Double pyramid stacked CoO nano-crystals induced by graphene at low temperatures as highly efficient Fenton-like catalysts.

Transition metal oxides are widely used as Fenton-like catalysts in the treatment of organic pollutants, but their synthesis usually requires a high temperature. Herein, an all-solid-state synthesis method controlled by graphene was used to prepare a double pyramid stacked CoO nano-crystal at a low temperature. The preparation temperature decreased by 200 °C (over 30% reduction) due to the introduction of graphene, largely reducing the reaction energy barrier. Interestingly, the corresponding degradation rate constants (kobs) of this graphene-supported pyramid CoO nano-crystals for organic molecules after their adsorption were over 2.5 and 35 times higher than that before adsorption and that of free CoO, respectively. This high catalytic efficiency is attributed to the adsorption of pollutants at the surface by supporting graphene layers, while free radicals activated by CoO can directly and rapidly contact and degrade them. These findings provide a new strategy to prepare low carbon-consuming transition metal oxides for highly efficient Fenton-like catalysts.

Unexpected higher corrosion in the gas phase region of metals caused by calcium and magnesium ions compared to sodium ions.

In the marine environment, Na+ ions have been the focus of attention owing to their high content, which is one of the important factors causing marine corrosion. With reference to the content of macro ions in seawater, circular iron samples were semi-immersed in 0.04 M MgCl2 and 0.6 M NaCl solutions containing different proportions of ethanol. Unexpectedly, we observed more severe corrosion effects in the gas phase region and at the gas-liquid interface of metal samples semi-immersed in the MgCl2 solution. Although the concentration of the MgCl2 solution was only 1/15 of that of the NaCl solution, the iron corrosion induced by MgCl2 was significantly more severe than that caused by NaCl when the ethanol content was increased. Mg2+ ions outperform Na+ ions in metal gas phase corrosion. Especially in the oxygen content of the gas phase corrosion product, MgCl2 caused an increase by up to 52.7%, while NaCl only resulted in a 10.3% increase. Ethanol is normally regarded as a corrosion inhibitor and exists in the liquid phase. Interestingly, in the gas phase and at the gas-liquid interface, ethanol aggravated rather than reducing iron corrosion, particularly in the presence of Mg2+ ions. In addition, we observed that Ca2+ ions produced more severe corrosion effects.

Different crystallographic Ni(OH)2 as highly efficient Fenton-like catalysts for sulfate radical activation.

By a simple hydrothermal method, a phase boundary between α- and ß-Ni(OH)2 can be obtained. The Fenton-like performance of α@ß-Ni(OH)2 is 1.56 times higher than that of single ß-Ni(OH). α@ß-Ni(OH)2 displays superior stability compared to α-Ni(OH)2, ß-Ni(OH)2, and amorphous Ni(OH)2, which makes significant contributions to developing advanced catalysts in diverse fields.

NiFe Layered Double Hydroxide (LDH) Nanosheet Catalysts with Fe as Electron Transfer Mediator for Enhanced Persulfate Activation.

A highly efficient, durable, and cost-effective Fenton-like catalyst is desired to produce the sulfate radicals (•SO4-) for energy and environmental applications. The M(n+1)+/Mn+ redox cycle in metal catalysts requires a high redox potential for •SO4- generation. NiFe layered double hydroxide (LDH) nanosheets with a suitable redox potential for persulfate (PDS) activation were prepared via incorporating Fe into the Ni based LDH. With the help of Fe, the charge-transfer kinetics for the reduction of Ni3+ to Ni2+ was improved and the formation of unwanted Ni component with higher oxidation state was suppressed. The incorporated Fe as the electron transfer mediator enhanced the process of Ni(OH)2/NiOOH redox cycle. Therefore, NiFe LDH exhibited superior performance in PDS activation with exceptionally high activity for the phenolic compounds' degradation in neutral and basic conditions. This work is expected to inspire the rational design of LDHs based catalysts for PDS activation.

Highly Efficient Utilization of Nano-Fe(0) Embedded in Mesoporous Carbon for Activation of Peroxydisulfate.

Nanoscale zerovalent iron (nZVI) particles have received much attention in environmental science and technology due to their unique electronic and chemical properties. However, the aggregation and oxidation of nZVI brings much difficulty in practical application of environmental remediation. In this study, we reported a composite nano-Fe(0)/mesoporous carbon by a chelation-assisted coassembly and carbothermal reduction strategy. Nano-Fe(0) particles with surface iron oxide (Fe2O3·FeO) were wrapped with graphitic layers which were uniformly dispersed in mesoporous carbon frameworks. The unique structure made the nano-Fe(0) particles stable in air for more than 20 days. It was used as a peroxydisulfate (PDS) activator for the oxidation treatment of 2,4,6-trichlorophenol (TCP). The TOF value of MCFe for TCP degradation is nearly 3 times higher than those of FeSO4 and Fe2O3·FeO and nearly 2 times than that of commercial nZVI. The reactive oxygen species (ROS) including •SO4-, HO•, and •O2-, 1O2 are efficiently generated by PDS activation with MCFe. The PDS activation process by nano-Fe(0) particles was intrinsically induced by the ferrous ions (Fe(II)) continuously generated at the solid/aqueous interface. Namely, the nano-Fe(0) particles were highly efficiently utilized in sulfate radical-based advanced oxidation processes (SR-AOP). The porous structure also assists the absorption and transfer of TCP during the degradation process.

Visible Light Assisted Heterogeneous Fenton-Like Degradation of Organic Pollutant via α-FeOOH/Mesoporous Carbon Composites.

A novel α-FeOOH/mesoporous carbon (α-FeOOH/MesoC) composite prepared by in situ crystallization of adsorbed ferric ions within carboxyl functionalized mesoporous carbon was developed as a novel visible light assisted heterogeneous Fenton-like catalyst. The visible light active α-FeOOH nanocrystals were encapsulated in the mesoporous frameworks accompanying with surface attached large α-FeOOH microcrystals via C-O-Fe bonding. Assisting with visible light irradiation on α-FeOOH/MesoC, the mineralization efficiency increased owing to the photocatalytic promoted catalyzing H2O2 beyond the photothermal effect. The synergistic effect between α-FeOOH and MesoC in α-FeOOH/MesoC composite improved the mineralization efficiency than the mixture catalyst of α-FeOOH and MesoC. The iron leaching is greatly suppressed on the α-FeOOH/MesoC composite. Interestingly, the reused α-FeOOH/MesoC composites showed much higher phenol oxidation and mineralization efficiencies than the fresh catalyst and homogeneous Fenton system (FeSO4/H2O2). The XPS, XRD, FTIR, and textural property results reveal that the great enhancement comes from the interfacial emerged oxygen containing groups between α-FeOOH and MesoC after the first heterogeneous Fenton-like reaction. In summary, visible light induced photocatalysis assisted heterogeneous Fenton-like process in the α-FeOOH/MesoC composite system improved the HO• production efficiency and Fe(III)/Fe(II) cycle and further activated the interfacial catalytic sites, which finally realize an extraordinary higher degradation and mineralization efficiency.

Uptake of perchlorate from aqueous solutions by amine-crosslinked cotton stalk.

Virgin cotton stalk was produced into an effective biosorbent for perchlorate adsorption. Surface analysis including BET surface area and SEM illustrated the reduction of porous structure in amine-crosslinked cotton stalk (AC-CS). Elemental and zeta potential analysis validated the graft of some positively charged amine groups on surface of AC-CS. Spectra analysis (XPS, FTIR and Raman spectra) suggested that interaction between AC-CS and ClO4(-) should be based on electrostatic attraction. The maximum adsorption capacity (qmax) of AC-CS for perchlorate at different pHs (3.0, 6.0, 9.0 and 11.0) were calculated as 29.6, 42.6, 41.0 and 33.0 mg/g, respectively. The saturated perchlorate uptakes in column were in range of 25.0-38.1 mg/g at different pHs. In addition, the exhausted AC-CS column was regenerated by 0.5 mol/L of NaCl solution, which was adequate for almost complete desorption of the perchlorate.