Weakened Mn-O bond in Mn-Ce catalysts through K doping induced oxygen activation for boosting benzene oxidation at low temperatures.

K-doped Mn-Ce solid solution catalysts were synthesized using a combination of coprecipitation and hydrothermal methods, demonstrating excellent performance in benzene oxidation. The catalyst K1Ce5Mn5 exhibited comparable activity to noble metal catalysts, achieving a 90 % benzene conversion at approximately 194 ℃. Durable tests under dry and moist conditions revealed that the catalyst could maintain its activity for 50 h at 218 ℃ and 236 ℃, respectively. Characterization results indicated that the catalyst's enhanced activity resulted from the weakened Mn-O bonding caused by the introduction of K+, facilitating the activation of oxygen and its involvement in the reaction. CeOx, the main crystalline phase of Mn-Ce solid solutions, provided abundant oxygen vacancies for capturing and activating oxygen molecules for the weakened Mn-O structures. This conclusion was further supported by partial density of state analysis from density functional theory computations, revealing that the introduction of K+ weakened the orbital hybridization of Mn3d and O2p. Finally, in situ diffuse reflectance infrared Fourier-transform spectroscopy (in situ DRIFTS) studies on Ce5Mn5 and K1Ce5Mn5 catalysts suggested that the introduction of K+ promoted the conversion of adsorbed benzene. Furthermore, intermediate products were transformed more rapidly for K1Ce5Mn5 compared to Ce5Mn5.

Unraveling the intrinsic mechanism behind the retention of arsenic in the co-gasification of coal and sewage sludge: Focus on the role of Ca and Fe compounds.

Minimizing the emission of arsenic (As) is one of the urgent problems during co-gasification of Shenmu coal (SM) and sewage sludge (SS). The intrinsic mechanism of As retention was obtained by analyzing the effect of different SM addition ratios on the As form transformation during co-gasification at 1000 °C under CO2 atmosphere. The results showed that the addition of SM effectively promoted the enrichment of As in the co-gasified residues. Especially, the best As retention rate of 65.71% was achieved with the 70 wt% addition ratio of SM. The addition of SM promoted the adsorption and chemical oxidation of As(III) to the less toxic As(V) through the coupling of Ca and Fe compounds in the co-gasified residues. XRD and XPS results indicated that Fe2O3 adsorbed As2O3(g) after partial conversion to Fe3O4 by the Boudouard reaction, while part of As2O3 was oxidized to As2O5 by lattice oxygen. Finally, the generated As2O5 was successively trapped by CaO and Fe2O3 to form stable Ca3(AsO4)2 and FeAsO4. HRTEM and TEM analysis comprehensively proved that As(III) was stabilized by the lattice cage of CaAl2Si2O8. In conclusion, the co-oxidation of Ca and Fe compounds and lattice stabilization simultaneously played a crucial role in the retention of As2O3(g) during co-gasification.

In-Furnace Control of Arsenic Vapor Emissions Using Fe2O3 Microspheres with Good Sintering Resistance.

The addition of Fe2O3 into furnaces is a promising method for arsenic pollution control. Nevertheless, Fe2O3 particles undergo serious sintering under actual furnace temperatures. To improve its sintering resistance, Fe2O3 hollow microspheres were synthesized by the template method and were tested in flue gas containing SO2 and NO in the range of 1000-1300 °C. The results demonstrated that the amount of arsenic captured could be steadily maintained above 5 mg/g throughout the operating temperature range, and Fe2O3 microspheres could maintain the originally developed pore structure and hollow morphology well even at 1200 °C. Based on product analysis and density functional theory calculations, the fixation pathway of arsenic was proposed. In no oxygen conditions, As2O3 was first bound to the Fe2O3 surface by forming an -O-As-O-Fe stable structure and then was oxidized by lattice oxygen. The introduction of O2 could regenerate the consumed lattice oxygen and therefore promote arsenic capture. Finally, the oxidized arsenic was fixed in products in the form of FeAsO4. Additionally, the impact of acid gases was also investigated. SO2 showed a notable inhibiting effect on arsenic capture, while the impact of NO was less noticeable.

Promoting adsorption of organic pollutants via tailoring surface physicochemical properties of biomass-derived carbon-attapulgite.

Biomass-derived carbon-attapulgite adsorbent was developed for organic pollutants removal. All the batch assays were performed to evaluate the effects of organic components, contact time, and initial concentration of organic pollutants on the adsorption performance of the as-prepared adsorbent. The samples were characterized via Brunauer-Emmett-Teller (BET), Fourier transform infrared (FTIR), X-ray diffractometer (XRD), and scanning electron microscopy (SEM). The results demonstrated that the acid-treated carbon-attapulgite adsorbent (H-ATP/BC) showed a large specific surface area (237 m2 g-1) and possessed abundant oxygen-containing functional groups and silicon-oxygen bonds (i.e., O-Si-O and O-Si), which provided more active sites and conduced to the adhesive of organic pollutants. Both physical adsorption and chemical adsorption were involved in the adsorption process, and competitive adsorption occurred when two or more target pollutants coexist. Especially, phenol and/or aniline with an aromatic ring were much more likely to adhere to the H-ATP/BC surface than pyridine, and the selectivity order of H-ATP/BC for these pollutants was phenol > aniline > pyridine. From the model fitting, it was observed that the adsorption data could be described well by a pseudo-second-order model and Freundlich isotherms. The theoretical maximum phenol, aniline, and pyridine adsorption capacities of the H-ATP/BC were 14.31 mg g-1, 15.21 mg g-1, and 20.74 mg g-1, respectively. Comparison among the commercial adsorbents price also illustrated that H-ATP/BC could be a promising material for efficient treatment of organic pollutants.Graphical abstract.

COx co-methanation over coal combustion fly ash supported Ni-Re bimetallic catalyst: Transformation from hazardous to high value-added products.

The hazardous industrial waste, coal combustion fly ash (CCFA), was creatively applied as Ni-Re bimetallic catalyst support. The expected catalyst was facilely prepared by co-impregnation method and further tested for COx co-methanation in a continuous fixed-bed reactor. The physico-chemical properties of the catalyst were examined by a series of techniques including XRF, ICP, XRD, N2 isothermal adsorption, H2-TPR, SEM and TEM. The results showed that compared to non-promoted monometallic Ni catalyst, the addition of Re promoter forming Ni-Re bimetallic catalyst was able to facilitate NiO reduction and increase Ni dispersion as well as inhibit carbon deposition and Ni sintering during reaction. The performance tests revealed that Ni15Re1.0 presented superior COx co-methanation activity over Ni15Re0, Ni15Re0.5 and Ni15Re1.5 due to its better anti-coking and anti-sintering ability. Based on in-situ DRIFTS analysis, a possible cycle reaction mechanism of COx co-methanation was reasonably proposed in the end. The reaction pathway for CO and CO2 methanation differed from each other, where CO was linearly adsorbed on Ni metals followed by stepwise hydrogenation while CO2 was first immobilized by the surface hydroxyl group and then gradually reacted with H2 to form CH4.

Enhanced degradation of Rhodamine B via α-Fe2O3 microspheres induced persulfate to generate reactive oxidizing species.

The porous α-Fe2O3 microspheres (MS-Fe2O3) were obtained through in-situ ion exchange-calcination method and then utilized to activate persulfate (PS) for Rhodamine B (Rh B) degradation. The influences of some important operational parameters were investigated for the MS-Fe2O3/PS system. Additionally, the physicochemical properties of the as-fabricated MS-Fe2O3 were revealed with the assistance of some analytical instruments (i.e., X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectra (XPS), Brunauer-Emmett-Teller (BET) and vibrating sample magnetometer (VSM)). The results showed that the physicochemical properties of MS-Fe2O3 played an important role in the activation of PS, which promoted MS-Fe2O3 to effectively induce PS to generate reactive oxidizing species, thus Rh B could be nearly 100% degraded within 30 min under near-neutral pH solution. Noticeably, the as-prepared MS-Fe2O3 revealed magnetism and could be separated conveniently through external magnetic, which was beneficial to reuse the catalyst. Finally, the reactive oxidizing species (SO4- and OH) participating in the oxidation process were illustrated by electron paramagnetic resonance (EPR) and radical quenching studies, and then a rational mechanism was proposed to better understand the catalytic oxidation degradation of organic pollutants.

Incorporation of humic acid into biomass derived carbon for enhanced adsorption of phenol.

In the present work, the biomass derived carbon decorated with humic acid (HC), was synthesized through impregnation method for the adsorption of phenol from water environment. Humic acids contain more oxygen-containing functional groups and hydrogen bonds, which promotes the binding between HC and phenol molecules. The results indicated that the adsorption performance of HC to phenol was better than that of commercial activated carbon. Moreover, in addition to physical absorption, the chemical reaction between carboxylic groups on the carbon surface and hydroxyl in phenol also played an important role during the process. The adsorption behavior of HC was described by equilibrium and kinetics parameters. Pseudo-second order model can describe the adsorption process well. Langmuir model was more suitable for the equilibrium adsorption data fitting, indicating that the adsorption mechanism of phenol on carbon surface tends to be monolayer adsorption. Considering practical application, UV254, chemical oxygen demand (COD) and ammonia from raw wastewater were selected as target contaminants and the corresponding adsorption experiments were carried out. The results displayed that HC exhibited excellent adsorption performance, especially for UV254, indicating that as-prepared carbon material had potential application for the control of certain organic pollutants in actual wastewater.

Plasma Treating Mixed Metal Oxides to Improve Oxidative Performance via Defect Generation.

The generation of structural defects in metal oxide catalysts offers a potential pathway to improve performance. Herein, we investigated the effect of thermal hydrogenation and low-temperature plasma treatments on mixed SiO2/TiO2 materials. Hydrogenation at 500 °C resulted in the reduction of the material to produce Ti3+ in the bulk TiO2. In contrast, low temperature plasma treatment for 10 or 20 min generated surface Ti3+ species via the removal of oxygen on both the neat and hydrogenated material. Assessing the photocatalytic activity of the materials demonstrated a 40-130% increase in the rate of formic acid oxidation after plasma treatment. A strong relationship between the Ti3+ content and catalyst activity was established, although a change in the Si-Ti interaction after plasma treating of the neat SiO2/TiO2 material was found to limit performance, and suggests that performance is not determined solely by the presence of Ti3+.

The contribution of oxygen-containing functional groups to the gas-phase adsorption of volatile organic compounds with different polarities onto lignin-derived activated carbon fibers.

Lignin-based activated carbon fibers (LCFK) were prepared by electrospinning method and evaluated in adsorption of volatile organic compounds (VOCs). Batch adsorption experiments for various component were carried out in a fixed-bed reactor. The molecular polarity of VOCs plays a pivotal role in the monocomponent dynamic adsorption. As a result, the adsorption capacity of toluene was larger than that of methanol or acetone. In the various multicomponent atmospheres (without water), the components interact with each other and competitive adsorption phenomenon occurs, resulting in the adsorption capacity of each component decreased significantly. Also, the samples before and after adsorption were characterized via Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and Boehm titration. The results reveal that methanol and acetone, controlled by physical adsorption, prefer to be adsorbed on polar groups on the surface of LCFK through the dipole-dipole interactions (i.e., van der Waals' forces). Differently, the adsorption of toluene onto LCFK was controlled by physical and chemical processes, and the lactone groups have a positive contribution to the adsorption of toluene. It was also observed that water vapor can enhance the negative effect on the adsorption of VOCs, especially for toluene. The results from this study will be valuable for explaining the mechanisms of competitive adsorption among each component in the various multicomponent atmospheres and understanding the contribution of chemical functional groups on the surface of LCFK in the adsorption process.

Study on adsorption properties and mechanism of Pb2+ with different carbon based adsorbents.

Different activated carbon materials are prepared from a series of solid wastes (sawdust, acrylic fabric, tire powder and rice husk) by combination of the KOH activation method and steam activation method. The influences of several parameters such as pH, contact time, adsorbent dosage and temperature on adsorption performance of Pb2+ with those different carbon adsorbents are investigated. The results demonstrate that Crice husk performance well in the adsorption process. In the following, the Crice husk is used to explain the adsorption mechanism of Pb2+ by SEM-EDS, FT-IR and XPS. The results illustrate that the surface oxygen-containing functional groups such as carboxyl, lactone group, phenolic hydroxyl and other alkaline metal ions like Na+ and K+ have significant effect on the adsorption process. A reasonable mechanism of Pb2+ adsorption is proposed that the ion exchange play key roles in the adsorption process. In addition, the effects of Cu2+, Zn2+ on the Pb2+ adsorption capacity with the four carbon adsorbents are also studied and the results demonstrate that other heavy metals play positive effects on the adsorption of Pb2+.

The application of prepared porous carbon materials: Effect of different components on the heavy metal adsorption.

In this study, five typical municipal solid waste (MSW) components (tyres, cardboard, polyvinyl chloride (PVC), acrylic textile, toilet paper) were used as raw materials to prepare four kinds of MSW-based carbon materials (paperboard-based carbon materials (AC1); the tyres and paperboard-based carbon materials (AC2); the tyres, paperboard and PVC-based carbon materials (AC3); the tyres, paperboard, toilet paper, PVC and acrylic textile-based carbon materials (AC4)) by the KOH activation method. The characteristic results illustrate that the prepared carbon adsorbents exhibited a large pore volume, high surface area and sufficient oxygen functional groups. Furthermore, the application of AC1, AC2, AC3, AC4 on different heavy metal (Cu(2+), Zn(2+), Pb(2+), Cr(3+)) removals was explored to investigate their adsorption properties. The effects of reaction time, pH, temperature and adsorbent dosage on the adsorption capability of heavy metals were investigated. Comparisons of heavy metal adsorption on carbon of different components were carried out. Among the four samples, AC1 exhibits the highest adsorption capacity for Cu(2+); the highest adsorption capacities of Pb(2+) and Zn(2+) are obtained for AC2; that of Cr(3+) are obtained for AC4. In addition, the carbon materials exhibit better adsorption capability of Cu(2+) and Pb(2+) than the other two kind of metal ions (Zn(2+) and Cr(3+)).