4H₂O (1), (Him)₂{Mo^IV₃SO₃(im)₃[Mo^VIO₃(Hcit)]₂}·im·6H₂O (2), molybdenum(v) bipyridine homocitrate trans-[(Mo^VO)₂O(H₂homocit)₂(bpy)₂]·4H₂O (3) and molybdenum(vi) citrate (Et₄N)[Mo^VIO₂Cl(H₂cit)]·H₂O (4) (H₄cit = citric acid, H₄homocit = homocitric acid, im = imidazole and bpy = 2,2′-bipyridine) with different oxidation states were prepared. 1 and 2 are the coupling products of [Mo^VIO₃(Hcit)]³⁻ anions and incomplete cubane units [Mo^IV₃O₄]⁴⁺ ([Mo^IV₃SO₃]⁴⁺) with monodentate imidazoles, respectively, where tridentate citrates coordinate with α-hydroxy, α-carboxy and β-carboxy groups, forming pentanuclear skeleton structures. The molybdenum atoms in 1 and 2 show unusual +4 and +6 valences based on charge balances, theoretical bond valence calculations and Mo XPS spectrum. The coordinated citrates in 1 and 2 are protonated with α-hydroxy groups, while 3 and 4 with higher oxidation states of +5 and +6 are deprotonated with α-alkoxy group even under strong acidic condition, respectively. This shows the relationship between the oxidation state and protonation of the α-alkoxy group in citrate or homocitrate, which is related to the protonation state of homocitrate in FeMo-cofactor of nitrogenase. The homocitrate in 3 chelates to molybdenum(v) with bidentate α-alkoxy and monodentate α-carboxy groups. Molybdenum(vi) citrate 4 is only protonated with coordinated and uncoordinated β-carboxy groups. The solution behaviours of 1 and 2 are discussed based on ¹H and ¹³C NMR spectroscopies and cyclic voltammograms, showing no decomposition of the species.

Oxo and thiomolybdenum(iv/vi) citrates, molybdenum(v) homocitrate and molybdenum(vi) citrate were obtained, showing the influence of coordinated α-hydroxy and α-alkoxy groups with different oxidation states.     

NH2-MIL-88B (FeαIn1−α) mixed-MOFs designed for enhancing photocatalytic Cr(vi) reduction and tetracycline elimination

Aiming at solving the issue of wastewater purification, this work synthesized NH₂-MIL-88B (Fe_αIn_1−α) photocatalysts by a simple one-pot method, which was employed for photocatalytic reduction of Cr(vi) and oxidation of TC-HCl. Compared with traditional NH₂-MIL-88B (Fe) photocatalysts, NH₂-MIL-88B (Fe_0.6In_0.4) displayed excellent photocatalytic performance; the photocatalytic redox rate for Cr(vi) and TC-HCl reached 86.83% and 72.05%, respectively. The good photocatalytic performance might be attributed to the metal-to-metal charge transition (MMCT) between Fe–O clusters and In–O clusters formed by doping In(iii) into NH₂-MIL-88B (Fe), which provides effective active sites for the photocatalytic reduction and oxidation routes. Besides, the synergistic effect of the ligand-to-metal charge transition (LMCT) and MMCT expands the separation and transfer of photogenerated carriers and inhibits the recombination of electron–hole pairs, thus effectively improving the photocatalytic performance. Therefore, this work could provide a new method for the construction of mixed metal MOFs for the photocatalytic degradation of pollutants.

Aiming at solving the issue of wastewater purification, this work synthesized NH₂-MIL-88B (Fe_αIn_1−α) photocatalysts by a simple one-pot method, which was employed for photocatalytic reduction of Cr(vi) and oxidation of TC-HCl.     

Synthesis and evaluation of ion-imprinted composite membranes of Cr(vi) based on β-diketone functional monomers

Using Cr(vi) as the imprinted ions and 2-allyl-1,3-diphenyl-1,3-propanedione (ADPD) (a compound synthesized by independent design) as the functional monomer, a series of chromium ion-imprinted composite membranes (Cr(vi)-IICMs) and corresponding non-imprinted composite membranes (NICMs) were synthesized and tested. The results showed that the Cr(vi)-IICM₁₀ membrane prepared under optimal experimental conditions exhibited a high adsorption capacity towards Cr(vi) (Q = 30.35 mg g⁻¹) and a high imprinting factor (α = 2.70). The structural characteristics of Cr(vi)-IICM₁₀ and NICM₁₀ were investigated using FE-SEM, ATR-FTIR, and BET techniques combined with UV-Vis photometry and inductively coupled plasma emission spectrometry (ICP-OES) to evaluate the adsorption performance and permeation selectivity, while the effect on adsorption permeance of varying the experimental conditions including the solvent type, pH, and temperature was also investigated. The results showed that Cr(vi)-IICM₁₀ is a mesoporous material with excellent permeation selectivity, reusability, and favorable pH response, and that its adsorption behavior is in accordance with the Langmuir model and pseudo-first-order kinetics. Thus, Cr(vi)-IICM₁₀ shows great potential towards utilization as a “smart membrane” to control the separation and removal of Cr(vi) in wastewater, and also proved a reasonable design of the new functional monomer ADPD.

Using Cr(vi) as the imprinted ions and 2-allyl-1,3-diphenyl-1,3-propanedione (a compound of independent design) as the functional monomer, a series of chromium ion-imprinted composite membranes and corresponding non-imprinted composite membranes were synthesized and tested.     

MOF-derived (MoS2, γ-Fe2O3)/graphene Z-scheme photocatalysts with excellent activity for oxygen evolution under visible light irradiation

Constructing Z-scheme heterojunctions is considered as an effective strategy to obtain catalysts of high efficiency in electron–hole separation in photocatalysis. Unfortunately, suitable heterojunctions are difficult to fabricate because the direct interaction between two semiconductors may lead to unpredictable negative effects such as electron scattering or electron trapping due to the existence of defects which causes the formation of new substances. Furthermore, the van der Waals contact between two semiconductors also results in bad electron diffusion. In this work, a MOF-derived carbon material as a Z-scheme photocatalyst was synthesized via one-step thermal treatment of MoS₂ dots @Fe-MOF (MIL-101). Under visible light irradiation, the well-constructed Z-scheme (MoS₂, γ-Fe₂O₃)/graphene photocatalyst shows 2-fold photocatalytic oxygen evolution activity (4400 μmol g⁻¹ h⁻¹) compared to that of γ-Fe₂O₃/graphene (2053 μmol g⁻¹ h⁻¹). Based on ultraviolet photoelectron spectrometry (UPS), Mott–Schottky plot, photocurrent and photoluminescence spectroscopy (PL) results, the photo-induced electrons from the conduction band of γ-Fe₂O₃ could transport quickly to the valence band of MoS₂via highly conductive graphene as an electron transport channel, which could significantly enhance the electron–hole separation efficiency as well as photocatalytic performance.

The heterojunction between MoS₂ and γ-Fe₂O₃ was constructed via linking by in situ formed graphene, which resulted in a good photocatalyst for the oxygen evolution reaction, showing O₂ evolution activity of 4400 μmol g⁻¹ h⁻¹.     

Removal of arsenic(v) from aqueous solutions using sulfur-doped Fe3O4 nanoparticles

In this study, magnetic sulfur-doped Fe₃O₄ nanoparticles (Fe₃O₄:S NPs) were applied as adsorbents for the removal of As(v). Fe₃O₄:S NPs were fabricated by a two-step route, which included low-temperature mixing and high-temperature sintering. The as-prepared Fe₃O₄:S NPs could effectively remove As(v) under a wide pH range of 2–10 and presented a high As(v) adsorption capacity of 58.38 mg g⁻¹, which was much better than undoped Fe₃O₄ nanoparticles (20.24 mg g⁻¹). Adsorption experiments exhibited a pseudo-second-order model of adsorption kinetics and a Langmuir isotherm model of adsorption isotherms. Additionally, the coexisting ions such as NO₃⁻, SO₄²⁻, and CO₃²⁻ had no significant effect on As(v) adsorption and the adsorbent worked well in actual smelting wastewater. XPS and FTIR spectra of Fe₃O₄:S NPs before and after As(v) adsorption showed that Fe–OH groups played a significant role in the adsorption mechanisms. Moreover, the magnetic Fe₃O₄:S NPs adsorbents after adsorption could be rapidly separated from wastewater with an external magnetic field. Therefore, Fe₃O₄:S NPs could be an ideal candidate for the removal of As(v) from water.

Magnetic Fe₃O₄:S NPs presented a much better As(v) adsorption performance than undoped Fe₃O₄ NPs due to sulfur doping.     

Simultaneous removal of Sb(iii) and Cd(ii) in water by adsorption onto a MnFe2O4–biochar nanocomposite

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption. The MnFe₂O₄–BC nanocomposite was prepared via a co-precipitation method and analyzed using various techniques. The results confirm the successful decoration of the biochar surface with MnFe₂O₄ nanoparticles. The maximum Sb(iii) removal efficiency was found to be higher from bi-solute solutions containing Cd(ii) than from single-solute systems, suggesting that the presence of Cd(ii) enhances the removal of Sb(iii). The Langmuir isotherm model describes well Sb(iii) and Cd(ii) removal via adsorption onto the MnFe₂O₄–BC nanocomposite. The maximum adsorption capacities are 237.53 and 181.49 mg g⁻¹ for Sb(iii) and Cd(ii), respectively, in a bi-solute system. Thus, the prepared MnFe₂O₄–BC nanocomposite is demonstrated to be a potential adsorbent for simultaneously removing Sb(iii) and Cd(ii) ions from aqueous solutions.

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption.     

Adsorption and reduction of hexavalent chromium on magnetic greigite (Fe3S4)-CTAB: leading role of Fe(ii) and S(−ii)

In this study, a facile one-step route was used to synthesize a novel magnetic mesoporous greigite (Fe₃S₄)-CTAB composite, which was utilized to remove hexavalent chromium (Cr(vi)). The optimized Fe₃S₄-CTAB_0.75 composite with a CTAB dosage of 0.75 g possessed the maximum specific surface, showing the highest Cr(vi) adsorption capacity of 330.03 mg g⁻¹. The mechanism analysis revealed that Fe(ii) and S(−ii) were critical for the reduction of Cr(vi). CTAB can promote the removal of Cr(vi) by Fe₃S₄-CTAB composites, possibly due to increased S(−ii) concentration, better dispersion of nanoparticles, and greater zeta potential. Besides, there is mild effect of Fe⁰ on Cr(vi) removal, which is confirmed by the disappearance of the Fe⁰ peak from the XPS analysis. The pseudo-second-order kinetic model could explain the Cr(vi) removal processes well. The adsorption of Cr(vi) at different initial concentrations was more consistent with a Langmuir isotherm. The existence of H⁺ was beneficial for Cr(vi) removal by Fe₃S₄-CTAB_0.75. Our work confirmed that the obtained Fe₃S₄-CTAB_0.75 composites exhibit considerable potential for Cr(vi) removal from aqueous solution.

The presence of CTAB can promote the removal of hexavalent chromium from the Fe₃S₄-CTAB surface.     

Promoted adsorptive removal of chromium(vi) ions from water by a green-synthesized hybrid magnetic nanocomposite (NFe3O4Starch-Glu-NFe3O4ED)

A novel magnetic starch-crosslinked-magnetic ethylenediamine nanocomposite, NFe₃O₄Starch-Glu-NFe₃O₄ED, was synthesized via microwave irradiation. The characteristics of the assembled NFe₃O₄Starch-Glu-NFe₃O₄ED nanocomposite were evaluated via XRD, FT-IR, TGA, BET, SEM and HR-TEM analyses. Its particle size was confirmed to be in the range 11.25–17.16 nm. The effectiveness of the designed nanocomposite for the removal of Cr(vi) ions was explored using the batch adsorption technique. Equilibrium results proved that the adsorptive removal of the target metal ions from aqueous solution was highly dependent on the optimized experimental parameters. The maximum adsorptive removal percentage values (%R) of Cr(vi) ions on NFe₃O₄Starch-Glu-NFe₃O₄ED obtained at pH 2.0 were 85.27%, 91.90%, and 96.47% using 10.0, 25.0, and 50.0 mg L⁻¹ Cr(vi), respectively, for an equilibrium time of 30 min. The adsorption process was found to be strongly influenced by the presence of interfering salts including NaCl, CaCl₂, KCl, MgCl₂, and NH₄Cl. Kinetic studies were performed and it was found that the pseudo-second and Elovich models well fitted the experimental data with the possible suggested ion-pair interaction mechanism. Different isotherm models were employed to assess the adsorption equilibrium, which was revealed by fitting Langmuir, Temkin and Freundlich models. The maximum uptake capacity based on the Langmuir model was 210.741 mg g⁻¹. The effect of temperature and thermodynamics confirmed that adsorption was spontaneous, feasible, and endothermic in nature. Finally, the validity and applicability of using the NFe₃O₄Starch-Glu-NFe₃O₄ED nanocomposite to remove Cr(vi) ions from real water matrices were confirmed in the range of 91.2–94.7 ± 2.2–3.7%.

A novel magnetic starch-crosslinked-magnetic ethylenediamine nanocomposite, NFe₃O₄Starch-Glu-NFe₃O₄ED, was synthesized via microwave irradiation for the removal of Cr(vi) ions from aquous solution using the batch adsorption technique.     

Structure and transport properties of triple-conducting BaxSr1−xTi1−yFeyO3−δ oxides

In this work, Ba_xSr_1−xTi_1−yFe_yO_3−δ perovskite-based mixed conducting ceramics (for x = 0, 0.2, 0.5 and y = 0.1, 0.8) were synthesized and studied. The structural analysis based on the X-ray diffraction results showed significant changes in the unit cell volume and Fe(Ti)–O distance as a function of Ba content. The morphology of the synthesized samples studied by means of scanning electron microscopy has shown different microstructures for different contents of barium and iron. Electrochemical impedance spectroscopy studies of transport properties in a wide temperature range in the dry- and wet air confirmed the influence of barium cations on charge transport in the studied samples. The total conductivity values were in the range of 10⁻³ to 10⁰ S cm⁻¹ at 600 °C. Depending on the barium and iron content, the observed change of conductivity either increases or decreases in humidified air. Thermogravimetric measurements have shown the existence of proton defects in some of the analysed materials. The highest observed molar proton concentration, equal to 5.0 × 10⁻² mol mol⁻¹ at 300 °C, was obtained for Ba_0.2Sr_0.8Ti_0.9Fe_0.1O_2.95. The relations between the structure, morphology and electrical conductivity were discussed.

Ba_xSr_1−xTi_1−yFe_yO_3−δ-based perovskite materials with different barium and iron contents are reported as triple conducting oxides (TCOs), which may conduct three charge carriers: oxygen ions, protons and electrons/holes.     

A visible light active,carbon–nitrogen–sulfur co-doped TiO2/g-C3N4 Z-scheme heterojunction as an effective photocatalyst to remove dye pollutants

Heterojunction formation and heteroatom doping could be viewed as promising strategies for constructing composite photocatalysts with high visible light catalytic activity. In this work, we fabricated a carbon, nitrogen and sulfur co-doped TiO₂/g-C₃N₄ (CNS-TiO₂/g-C₃N₄) Z-scheme heterojunction photocatalyst composite via one-step hydrothermal and calcination methods. Compared with pure TiO₂ and g-C₃N₄, the CNS-TiO₂/g-C₃N₄ Z-scheme heterojunction photocatalyst possessed excellent degradation performance under visible light irradiation. Due to the formation of the Z-scheme heterostructure, the utilization rate of the photogenerated electrons–holes generated by the catalyst was increased, which enhanced the catalytic activity. Moreover, the heteroatom doping (C, N and S) could efficiently tailor the band gap of TiO₂ and facilitate electron transition, contributing to enhancing the degradation ability under visible light. The CNS-TiO₂/g-C₃N₄-2 exhibited a superior photocatalytic degradation efficiency (k = 0.069 min⁻¹) for methyl orange dye (MO), which is higher than those of pure TiO₂ (k = 0.001 min⁻¹) and g-C₃N₄ (k = 0.012 min⁻¹), showing excellent photocatalytic activity against organic pollutants.

The CNS-TiO₂/g-C₃N₄ photocatalyst with excellent visible light catalytic activity was successfully manufactured, benefiting from the construction of the Z-scheme heterojunction and the co-doping of heteroatoms (C, N and S).     

Ti surface doping of LiNi0.5Mn1.5O4−δ positive electrodes for lithium ion batteries

The particle surface of LiNi_0.5Mn_1.5O_4−δ (LNMO), a Li-ion battery cathode material, has been modified by Ti cation doping through a hydrolysis–condensation reaction followed by annealing in oxygen. The effect of different annealing temperatures (500–850 °C) on the Ti distribution and electrochemical performance of the surface modified LNMO was investigated. Ti cations diffuse from the preformed amorphous ‘TiO_x’ layer into the LNMO surface during annealing at 500 °C. This results in a 2–4 nm thick Ti-rich spinel surface having lower Mn and Ni content compared to the core of the LNMO particles, which was observed with scanning transmission electron microscopy coupled with compositional EDX mapping. An increase in the annealing temperature promotes the formation of a Ti bulk doped LiNi_(0.5−w)Mn_(1.5+w)−tTi_tO₄ phase and Ti-rich LiNi_0.5Mn_1.5−yTi_yO₄ segregates above 750 °C. Fourier-transform infrared spectrometry indicates increasing Ni–Mn ordering with annealing temperature, for both bare and surface modified LNMO. Ti surface modified LNMO annealed at 500 °C shows a superior cyclic stability, coulombic efficiency and rate performance compared to bare LNMO annealed at 500 °C when cycled at 3.4–4.9 V vs. Li/Li⁺. The improvements are probably due to suppressed Ni and Mn dissolution with Ti surface doping.

LiNi_0.5Mn_1.5O_4−δ surface is doped with Ti ion maintaining the spinel structure at 500 °C, higher annealing temperatures cause Ti diffusion from surface towards the core.     

Modification of bio-based β-diketone from wheat straw wax: synthesis of polydentate lipophilic super-chelators for enhanced metal recovery

Bio-derived lipophilic polydentate chelators have been synthesized and tested for their chelating ability using a range of metal salts of Cu, Co, Ni, Fe, and Cr. These novel molecules were produced by the Michael addition reaction of 14,16-hentriacontanedione, isolated from wheat straw wax, with methyl acrylate or bio-derived dimethyl itaconate via microwave heating. The Michael adducts could either be used directly as esters or be hydrolysed to their acid form. Critically, the creation of additional binding sites via the carboxylate moieties leads to an enhanced metal uptake over both a non-renewable commercially available lipophilic β-diketone (dibenzoylmethane) and the unmodified hentriacontane-14,16-dione, for the chelation of Fe(iii), Cr(iii) and Ni(ii). The modified β-diketone containing a single carboxylic acid functionality was able to extract 167 mg L⁻¹ of Fe(iii) from an FeCl₃ solution with no pH adjustment. In comparison, no chelation was observed with dibenzoylmethane, while unmodified hentriacontane-14,16-dione was able to extract 81 mg L⁻¹. The modified chelators containing one and two ester carboxylates extracted 255 and 305 mg L⁻¹ Cr(iii) from a solution of CrCl₃ at pH 5–6, 238 mg L⁻¹ was extracted by the unmodified β-diketone whilst no extraction was observed using dibenzoylmethane. This suggest some minor contribution or positive effect to chelation due to neighbouring ester groups. The chelator containing two carboxylic acid groups (tetra-dentate when combined with the diketone) was the most proficient in this study for removal of Ni from an NiCl₂ solution (140 mg L⁻¹). It was also found that at higher pH almost quantitative extraction was achieved using the polydentate chelators.

Bio-derived lipophilic polydentate chelators have been synthesized and tested for their chelating ability using a range of metal salts of Cu, Co, Ni, Fe, and Cr.     

Experimental and theoretical interpretation of the magnetic behavior of two Dy(iii) single-ion magnets constructed through β-diketonate ligands with different substituent groups (–Cl/–OCH3)

Two Dy(iii) single-ion magnets, formulated as [Dy(Phen)(Cl-tcpb)₃] (Cl-1) and [Dy(Phen)(CH₃O-tmpd)₃] (CH₃O-2) were obtained through β-diketonate ligands (Cl-tcpb = 1-(4-chlorophenyl)-4,4,4-trifluoro-1,3-butanedione and CH₃O-tmpd = 4,4,4-trifluoro-1-(4-methoxyphenyl)-1,3-butanedione) with different substituent groups (–Cl/–OCH₃) and auxiliary ligand, 1,10-phenanthroline (Phen). The Dy(iii) ions in Cl-1 and CH₃O-2 are eight-coordinate, with an approximately square antiprismatic (SAP, D_4d) and trigonal dodecahedron (D_2d) N₂O₆ coordination environment, respectively, in the first coordination sphere. Under zero direct-current (dc) field, magnetic investigations demonstrate that both Cl-1 and CH₃O-2 display dynamic magnetic relaxation of single-molecule magnet (SMM) behavior with different effective barriers (U_eff) of 105.4 cm⁻¹ (151.1 K) for Cl-1 and 132.5 cm⁻¹ (190.7 K) for CH₃O-2, respectively. As noted, compound CH₃O-2 possesses a higher effective barrier than Cl-1. From ab initio calculations, the energies of the first excited state (KD₁) are indeed close to the experimental U_eff as 126.7 cm⁻¹vs. 105.4 cm⁻¹ for Cl-1 and 152.8 cm⁻¹vs. 132.5 cm⁻¹ for CH₃O-2. The order of the calculated energies of KD₁ is same as that of the experimental U_eff. The superior SIM properties of CH₃O-2 could have originated from the larger axial electrostatic potential (ESP_(ax)) felt by the central Dy(iii) ion when compared with Cl-1. The larger ESP_(ax) of CH₃O-2 arises from synergic effects of the more negative charge and shorter Dy–O distances of the axial O atoms of the first sphere. These charges and distances could be influenced by functional groups outside the first sphere, e.g., –Cl and –OCH₃.

Further studies from the viewpoint of electrostatic potential demonstrate that the larger axial electrostatic potential (ESP) felt by the central Dy (iii) ion of CH₃O-2 is responsible for its better SIM property when compared with Cl-1.     

Construction of g-C3N4 and FeWO4 Z-scheme photocatalyst: effect of contact ways on the photocatalytic performance

Photocatalysis has been regarded as an attractive strategy for the elimination of contaminants, but its performance is usually limited by the fast recombination of photogenerated electron–holes. A heterojunction photocatalyst could achieve the effective separation of electron–holes. However, the electrons migrate to the less negative band while holes move to the less positive band, leading to a weakened redox ability. Z-scheme photocatalysis is a feasible way to realize the efficient separation of photogenerated electron–holes without sacrificing the reductive ability of electrons and oxidative ability of holes. In this work, a new Z-scheme photocatalyst, composed of g-C₃N₄ (photocatalyst I), FeWO₄ (photocatalyst II) and RGO (electron mediator), was fabricated through a facile hydrothermal and mixing method. The effect of contact ways (the electron mediator firstly combined with photocatalyst I or with photocatalyst II) on the Z-scheme photocatalytic performance was investigated. The photocatalytic removal rate of rhodamine B (RhB) was largely enhanced by the construction of a Z-scheme photocatalyst, compared with the g-C₃N₄/FeWO₄ composite without RGO. The contact ways could affect the photocatalytic ability of a Z-scheme photocatalyst. The enhanced photocatalytic performance was attributed to the Z-scheme induced efficient separation of photogenerated charge carriers. Furthermore, remaining holes (on the VB of FeWO₄) or remaining electrons (on the CB of g-C₃N₄) with powerful oxidation or reduction ability would promote the photocatalytic degradation of RhB.

g-C₃N₄ (photocatalyst I), FeWO₄ (photocatalyst II) and RGO (electron media) constitutes a novel Z-scheme photocatalyst for effective RhB removal.     

Synthesis,structural characterization and Cu(ii) adsorption behavior of manganite (γ-MnOOH) nanorods

New alternatives for the removal of transition metal ions that present an environmental risk are required. The chemical adsorption of these ions on surfaces with chemisorbent properties represents a promising area of research. In this work, manganite (γ-MnOOH) nanorods were synthesized, with a surface area of 20.22 m² g⁻¹, pore size of 32.18 nm and pore volume of 0.1627 cm³ g⁻¹. After chemical and structural characterization of the manganite sample, it was evaluated as an adsorbent of Cu(ii) from aqueous solution. The equilibrium adsorption data were well fitted by the Langmuir isotherm, and the results indicated that the maximum adsorption capacity of Cu(ii) was 11.926 mg g⁻¹. Cu(ii) ion adsorption on the manganite surface is a spontaneous and exothermic process (ΔG°< 0 and ΔH°< 0). The negative value of ΔS° suggests the stability of the adsorption process without structural change at the manganite–aqueous solution interface. A scheme for chemisorption of Cu(ii) ions on the hydroxylated surface of manganite is proposed.

Manganite (γ-MnOOH) nanorods were synthesized and Cu(ii) adsorption on their hydroxylated surface was a spontaneous process (ΔG° < 0).     

Additive effects of alkali metals on Cu-modified CH3NH3PbI3−δClδ photovoltaic devices

We investigated the addition of alkali metal elements (namely Na⁺, K⁺, Rb⁺, and Cs⁺) to Cu-modified CH₃NH₃PbI_3−δCl_δ photovoltaic devices and their effects on the photovoltaic properties and electronic structure. The open-circuit voltage was increased by CuBr₂ addition to the CH₃NH₃PbI_3−δCl_δ precursor solution. The series resistance was decreased by simultaneous addition of CuBr₂ and RbI, which increased the external quantum efficiencies in the range of 300–500 nm, and the short-circuit current density. The energy gap of the perovskite crystal increased through CuBr₂ addition, which we also confirmed by first-principles calculations. Charge carrier generation was observed in the range of 300–500 nm as an increase of the external quantum efficiency, owing to the partial density of states contributed by alkali metal elements. Calculations suggested that the Gibbs energies were decreased by incorporation of alkali metal elements into the perovskite crystals. The conversion efficiency was maintained for 7 weeks for devices with added CuBr₂ and RbI.

Addition of alkali metal elements (Na⁺, K⁺, Rb⁺, and Cs⁺) to Cu-modified CH₃NH₃PbI_3−δCl_δ devices improved the photovoltaic properties.     

Metal-bio functionalized bismuthmagnetite [Fe3−xBixO4/SiO2@l-ArgEt3+I−/Zn(ii)]: a novel bionanocomposite for the synthesis of 1,2,4,5-tetrahydro-2,4-dioxobenzo[b][1,4]diazepine malononitriles and malonamides at room temperature and under sonication

In this work, a new magnetized composite of bismuth (Fe_3−xBi_xO₄) was prepared and functionalized stepwise with silica, triethylargininium iodide ionic liquid, and Zn(ii) to prepare a multi-layered core–shell bio-nanostructure, [Fe_3−xBi_xO₄/SiO₂@l-ArgEt₃⁺I⁻/Zn(ii)]. The modified bismuth magnetic amino acid-containing nanocomposite was characterized using several techniques including Fourier-transform infrared (FT-IR), X-ray fluorescence (XRF), vibrating sample magnetometer (VSM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDAX), thermogravimetric/differential scanning calorimetric (TGA/DSC) analysis, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), and inductively coupled plasma-optical emission spectrometry (ICP-OES). The magnetized bionanocomposite exhibited high catalytic activity for the synthesis of 1,2,4,5-tetrahydro-2,4-dioxobenzo[b][1,4]diazepine malononitriles via five-component reactions between 1,2-phenylenediamines, Meldrum''s acid, malononitrile, aldehydes, and isocyanides at room temperature in ethanol. The efficacy of this protocol was also examined to obtain malonamide derivatives via pseudo six-component reactions of 1,4-phenylenediamine, Meldrum''s acid, malononitrile, aldehydes, and isocyanides. When the above-mentioned MCRs were repeated under the same conditions with the application of sonication, a notable decrease in the reaction time was observed. The recovery and reusability of the metal-bio functionalized bismuthmagnetite were examined successfully in 3 runs. Furthermore, the characteristics of the recovered Fe_3−xBi_xO₄/SiO₂@l-ArgEt₃⁺I⁻/Zn(ii) were investigated though FESEM and EDAX analysis.

In this work, a new magnetized composite of bismuth (Fe_3−xBi_xO₄) was prepared and functionalized stepwise with silica, triethylargininium iodide ionic liquid, and Zn(ii) to prepare a multi-layered core–shell bio-nanostructure, [Fe_3−xBi_xO₄/SiO₂@l-ArgEt₃⁺I⁻/Zn(ii)].     

β-Ga2O3 nanorod arrays with high light-to-electron conversion for solar-blind deep ultraviolet photodetection

Vertically aligned nanorod arrays (NRAs), with effective optical coupling with the incident light and rapid electron transport for photogenerated carriers, have attracted much interest for photoelectric devices. Herein, the monoclinic β-Ga₂O₃ NRAs with an average diameter/length of 500 nm/1.287 μm were prepared by the hydrothermal and post-annealing method. Then a circular Ti/Au electrode was patterned on β-Ga₂O₃ NRAs to fabricate solar-blind deep ultraviolet photodetectors. At zero bias, the device shows a photoresponsivity (R_λ) of 10.80 mA W⁻¹ and a photo response time of 0.38 s under 254 nm light irradiation with a light intensity of 1.2 mW cm⁻², exhibiting a self-powered characteristic. This study presents a promising candidate for use in solar-blind deep ultraviolet photodetection with zero power consumption.

Vertically aligned β-Ga₂O₃ nanorod arrays with high light coupling and rapid electron transport were assembled for solar-blind deep UV detection.     

Retraction: Magnetic Fe3O4@NiO hierarchical structures: preparation and their excellent As(v) and Cr(vi) removal capabilities

Retraction of ‘Magnetic Fe₃O₄@NiO hierarchical structures: preparation and their excellent As(v) and Cr(vi) removal capabilities’ by Shouwei Zhang et al., RSC Adv., 2013, 3, 2754–2764, DOI: 10.1039/C2RA22495J.

The Royal Society of Chemistry, with the agreement of the named authors, hereby wholly retracts this RSC Advances article due to concerns with the reliability of the data in the published article. The authors requested to retract this article because they admitted that the TEM characterization of the Fe₃O₄@NiO hierarchical microspheres in Fig. 4c was duplicated from the characterization of Fe₃O₄@NiAl-LDH microspheres in Fig. S4B from a J. Am. Chem. Soc. paper by Mingfei Shao et al. without permission.¹ The authors would like to apologise to the authors of ref. 1, and for any inconvenience to readers.Signed: Shouwei Zhang, Jiaxing Li, Jinzhang Xu and Xiangke WangDate: 11th August 2021Tao Wen was contacted but did not respondRetraction endorsed by Laura Fisher, Executive Editor, RSC Advances     

Direct β-selectivity of α,β-unsaturated γ-butyrolactam for asymmetric conjugate additions in an organocatalytic manner

The β-selective asymmetric addition of γ-butyrolactam with cyclic imino esters catalyzed by a bifunctional chiral tertiary amine has been developed, which provides an efficient access to optically active β-position functionalized pyrrolidin-2-one derivatives in both high yield and enantioselectivity (up to 78% yield and 95 : 5 er). This is the first catalytic method to access chiral β-functionalized pyrrolidin-2-one via a direct organocatalytic approach.

The asymmetric addition of γ-butyrolactam with cyclic imino esters catalyzed by (DHQD)₂AQN has been developed, which provides an access to β-position functionalized pyrrolidin-2-one derivatives in high levels yield and enantioselectivity.

Metal-free organocatalytic asymmetric transformations have successfully captured considerable enthusiasm of chemists as powerful methods for the synthesis of various kinds of useful chiral compounds ranging from the preparation of biologically important molecules through to novel materials.¹ Chiral pyrrolidin-2-ones have been recognized as important structural motifs that are frequently encountered in a variety of biologically active natural and synthetic compounds.² In particular, the β-position functionalized pyrrolidin-2-one backbones, which can serve as key synthetic precursors for inhibitory neurotransmitters γ-aminobutyric acids (GABA),³ selective GABA_B receptor agonists⁴ as well as antidepressant rolipram analogues,⁵ have attracted a great deal of attention. Therefore, the development of highly efficient, environmentally friendly and convenient asymmetric synthetic methods to access these versatile frameworks is particularly appealing.As a direct precursor to pyrrolidin-2-one derivatives, recently, α,β-unsaturated γ-butyrolactam has emerged as the most attractive reactant in asymmetric organometallic or organocatalytic reactions for the synthesis of chiral γ-position functionalized pyrrolidin-2-ones (Scheme 1). These elegant developments have been achieved in the research area of catalytic asymmetric vinylogous aldol,⁶ Mannich,⁷ Michael⁸ and annulation reactions⁹ in the presence of either metal catalysts or organocatalysts (a, Scheme 1). These well-developed catalytic asymmetric methods have been related to the γ-functionalized α,β-unsaturated γ-butyrolactam to date. However, in sharp contrast, the approaches toward introducing C-3 chirality at the β-position of butyrolactam through a direct catalytic manner are underdeveloped (b, Scheme 1)¹⁰ in spite of the fact that β-selective chiral functionalization of butyrolactam can directly build up α,β-functionalized pyrrolidin-2-one frameworks.Open in a separate windowScheme 1Different reactive position of α,β-unsaturated γ-butyrolactam in catalytic asymmetric reactions.So far, only a few metal-catalytic enantioselective β-selective functionalized reactions have been reported. For examples, a rhodium/diene complex catalyzed efficient asymmetric β-selective arylation^10a and alkenylation^10b have been reported by Lin group (a, Scheme 2). Procter and co-workers reported an efficient Cu(i)–NHC-catalyzed asymmetric silylation of unsaturated lactams (b, Scheme 2).^10c Despite these creative works, considerable challenges still exist in the catalytic asymmetric β-selective functionalization of γ-butyrolactam. First, the scope of nucleophiles is limited to arylboronic acids, potassium alkenyltrifluoroborates and PhMe₂SiBpin reagents. Second, the catalytic system and activation mode is restricted to metal/chiral ligands. To our knowledge, an efficient catalytic method to access chiral β-functionalized pyrrolidin-2-one via a direct organocatalytic approach has not yet been established. Therefore, the development of organocatalytic asymmetric β-selective functionalization of γ-butyrolactam are highly desirable. In conjunction with our continuing efforts in building upon chiral precedents by using chiral tertiary amine catalytic system,¹¹ we rationalized that the activated α,β-unsaturated γ-butyrolactam might serve as a β-position electron-deficient electrophile. This γ-butyrolactam may react with a properly designed electron-rich nucleophile to conduct an expected β-selective functionalized reaction of γ-butyrolactam under a bifunctional organocatalytic fashion, while avoiding the direct γ-selective vinylogous addition reaction or β,γ-selective annulation as outlined in Scheme 2. Herein we report the β-selective asymmetric addition of γ-butyrolactam with cyclic imino esters¹² catalyzed by a bifunctional chiral tertiary amine, which provides an efficient and facile access to optically active β-position functionalized pyrrolidin-2-one derivatives with both high diastereoselectivity and enantioselectivity.Open in a separate windowScheme 2β-Selective functionalization of γ-butyrolactam via metal- (previous work) or organo- (this work) catalytic approach.To begin our initial investigation, several bifunctional organocatalysts¹³ were firstly screened to evaluate their ability to promote the β-selective asymmetric addition of γ-butyrolactam 2a with cyclic imino ester 3a in the presence of 15 mol% of catalyst loading at room temperature in CH₂Cl₂ (entries 1–6,