Dual-functional Materials Research Articles

Dual-functional lanthanide ions doped lanthanum titanate microcrystals for simultaneous temperature detection and photothermal conversion

The dual-functional optical materials that can achieve accurate temperature sensing and effective photothermal conversion have aroused great concern in biomedical and industrial fields. However, the lack of optical functional materials limits the photothermal devices in practical applications. In this work, the pure monoclinic Ho3+/Yb3+ codoped La2Ti2O7 microcrystals have been successfully synthesized for optical thermometry and photothermal conversion. Different from the partial overlap of thermal coupling energy levels in Er3+, the wide separation of emission bands in Ho3+ reduce the calculation error of ratio-metric thermometry. The maximum value of sensitivity reaches 1.41% K−1. And the light-to-heat energy conversion of the sample has been explored by some photothermal experiments. It is confirmed that the sample can be heated to the specified temperature by adjusting the power of the heating light source. Meanwhile, the photothermal imaging can be achieved because of the high photothermal conversion of the material. Besides, the dual-functional prototype probe based on La2Ti2O7:Ho3+/Yb3+ microcrystals has been made to investigate the temperature sensing and photothermal conversion performance. These results illustrated the sample has potential applications in optical thermometry and biological photothermal therapy.

Dual-functional 3D multi-wall carbon nanotubes/graphene/silicone rubber elastomer: Thermal management and electromagnetic interference shielding

To address overheating and electromagnetic interference of integrated electronics, the design of multi-functional materials with high out-of-plane thermal conductivity and excellent electromagnetic interference shielding effectiveness is desirable. In this contribution, an anisotropy graphene/multi-walled carbon nanotubes with 3D continuous network is fabricated by KOH induced hydrothermal reaction and subsequent graphitization at 2800 °C. When the graphene oxide to multi-walled carbon nanotubes ratio is 1:3, the balance between the decline of sp2 crystallite size in horizontal direction and the enhancement of turbostratic-stacking is achieved, which facilities the phonon transfer and electron transport. The optimal thermal conductivity of composites reaches up to 1.30 W m−1 K−1 at a low loading of 2.77 wt%, which is 465% higher than that of pure silicon rubber (0.23 W m−1 K−1). Meanwhile, the composite exhibits the maximum electric conductivity and electromagnetic interference shielding effectiveness of 42 dB in K-band. Moreover, it still retains the flexibility of matrix. This work paves the way of lightweight dual-function integrated materials.

A dual functional material: Spirulina Platensis waste-supported Pd-Co catalyst as a novel promising supercapacitor electrode

In the present study, Spirulina Platensis waste-supported Pd-Co (SPW-Pd-Co) catalyst was used as an efficient catalyst for the methanolysis reaction of sodium borohydride (NaBH4); moreover, the produced SPW-Pd-Co catalyst was tested as a supercapacitor electrode material for the first time. In this context, the SPW-Pd-Co catalyst was synthesized by the treatment of the Spirulina Platensis waste (SPW) with 1–7 M HCl, 1 mL PdCl2 solution (2% w/w) and 1, 2, 3, 4, and 5 mL CoCI2·6H2O solution (5% w/w). Under optimum conditions, the most active catalyst was obtained by burning with 3 M HCl-Pd-4 mL Co2+ solution at 600 °C for 90 min. The maximum rate of hydrogen generation (HGR) obtained at 30 °C from the NaBH4 methanolysis reaction was found to be 5497.7 mLmin-1gcat−1, and the catalyst activation energy was found to be 10.32 kJ mol−1. The gravimetric capacitance of the prepared electrode was calculated as 50 F/g at 2 A/g current density. The capacitance values of the supercapacitor are at a significant level in terms of capacity and the cost.

Production of dual functional carbon material from biomass treated with NaOH for supercapacitor and catalyst

AbstractIn this research, tea factory waste (TFW), an organic biomass source, was used as a metal free basic catalyst for the production of hydrogen from NaBH4 by methanolysis. In the preparation of the catalysts, tea factory wastes taken from the tea factory and released during tea production were used. For the production of H2 from NaBH4 by methanolysis, TFW was pre‐treated with different base materials (KOH, NH4Cl, and NaOH). Tests have been made on different mixing ratios, combustion temperatures, and durations for catalyst optimization by selecting the base with the highest hydrogen yield. Hydrogen production efficiency was recorded as 2832.2 and 6560.8 mL min−1 g−1 at 30°C and 60°C, respectively. The activation energy of the catalyst was defined as 18.07 kJ mol−1. Characterization of TFW catalyst was examined by SEM‐EDX, XRD, and FT‐IR analysis. When the obtained data were evaluated and some studies available in the literature were considered, it was concluded that tea factory wastes, which are a biomass resource, can be used in catalyst production. The capacitance value of the electrode was computed as 8 to 12.9 F g−1.

Electrochromic/electrofluorochromic poly(urea-urethane) bearing oligoaniline and tetraphenylethylene groups: Synthesis, characterization, and H2O2 visualized determination

The elegant electroswitchable color/emission properties of electrochromic/electrofluorochromic dual-functional materials motivates the exploration of their new applications. In this work, a new poly (urea-urethane) was synthesized via nucleophilic copolymerization of electroactive oligoaniline derivative, solid-emissive tetraphenylethylene groups, and alkyl isocyanate. The resultant poly (urea-urethane) exhibited good electroactivity and desirable aggregation-induced emission properties. High-performance electrochromic/electrofluorochromic behavior had been disclosed with a high optical contrast ratio of ΔT = 50.4%, a moderate fluorescence on/off ratio of 10.5, and high coloration efficiency of 503 cm2/C at 768 nm. A reflective/emissive dual-mode display device had also been manufactured based on the resultant poly (urea-urethane) and charge-balancing V2O5, exhibiting a reversible color change and tunable fluorescence conversion upon the electric stimulus. Furthermore, this polymer showed an interesting color/fluorescence response to H2O2, due to the linkage mechanism between its redox states and optical properties. The spray-coated poly (urea-urethane) test strips were employed in visualized dual-determination of H2O2 with gradual color change from gray to dark green, along with an obvious fluorescence change from light blue to dark, which displays easy operation and rapid detection.

Dual Functions of Riboflavin-functionalized Poly(lactic-co-glycolic acid) Nanoparticles for Enhanced Drug Delivery Efficiency and Photodynamic Therapy in Triple-negative Breast Cancer Cells.

Combating triple-negative breast cancer (TNBC) is one of the greatest challenges in cancer therapy. This is primarily due to the difficulties in developing drug delivery systems that can effectively target cancer sites. In this study, we demonstrated a proof-of-principle concept using modified surfaces of poly(lactic-co-glycolic acid) nanoparticles linked with a riboflavin analogue (PLGA-CSRf) to obtain a dual-functional material. PLGA-CSRf nanoparticles were able to function as a drug delivery ligand and a photodynamic therapy agent for TNBC cells (MDA-MB-231). Biocompatibility of novel PLGA-CSRf nanoparticles was evaluated with both breast cancer and normal breast (MCF-10A) cells. In vitro studies revealed a six-fold increase in the cellular uptake of PLGA-CSRf nanoparticles in cancer cells compared with normal cells. The results demonstrate the ability of riboflavin (Rf) to enhance the delivery of PLGA nanoparticles to TNBC cells. The viability of TNBC cells was decreased following treatment with doxorubicin-encapsulated PLGA-CSRf nanoparticles in combination with UV irradiation, due to the photosensitizing property of Rf on the surface of the nanoparticles. This work demonstrated the ability of PLGA-CSRf to function both as an effective drug delivery carrier and as a therapeutic entity, with the potential to enhance photodynamic effects in the highly aggressive TNBC model.

Functionalized hollow mesoporous silica for detection of Staphylococcus aureus and sterilization

A dual-functional smart material for both bacterial detection and sterilization was prepared through the electrostatic interaction between Rhodamine B-loaded amino-modified hollow mesoporous silica spheres (RAHMSN) and Staphylococcus aureus (S. aureus)-specific aptamer-modified gold nanorods (AGNR). The internal RAHMSN portion was used for detection of S. aureus, while the external AGNR was used for photothermal sterilization. In the presence of S. aureus, it would specifically bind to the aptamer that modified on AGNR, resulting in the removal of AGNR from RAHMSN. Subsequently, Rhodamine B could be released from the AHMSN for the fluorescent detection of S. aureus. Then, upon near-infrared (NIR) light irradiation, the photothermal effect of AGNR was utilized to kill the specifically bound S. aureus, exerting the function of photothermal sterilization. When the ratio of RAHMSN to AGNR is 8 and the concentration of Rhodamine B is 11 μg/mL, the dual-functions of the composite material are harmoniously combined. The assay exhibited a wide detection range from 6.5 × 102 CFU/mL to 6.5 × 107 CFU/mL with the limit of detection of 51 CFU/mL, as well as good specificity. In terms of sterilization, 100% sterilization can be achieved after 5 min of irradiation. Based on these excellent properties, the dual-functional material will be very helpful to save resources and avoid the abuse of antibiotics in the potential applications in environmental sterilization and testing.

Constructing MOF-derived CoP-NC@MXene sandwich-like composite by in-situ intercalation for enhanced lithium and sodium storage

The development of dual-function anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) is exceedingly essential. Herein, with rationally designed hierarchical metal-organic framework (MOF)@MXene as a precursor, a novel sandwich-like CoP-NC@Ti3C2Tx composite has been successfully fabricated by the following phosphorization reaction. As anode material for LIBs, the CoP-NC@Ti3C2Tx composite exhibits remarkable electrochemical performance with high-rate capability (147.8 mAh g−1 at 2000 mA g−1; 245.6 mAh g−1 at 100 mA g−1) and ultralong cycling life (2000 cycles with a capacity retention over 100%). For SIBs, it delivers a discharge capacity of 101.6 mAh g−1 at a current density of 500 mA g−1 after 500 cycles. The well-designed sandwich-like composite effectively supports the easy access to electrolyte, facilitate the Li/Na ion transportation, and protect the active material from pulverization upon long cycling. In addition, the electrochemical reaction kinetics and Li-migration kinetics of the CoP-NC@Ti3C2Tx composite have been pioneeringly illuminated by pseudocapacitive behavior calculation and density functional theory (DFT) computations, respectively. This work sheds light on the rational design and development of MOF/MXene-derived dual-function anode materials for Li/Na-storage.

Separation and stabilization of arsenic in copper smelting wastewater by zinc slag

Copper smelting wastewater shows strong acidity, has a high arsenic concentration and has many types of heavy metals, which not only restricts the sustainable development of copper smelting enterprises but also poses a danger to the ecological environment. Here, we propose a new process for treating copper smelting wastewater with zinc slag. We studied both the solid-liquid chemical reaction process as well as the mechanism by which zinc slag removes arsenic in copper smelting wastewater in a water bath at 85 °C under atmospheric pressure. Specifically, 5 g of zinc slag reacted with copper smelting wastewater with an initial arsenic concentration of 6000 mg/L for 4 h resulted in an arsenic removal rate of 99.65%, and the leaching concentration of arsenic in the toxicity characteristic leaching procedure experiment was only 0.52 mg/L. Zinc slag is dissolved in Copper smelting wastewater to release iron ions and silicate. The solid-liquid reaction of the two is accompanied by coprecipitation of iron arsenate and the in-situ covering of silica gel, resulting in a core-shell precipitate with iron arsenate as the core and silica gel as the shell. The colloidal chemistry of silica gel and cations and its chemical stability can effectively prevent the dissolution of arsenic ions and significantly improve the stability of iron arsenate. Zinc slag, a dual functional material for removing arsenic and fixing arsenic, shows extraordinary potential for the removal and fixation of arsenic in copper smelting wastewater. This approach could further improve wastewater treatment in the non-ferrous smelting industry.

An Imidazole Thione-Modified Polyhedral Oligomeric Silsesquioxane for Selective Detection and Adsorptive Recovery of Au(III) from Aqueous Solutions.

Developing a material toward simultaneous detection and recovery of gold ions (Au(III)) is highly desirable for the economy and the environment. Herein, we report a highly efficient dual-function material for simultaneous Au(III) detection and recovery by simply introducing abundant imidazole thione and thioether groups in one system. This material, that is, an imidazole thione-modified polyhedral oligomeric silsesquioxane (POSS-2), was prepared by a mild reaction of an imidazolium-containing POSS and sulfur at ambient temperature. The POSS-2 suspension in water can rapidly and selectively detect Au(III) with a very low limit of detection of 1.2 ppb by fluorescence quenching or a visualized color change from white to dark orange. POSS-2 can also selectively and efficiently capture Au(III) with a maximum adsorption uptake of 1486.5 mg/g. The adsorption process well fits with the pseudo-second-order kinetic and Langmuir models. The intriguing dual-function performance is better than most of the previous Au(III) probes or adsorbents. The mechanism study reveals that the detection and adsorption behavior are mainly caused by the redox reaction and coordination between imidazole thione and thioether groups and Au(III). Furthermore, POSS-2 was successfully utilized to extract gold without interference from a discard CPU. These results indicate the potential application of the present dual-function material for Au(III) detection and recovery from aqueous solutions. More dual-functional materials could be designed and prepared by this simple strategy.

Microcystis aeruginosa supported-Mn catalyst as a new promising supercapacitor electrode: A dual functional material

In the present study, a Mn-supported catalyst material developed from Microcystis aeruginosa microalgae for hydrogen generation was tested as a supercapacitor electrode material for the first time. The catalyst material (MA-HCl-Mn) was examined for hydrogen generation through methanolysis of NaBH4, and it demonstrated good catalytic activity. Symmetric and asymmetric supercapacitor cells were prepared using MA-HCl-Mn as the electrode material. The electrochemical performance of the cells were evaluated by a two-electrode system using 2 M KOH as the electrolyte. The gravimetric capacitance of the symmetric and asymmetric cells found to be 40 F/g and 71 F/g, respectively. It was concluded that MA-HCl-Mn served as a sustainable, dual functional material showing a high catalytic activity for the hydrogen generation and a promising electrochemical performance as the supercapacitor electrode.

Hydrogen sulfide removal technology: A focused review on adsorption and catalytic oxidation

The principal technologies for H2S removal are reviewed herein. Two technologies in particular, adsorption and catalytic oxidation, are considered as promising for desulfurization in terms of process simplicity, H2S removal performance, and operational cost. Nanoporous materials such as activated carbons, zeolites, mesoporous silicas, and metal organic frameworks are extensively used as sorbents because their porous characteristics are suitable for efficient diffusion and capture of H2S. To improve the H2S adsorption performance, these materials are frequently modified with functional groups or doped with various metal oxides. For example, representative metal oxide-based catalysts (e.g., vanadium, magnesium, and iron oxides) have been investigated for the selective oxidation of H2S to elemental sulfur. In this context, the dispersion of active metals onto supports, or the addition of modifying metals, are reasonable strategies for inhibiting catalyst deactivation and enhancing catalytic activity. Emerging studies based on the combination of adsorption and catalytic oxidation have introduced the syntheses of dual-function materials, such as metal nanoparticle-dispersed or metal-free porous carbons. In conclusion, comprehensive research into catalyst synthesis and performance evaluation must continue in order to develop the most promising technology for H2S removal.

Enhancement of fluorescence and magnetic properties of CeF3:RE3+ (Tb, Gd) nanoparticles via multi-band UV excitation and Li doping regulation

In this study, hydrothermal synthesis of CeF3: Tb, Gd nanoparticles doped with Li+ alkali metal ions were demonstrated using introduction of Li+ ions through LiNO3 nitrate. These nanoparticles have dual properties of magnetic fluorescence. X-ray diffraction, Fourier transform infrared spectrometer, XPS and photoluminescence spectra, and vibrating sample magnetometry were used to characterize structural properties, surface functional groups, fluorescence, and magnetic properties of these particles. Results show that CeF3: Tb, Gd nanoparticles exhibit bright green light emission under excitation at 258 nm and 378 nm ultraviolet band. Through the modification of Li+ ions, luminous intensity of green light is further improved. Energy transfer between rare earth ions was investigated via photoluminescence spectroscopy. This work demonstrates potential applications of Li doped CeF3: Tb, Gd nanoparticles as photomagnetic dual-functional materials in fields of biological imaging, solid state lighting, and magnetic biological separation.

Dual-functional coordination polymers with high proton conduction behaviour and good luminescence properties.

Two coordination polymers, [M(5-hip)(H2O)3]n (M = Cd2+ (1), Zn2+ (2), 5-hip = 5-hydroxyisophthalic acid), have been synthesized under hydrothermal conditions. The crystal structure reveals that complexes 1 and 2 have 1D chain structures by the coordination of metal ions and 5-hip. 1D chains are connected by hydrogen bonds to form a 3D structure. AC impedance analysis shows that the proton conductivity of complexes 1 and 2 comes up to 1.58 × 10-3 S cm-1 (98%RH, 343 K) and 5.27 × 10-4 S cm-1 (98%RH, 353 K), respectively. To further improve the proton conductivity, a hybrid membrane was prepared by the solution casting method with complexes as fillers and sulfonated polyether ether ketone (SPEEK) as the organic matrix. The proton conductivity of hybrid membranes 1@SPEEK-5 and 2@SPEEK-5 is 1.97 and 1.58 times higher than that of pure SPEEK membranes, respectively. Furthermore, the two complexes are excellent fluorescent sensors, which could detect Cr2O72- in aqueous solution with high sensitivity and selectivity. Both of them have low detection limits for Cr2O72- in aqueous solution, where the detection limit of complex 1 is 0.8 μM and that of complex 2 is 1 μM. The above work demonstrates that the two complexes are dual-functional materials with high proton conduction and good fluorescence properties.

Facially Synthesis of Ni(OH) <sub>2</sub> Nanoarray on RGO@ Carbon Fabric as Dual-Functional Electrochemical Materials for Supercapacitors and Capacitive Desalination

A high performance Ni(OH)2 nanoarray on RGO@ carbon fabric nanocomposites with hierarchical nanostructures were facilely synthesized, which involves i. coating of graphene on carbon fabric; ii, in-situ growth of Ni(OH)2 nanoarray on graphene surface. It is found that Ni(OH)2 nanoplates grown evenly on the surfaces of graphene without stacking. This unique structure of electrode material favors to a higher electrochemical active sites, which endows the enhancing capacity performance. The morphology and the microstructure of the as-prepared composites were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM) techniques. Capacitive properties of the synthesized electrodes were studied using cyclic voltammetry, charge/discharge, and electrochemical impedance spectroscope in a three-electrode experimental setup. Favors from the unique structure of Ni(OH)2/RGO@carbon fabric nanocomposites, this material as dual-functional electrodes shows decent performance for both supercapacitor and capacitive desalination (CDI). The specific capacitance is calculated to be 1325 F g-1 at 1 A g-1, moreover, this material shows a high rate capability, the capacitance can be maintained at 612 F g-1 even at 10 A g-1. Besides, the performance of it as potential CDI electrodes were explored. Such high-performance Ni(OH)2/RGO@carbon fabric hierarchical nanostructures can offer great promise in large-scale energy storage device applications.

The synthesis and characterization of Zn(ii)/Cd(ii) based MOFs by a mixed ligand strategy: a Zn(ii) MOF as a dual functional material for reversible dye adsorption and as a heterogeneous catalyst for the Biginelli reaction

2D Zn(ii)/Cd(ii) based MOF involving mixed ligands have been synthesized. Zn(ii) based MOF has been utilized as a bifunctional material towards reversible dye adsorption and as an efficient heterogeneous catalyst in Biginelli reaction.

Application of Polypyrrole/Lead Sulphide Nanocomposite in UV Light Assisted Photocatalysis and Gas Sensing

The synthesis of ppy/lead sulphide nanocomposite was done using the co-precipitation method. The synthesized ppy/leadsulphide nanocomposite was characterized using Transmission Electron Microscopy (TEM), Selected Area Electron Diffraction (SAED), X-Ray Powder Defraction (XRD), Fourier Transformation Infra-Red Spectroscopy (FTIR), UV-Vis Spectroscopy techniques. The optical bandgap of the synthesized ppy/lead sulphide nanocomposite was observed to be 3.48 eV. The synthesized material is crystalline, with an average crystallite size of 2.51 nm. The photocatalytic and ammonia gas sensing potential of the synthesized lead sulphide nanocomposite was explored. The study indicated that the synthesized nanocomposite was able to degradation methyl orange up to 80.31% and had a sensing response of 49% at 10 ppm concentration of ammonia gas. The study indicated that the synthesized ppy/lead sulphide nanocomposites can be used as a dual functional material for environmental applications.

Recent advances in integrated CO2capture and utilization: a review

In this review, we summarize the recent progress of dual functional materials application in integrated CO2capture and utilization and discuss the superiority of the integrated process from the perspective of industrial applications.

Encapsulated anion-dominated photocatalytic and adsorption performances for organic dye degradation and oxoanion pollutant capture over cationic Cu(i)-organic framework semiconductors.

Decontamination of industrial wastewater containing toxic organic dye molecules and oxoanions is urgently desirable for environmental sustainability and human health. Water-stable porous metal-organic frameworks (MOFs) have emerged as highly efficient photocatalysts and/or adsorbents for water purification through controllable integration of the constitutive requirements. To reveal the inclusion anion effect of microporous MOFs on wastewater treatment, two isostructural MOFs incorporating positive charge and semiconductive characteristics, {[Cu(tpt)]·3H2O·0.5SO4}n (1) and {[Cu(tpt)]·2H2O·ClO4}n (2, tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine), have been synthesized and employed as dual-functional materials for both dye photodegradation and oxoanion removal. The two MOFs possess the same 3-fold interpenetrating cationic backbones but are encapsulated by highly disordered sulfate or perchlorate in the open channels. These included anions have significantly tuned the hydrophilicity of the channels, extended the visible-light absorption, optimized the bandgap and decreased the conduction band potential. Under the low-energy irradiation of a 30 W LED lamp, MOF 1 has selectively and efficiently degraded rhodamine B compared to 2 with accelerated kinetics, resulting from the stronger reduction ability and less migration resistance of the photogenerated electrons. Instead, MOF 2 can quickly capture harmful MnO4- and Cr2O72- by exchanging with the entrapped ClO4-, with maximum adsorption amounts of 557 and 168 mg g-1, respectively, under ambient conditions. The improved decolorization of the aqueous solution over 2 benefits essentially from the shape and charge memory effect and the smaller hydration energy of ClO4- than SO42-. These interesting observations highlight the importance of the included anions inside the porous MOF semiconductors on wastewater treatment.

Modeling the CO2 capture and in situ conversion to CH4 on dual function Ru-Na2CO3/Al2O3 catalyst

Abstract A dynamic kinetic model is proposed to describe the CO2 adsorption and in situ hydrogenation to CH4 on a 4%Ru-10%Na2CO3/Al2O3 catalyst. One dimensional isothermal heterogeneous plug flow reactor model with axial dispersion is considered. The reaction network and kinetic equations are deduced from experimental data analysis. The molecular modeling includes competitive adsorption of CO2 and H2O on same adsorption site. During CO2 storage period, CO2 is adsorbed onto Na2O species to form Na2CO3. Alternatively, CO2 can be also adsorbed onto NaOH species releasing H2O to the gas phase, which can further be adsorbed onto free adsorption sites located downstream. It was needed to consider formation of unstable bicarbonates to fit the experimental data. During CO2 hydrogenation step, adsorbed carbonates are decomposed, promoted by the presence of H2. CH4 is then formed through the Sabatier’s reaction and the as-formed H2O interacts with regenerated adsorption sites. Temporal evolution of CO2, CH4 and H2O during CO2 storage and hydrogenation cycles is accurately predicted by the model, for a wide range of reactant concentrations and temperature (250−400 °C), gaining understanding on mechanisms and dynamics of the process on dual function materials.