Dual Effect of Manganese Oxide Micromotors: Catalytic Degradation and Adsorptive Bubble Separation of Organic Pollutants

Manganese oxide (MnO₂) based micromotors exhibiting a dual effect, that is, catalytic degradation and adsorptive bubble separation, were employed for water remediation. The dual effect of MnO₂ microparticles led to a greater than 90 % of decolorization of non‐biodegradable organic dyes in just 1 h, without the need for external agitation or bubble generation. These findings suggest high potential of MnO₂ micromotors for decontamination of organic pollutants from wastewaters or natural water reserves.     

Visible‐Light‐Driven Janus Microvehicles in Biological Media

A light‐driven multifunctional Janus micromotor for the removal of bacterial endotoxins and heavy metals is described. The micromotor was assembled by using the biocompatible polymer polycaprolactone for the encapsulation of CdTe or CdSe@ZnS quantum dots (QDs) as photoactive materials and an asymmetric Fe₃O₄ patch for propulsion. The micromotors can be activated with visible light (470–490 nm) to propel in peroxide or glucose media by a diffusiophoretic mechanism. Efficient propulsion was observed for the first time in complex samples such as human blood serum. These properties were exploited for efficient endotoxin removal using lipopolysaccharides from Escherichia coli O111:B4 as a model toxin. The micromotors were also used for mercury removal by cationic exchange with the CdSe@ZnS core–shell QDs. Cytotoxicity assays in HeLa cell lines demonstrated the high biocompatibility of the micromotors for future detoxification applications.     

Micromotor‐Based Energy Generation

A micromotor‐based strategy for energy generation, utilizing the conversion of liquid‐phase hydrogen to usable hydrogen gas (H₂), is described. The new motion‐based H₂‐generation concept relies on the movement of Pt‐black/Ti Janus microparticle motors in a solution of sodium borohydride (NaBH₄) fuel. This is the first report of using NaBH₄ for powering micromotors. The autonomous motion of these catalytic micromotors, as well as their bubble generation, leads to enhanced mixing and transport of NaBH₄ towards the Pt‐black catalytic surface (compared to static microparticles or films), and hence to a substantially faster rate of H₂ production. The practical utility of these micromotors is illustrated by powering a hydrogen–oxygen fuel cell car by an on‐board motion‐based hydrogen and oxygen generation. The new micromotor approach paves the way for the development of efficient on‐site energy generation for powering external devices or meeting growing demands on the energy grid.     

Chemical/Light‐Powered Hybrid Micromotors with “On‐the‐Fly” Optical Brakes

Hybrid micromotors capable of both chemically powered propulsion and fuel‐free light‐driven actuation and offering built‐in optical brakes for chemical propulsion are described. The new hybrid micromotors are designed by combining photocatalytic TiO₂ and catalytic Pt surfaces into a Janus microparticle. The chemical reactions on the different surfaces of the Janus particle hybrid micromotor can be tailored by using chemical or light stimuli that generate counteracting propulsion forces on the catalytic Pt and photocatalytic TiO₂ sides. Such modulation of the surface chemistry on a single micromotor leads to switchable propulsion modes and reversal of the direction of motion that reflect the tuning of the local ion concentration and hence the dominant propulsion force. An intermediate Au layer (under the Pt surface) plays an important role in determining the propulsion mechanism and operation of the hybrid motor. The built‐in optical braking system allows “on‐the‐fly” control of the chemical propulsion through a photocatalytic reaction on the TiO₂ side to counterbalance the chemical propulsion force generated on the Pt side. The adaptive dual operation of these chemical/light hybrid micromotors, associated with such control of the surface chemistry, holds considerable promise for designing smart nanomachines that autonomously reconfigure their propulsion mode for various on‐demand operations.     

Micromotor‐Based Biomimetic Carbon Dioxide Sequestration: Towards Mobile Microscrubbers

We describe a mobile CO₂ scrubbing platform that offers a greatly accelerated biomimetic sequestration based on a self‐propelled carbonic anhydrase (CA) functionalized micromotor. The CO₂ hydration capability of CA is coupled with the rapid movement of catalytic micromotors, and along with the corresponding fluid dynamics, results in a highly efficient mobile CO₂ scrubbing microsystem. The continuous movement of CA and enhanced mass transport of the CO₂ substrate lead to significant improvements in the sequestration efficiency and speed over stationary immobilized or free CA platforms. This system is a promising approach to rapid and enhanced CO₂ sequestration platforms for addressing growing concerns over the buildup of greenhouse gas.     

SYNTHESIS AND CHARACTERIZATION OF POLY(ASPARTIC ACID) AND ITS DERIVATIVES AS BIODEGRADABLE MATERIALS

ABSTRACT

Three types of modified poly(aspartic acid)s, such as poly(aspartic acid-co-aminocarboxylic acid) (4), alkylamine modified poly(aspartic acid) (5) and crosslinked poly(aspartic acid) (6), were synthesized and calcium-ion chelating ability, hygroscopicity and water absorption were evaluated. The calcium-ion chelating ability of 4 depended on the kind of aminocarboxylic acids and the content of aminocarboxylic acid in the copolymer. The highest value was 3 times higher than that of poly(acrylic acid) with a M_w of 14000. The highly modified PASP, e.g., 50 mol% lauryl amine modified poly(aspartic acid), showed the highest by grogroscopicity among homopoly(aspartic acid)s and modified poly(aspartic acid)s. The maximum swelling of poly(aspartic acid) hydrogel prepared by the γ-irradiation of homopoly(as-partic acid) was 3400 g-deionized water/g-dry hydrogel.     

MnO2上氧气第一个电子转移步骤的从头计算研究

采用裸露簇和嵌入簇模型, 对β-MnO₂ (001), (110), (111)三个晶面以及O₂在(110)晶面的单址吸附模式(Pauling和Griffths模式), 进行从头计算. 从β-MnO₂ (001), (110), (111)三个晶面的电子结构差异以及O₂在(110)晶面吸附的吸附能、几何结构、集居数以及净电荷数分析得到: (001), (110), (111)三个晶面中(110)晶面的催化活性最高, 其活性顺序为(110)＞(111)＞(001). 氧气在(110)晶面的吸附, Pauling和Griffths两种吸附模式均存在, 属于化学吸附中的离子吸附. 氧气与MnO₂固体间发生了单电子转移, 氧气得到电子被还原成O₂^-, 转移电子属于整个体系, 具有离域性.     

In situ growth of MnO2 on pDA-templated cotton fabric for degradation of formaldehyde

Degradation of formaldehyde (HCHO) in interior decoration has been an urgent issue due to its toxicity nature and potential threats to human health. In this work, manganese dioxide nanoparticles (MnO₂ NPs) were in situ grown on the polydopamine (pDA)-templated cotton fabrics for environmentally friendly HCHO degradation applications. The morphology, elemental composition, and crystal structure of the cotton/pDA/MnO₂ were characterized by scanning electron microscopy–energy dispersive X-ray spectrum, Fourier transform infrared, X-ray diffractometer and X-ray photoelectron spectroscopy, respectively. The degradation of HCHO by the as-developed cotton/pDA/MnO₂ was measured in a self-made quartz reactor, and the stability of adsorption was evaluated by cyclic experiments. The results showed that the HCHO removal efficiency reached to 100% within 20 min after three cycles, suggesting that the as-prepared fabrics exhibited good stability for the degradation of HCHO. The development of MnO₂ NPs coated fabrics provides new strategies in degradation HCHO in interior decoration.

     

基于医用纱布负载的二氧化锰纳米颗粒用于亚甲蓝染料的去除

以医用纱布(medical gauze,MG)同时作为模板和还原剂,通过原位氧化还原反应,简便地制备了MG负载的MnO₂纳米颗粒(MnO₂ NPs/MG),并对其形貌、成分进行表征。结果表明,MnO₂ NPs均匀地分散于MG纤维表面。结合MnO₂纳米材料的吸附性能和MG复合材料的操作便捷性,将MnO₂ NPs/MG进一步应用于亚甲蓝染料的去除。结果表明,在中性条件下,通过简单的浸泡搅拌,MnO₂ NPs/MG对亚甲蓝的去除率可达85.09%,并且可以通过增大吸附材料用量与染料初始浓度的比例提高去除率。等温吸附和动力学研究证明,MnO₂ NPs/MG对亚甲蓝的吸附符合Langmuir吸附等温模型和拟二级动力学模型。     

基于医用纱布负载的二氧化锰纳米颗粒用于亚甲蓝染料的去除

以医用纱布（medical gauze,MG）同时作为模板和还原剂,通过原位氧化还原反应,简便地制备了MG负载的MnO₂纳米颗粒（MnO₂ NPs/MG）,并对其形貌、成分进行表征。结果表明,MnO₂ NPs均匀地分散于MG纤维表面。结合MnO₂纳米材料的吸附性能和MG复合材料的操作便捷性,将MnO₂ NPs/MG进一步应用于亚甲蓝染料的去除。结果表明,在中性条件下,通过简单的浸泡搅拌,MnO₂ NPs/MG对亚甲蓝的去除率可达85.09%,并且可以通过增大吸附材料用量与染料初始浓度的比例提高去除率。等温吸附和动力学研究证明,MnO₂ NPs/MG对亚甲蓝的吸附符合Langmuir吸附等温模型和拟二级动力学模型。     

Enhanced Performance of a Microbial Fuel Cell with a Capacitive Bioanode and Removal of Cr (VI) Using the Intermittent Operation

This study investigated a system which simultaneously produced electricity and stored energy in the MFC integrated MnO₂-modified capacitive bioanode. Compared to the noncapacitive anode, the maximum power density of MFC with MnO₂-modified bioanode reached 16.47 W m^?3, which was 3.5 times higher than that of the bare anode (4.71 W m^?3). During the charging-discharging experiment, the MFC with a capacitance bioanode has a higher average peak current density of 5.06 mA cm^?2 and 36 times larger than that with the bare bioanode. With the capacitive electrode, it is possible to let the MFC at the same time for production and storage of renewable electricity. Then two different operations (intermittent operation and continuous operation) of the MFC with a capacitive bioanode were studied to degrade Cr (VI) in cathode chamber. Results showed that the Cr (VI) removal rates of intermittent operation are much higher than that of continuous operation under the same time in the closed circuit state. This is due to the good ability of storing and releasing electron of the biological capacitor with MnO₂ modified material. And this study showed that MFC with a capacitive bioanode is better adapted to treat heavy metal pollutants by intermittent mode.     

In situ synthesis of MnO<Subscript>2</Subscript>-loaded biocomposite based on microcrystalline cellulose for Pb<Superscript>2+</Superscript> removal from wastewater

We fabricated a new MnO₂-loaded biocomposite based on microcrystalline cellulose (MCC–MnO₂) by an in situ synthesis method and investigated its adsorption behavior and mechanism for Pb²⁺ removal from aqueous medium. As-prepared MCC–MnO₂ was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier-transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) analyses. The effects of pH value, initial Pb²⁺ concentration, contact time, and solution temperature on the uptake of Pb²⁺ onto MCC–MnO₂ were investigated using a batch system. Adsorption equilibrium could be achieved in 3 h for various studied initial concentrations, and a pseudo-second-order model could fit the adsorption behavior well. The equilibrium data could be well described by the Langmuir isotherm model, and the maximum monolayer adsorption capacity of MCC–MnO₂ (with 7.98% MnO₂ loading) for Pb²⁺ was estimated to be 247.5 mg/g at 313 K. Thermodynamic studies indicated a spontaneous and endothermic adsorption process. X-ray photoelectron spectroscopy (XPS) was used to analyze the adsorption mechanism, revealing that the chemical speciation of Pb²⁺ on MCC–MnO₂ was similar to the compound PbO. Moreover, no variations in the valence of Mn were observed after adsorbing Pb²⁺. The regeneration study showed that the adsorption capacity retained about 89.6% of its initial value at the fifth sequential regeneration cycle, indicating that this material is an efficient and renewable hybrid adsorbent for Pb²⁺ removal.     

Rolled‐Up Monolayer Graphene Tubular Micromotors: Enhanced Performance and Antibacterial Property

The motion of catalytic tubular micromotors are driven by the oxygen bubbles generated from chemical reaction and is influenced by the resistance from the liquid environment. Herein, we fabricated a rolled‐up graphene tubular micromotor, in which the graphene layer was adopted as the outmost surface. Due to the hydrophobic property of the graphene layer, the fabricated micromotor performed a motion pattern that could escape from the attraction from the bubbles. In addition, Escherichia coli and Staphylococcus culture experiments proved that the graphene outer surface displays antibacterial property. Considering the bubble‐avoiding and antibacterial properties, the rolled‐up graphene tubular micromotor holds great potential for various applications such as in vivo drug delivery and biosensors.     

Photogenic MnO2/Ag metal nanocomposites and their dye adsorbing activities

• Manganese dioxide/silver (MnO₂/Ag) nanoparticles were fabricated by using KMnO₄-NaBH₄ redox reaction at room temperature. The optical and structural properties of MnO₂/Ag were determined using UV–visible and Fourier transform infrared spectroscopies. The morphology was established with scanning and transmission electron microcopies, and X-ray diffraction. MnO₂/Ag showed excellent adsorbing activity to the removal of Congo red. The various kinetic models were used to determine the rate of dye removal. Congo red adsorption onto MnO₂Ag proceeds through the pseudo-second-order kinetic model. Langmuir adsorption capacity (Q⁰_max = 97.1 mg/g), and sorption intensity (n = 1.6) were estimated with Langmuir and Freundlich adsorption isotherm models for 250 mg/L Congo red. Elovich model suggest the adsorption of Congo red with the MnO₂Ag proceeds through the film diffusion. The positive values of enthalpy changes (ΔH⁰), entropy changes (ΔS⁰), and negative Gibbs free energy changes (ΔG⁰) showed that the Congo red adsorption process was endothermic, spontaneous, and chemisorption process followed with physical mechanism. The results showed that the removal efficiency decreases from 98% to 89% after the six consecutive experiments.

     

Radium removal from aqueous solutions by adsorption on non-treated and chemically modified biomass by-product

The adsorption efficiency of a biomass by-product (olive cake) regarding the removal of radium (²²⁶Ra) from aqueous solutions has been investigated prior and after its chemical treatment. The chemical treatment of the biomass by-product included phosphorylation and MnO₂-coating. The separation/removal efficiency has been studied as a function of pH, salinity (NaCl) and calcium ion concentration (Ca²⁺) in solution. Evaluation of the experimental data shows clearly that the phosphorylated biomass by-product presents the highest adsorption capacity and efficiency followed by the MnO₂-coated material and the non-treated biomass by-product. However, regarding the effect of salinity and the presence of competitive cations (e.g. Ca²⁺) on the adsorption/removal efficiency, the MnO₂-coated material shows the lowest decline in efficiency (only 2 % of the relative adsorption efficiency) followed by the non-treated and the phosphorylated biomass by-product. The results of the present study indicate that depending on the physicochemical characteristics of the radium-contaminated water, all three types of the biomass by-product could be effectively used for the treatment of radium-contaminated waters. Nevertheless, the MnO₂-coated material is expected to be the most effective adsorbent and an alternative to MnO₂ resins for the treatment of environmentally relevant waters.     

Preparation and Pb (II) adsorption in aqueous of 2D/2D g‐C3N4/MnO2 composite

A novel g‐C₃N₄/MnO₂ composite was prepared by in situ deposition of MnO₂ on graphitic carbon nitride (g‐C₃N₄) nanosheets, and its adsorption properties were evaluated for removal of Pb (II) in aqueous. Fourier transform‐infrared, spectrometer scanning electron microscopy and transmission electron microscopy characterization showed the g‐C₃N₄/MnO₂ composite had a two‐dimensional/two‐dimensional (2D/2D) structure with ample active sites. The Brunauer–Emmett–Teller specific surface area of g‐C₃N₄/MnO₂ composites (234.9 m²/g) was 13.5 times larger than that of g‐C₃N₄ (17.37 m²/g), providing better conditions for adsorption. The adsorption kinetic data were better fitted with the pseudo‐second‐order model. The Langmuir model was more suitable for describing the experimental equilibrium data of g‐C₃N₄/MnO₂, and the maximum adsorption capacity was 204.1 mg/g for Pb (II). The adsorption of g‐C₃N₄/MnO₂ composite for Pb (II) was an endothermic and spontaneous process, and reached adsorption equilibrium rapidly within initial 150 min. This composite was an excellent adsorbent because of its higher adsorption capacity and facile preparation progress.     

Uranium adsorption by non-treated and chemically modified cactus fibres in aqueous solutions

The adsorption efficiency of Opuntia ficus indica fibres regarding the removal of hexavalent uranium [U(VI)] from aqueous solutions has been investigated prior and after the chemical treatment (e.g. phosphorylation and MnO₂-coating) of the biomass. The separation/removal efficiency has been studied as a function of pH, uranium concentration, adsorbent mass, ionic strength, temperature and contact time. Evaluation of the experimental data shows that biosorption is strongly pH-depended and that the MnO₂-coated product presents the highest adsorption capacity followed by the phosphorylated and non-treated material. Experiments with varying ionic strength/salinity don’t show any significant effect on the adsorption efficiency, indicating the formation of inner-sphere surface complexes. The adsorption reactions are in all cases exothermic and relatively fast, particularly regarding the adsorption on the MnO₂-coated product. The results of the present study indicate that adsorption of uranium from waters is very effective by cactus fibres and particularly the modified treated fibres. The increased adsorption efficiency of the cactus fibres is attributed to their primary and secondary fibrillar structure, which result in a relative relative high specific surface available for sorption.     

Oxidative degradation of dipeptide (glycyl–glycine) by water-soluble colloidal manganese dioxide in the aqueous and micellar media

The kinetics of the oxidative degradation of dipeptide glycyl–glycine (Gly-Gly) by water-soluble colloidal MnO₂ in acidic medium has been studied by employing visible spectrophotometer in the aqueous and micellar media at 35 °C. To obtain the rate constants as functions of [Gly-Gly], [MnO₂] and [HClO₄], pseudo-first-order conditions were maintained in each kinetic run. The first-order-rate is observed with respect to [MnO₂], whereas fractional-order-rates are determined in both [Gly-Gly] and [HClO₄]. The addition of sodium pyrophosphate and sodium fluoride has composite effects (catalytic and inhibition). The reaction proceeds through the fast adsorption of Gly-Gly on the surface of the colloidal MnO₂. The observed results are discussed in terms of Michaelis–Menten/Langmuir–Hinshelwood model. The Arrhenius and Eyring equations are found valid for the reaction over a range of temperatures and different activation parameters have been evaluated. A probable reaction mechanism, in agreement with the observed kinetic results, has been proposed and discussed. The influence of changes in the surfactant concentrations on the observed rate constant is also investigated and the reaction followed the same type of kinetic behavior in micellar media. The pseudo-first-order rate constant (k_ψ) is found to increase about two-fold with increase in [TX-100]. The catalytic effect of nonionic surfactant TX-100 is explained in terms of the mathematical model proposed by Tuncay et al.     

High-power ultrasonic-assisted phenol and dye degradation on porous manganese oxide doped titanium dioxide catalysts

In this study, a high-power ultrasonicator (600 W) is employed to examine dye degradation and phenol decomposition efficiencies in the presence of catalysts such as K-OMS-2, TiO₂, K-OL-1 doped TiO₂ and K-OMS-2 doped TiO₂. Methylene blue and phenol are chosen as the model pollutants to test the catalytic activity. Effects of ultrasonic power level or ultrasonic intensity, amount of catalysts used and ultrasonic irradiation time for catalytic degradation and removal of phenol were studied. No d-spacing peak shift was observed in intense XRD peaks of K-OMS-2- and K-OL-1-doped TiO₂ materials when compared with commercial TiO₂. Scanning and transmission electron micrographs (SEM and TEM) show aggregated particle morphology with spherical and rectangular particles for 5 wt % K-OMS-2/TiO₂. Methylene blue dye degradation efficiency in the presence of catalytic ultrasonication follows the order like TiO₂ > 5 wt % K-OMS-2/TiO₂ > 5 wt % K-OL-1/TiO₂. The K-OMS-2- and 5 wt % K-OMS-2-doped TiO₂ catalyst showed the best and most promising efficiency for phenol removal in ultrasonication process. K-OMS-2 shows the best phenol removal efficiency of 58% within a short duration (30 min) of catalytic ultrasonic-assisted reaction.     

Effective ultrasound-assisted removal of heavy metal ions As(III), Hg(II), and Pb(II) from aqueous solution by new MgO/CuO and MgO/MnO<Subscript>2</Subscript> nanocomposites

A series of new (MgO) _x CuO and (MgO) _x MnO₂ nanocomposites were prepared and used as adsorbent for removal of As³⁺, Hg²⁺, and Pb²⁺ ions from aqueous solution with high capacity and detection limit. These nanocomposites were synthesized with different molar ratios by sonochemical method in alkaline solution using polyvinylpyrrolidone as a capping agent and were characterized by FTIR, AAS, UV–Vis spectroscopy, and TEM and SEM imaging. The maximum heavy metal ions adsorption was achieved for (MgO)_0.32CuO and (MgO)_2.9MnO₂ nanocomposites assisted by 3-min sonication using ultrasound. Adsorbent capacity of (MgO)_0.32CuO reached 500.0 mg/g and detection limit was 0.1 ppb for As³⁺. Also (MgO)_2.9MnO₂ nanocomposite adsorbed 457.1 mg/g of Hg²⁺ and 461.2 mg/g of Pb²⁺. Extremely low detection limits of 1.5 and 2.0 ppb were obtained for Hg(II) and Pb(II) ions, respectively, which are much lower than the WHO allowable limits. So, these nanocomposites should be excellent candidate for heavy metal removal with advantage of high capacity, high sensitivity, cost effectiveness and easy preparation.