Selective CO2 reduction to CH3OH over atomic dual-metal sites embedded in a metal-organic framework with high-energy radiation.

The efficient use of renewable X/γ-rays or accelerated electrons for chemical transformation of CO2 and water to fuels holds promise for a carbon-neutral economy; however, such processes are challenging to implement and require the assistance of catalysts capable of sensitizing secondary electron scattering and providing active metal sites to bind intermediates. Here we show atomic Cu-Ni dual-metal sites embedded in a metal-organic framework enable efficient and selective CH3OH production (~98%) over multiple irradiated cycles. The usage of practical electron-beam irradiation (200 keV; 40 kGy min-1) with a cost-effective hydroxyl radical scavenger promotes CH3OH production rate to 0.27 mmol g-1 min-1. Moreover, time-resolved experiments with calculations reveal the direct generation of CO2•‒ radical anions via aqueous electrons attachment occurred on nanosecond timescale, and cascade hydrogenation steps. Our study highlights a radiolytic route to produce CH3OH with CO2 feedstock and introduces a desirable atomic structure to improve performance.

Gamma Radiation Synthesis of Ag/P25 Nanocomposites for Efficient Photocatalytic Degradation of Organic Contaminant.

Titanium dioxide (TiO2) has garnered significant attention among various photocatalysts, whereas its photocatalytic activity is limited by its wide bandgap and inefficient charge separation, making the exploration of new strategies to improve its photocatalytic performance increasingly important. Here, we report the synthesis of Ag/P25 nanocomposites through a one-step gamma-ray radiation method using AgNO3 and commercial TiO2 (Degussa P25). The resulting products were characterized by powder X-ray diffraction, UV-Vis diffused reflectance spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The effect of free radical scavengers, feed ratios of Ag/P25, and dose rates on the photocatalytic activity of the Ag/P25 nanocomposites were systematically investigated using rhodamine B under Xenon light irradiation. The results showed that the Ag/P25 photocatalyst synthesized with a feed ratio of 2.5 wt% and isopropyl alcohol as the free radical scavenger at a dose rate of 130 Gy/min exhibited outstanding photocatalytic activity, with a reaction rate constant of 0.0674 min-1, much higher than that of P25. Additionally, we found that the particle size of Ag could be effectively controlled by changing the dose rate, and the Ag/P25 nanocomposites doped with smaller size of Ag nanoparticles performed higher photocatalytic activities. The synthesis strategy presented in this study offers new insight into the future development of highly efficient photocatalysts using radiation techniques.

Radiation synthesis of MXene/Ag nanoparticle hybrids for efficient photothermal conversion of polyurethane films.

Flexible conductive films based on light-to-heat conversion are promising for the next-generation electronic devices. A flexible waterborne polyurethane composite film (PU/MA) with excellent photothermal conversion performance was obtained by combination of PU and silver nanoparticle decorated MXene (MX/Ag). The silver nanoparticles (AgNPs) uniformly decorated on the MXene surface by γ-ray irradiation induced reduction. Because of the synergistic effect of MXene with outstanding light-to-heat conversion efficiency and the AgNPs with plasmonic effect, the surface temperature of the PU/MA-II (0.4%) composite with lower MXene content increased from room temperature to 60.7 °C at 5 min under 85 mW cm-2 light irradiation. Besides, the tensile strength of PU/MA-II (0.4%) increased from 20.9 MPa (pure PU) to 27.5 MPa. The flexible PU/MA composite film shows great potential in the field of thermal management of flexible wearable electronic devices.

Radiation synthesis of imidazolium-based polymeric ionic liquid gel for efficient adsorption of Re(VII) and U(VI) from aqueous solution.

In this research, an imidazolium-based polymeric ionic liquid (PIL) gel was effectively synthesized in one step via electron beam (EB) radiation technology. The synthesized gel with gel fraction of 78% under 80 kGy was used for the adsorption and separation of Re(VII) and U(VI). The structure of the gel was characterized by FTIR, SEM, BET, and XPS. Furthermore, batch adsorption was experimented to explore its performance of Re(VII) and U(VI) removal. The two adsorption processes all more fitted the Langmuir isotherm model with the maximum adsorption capacities of 892.9 mg/g for Re(VII) and 243.9 mg/g for U(VI). The adsorption reached equilibrium within 1 min for Re(VII), while within 4 min for U(VI), showing its greatly rapid adsorption rate because of its three-dimensional porous network structure. In addition, the separation experiments of Re/U replied that PIL gel could effectively separate Re(VII) from the simulated uranium leaching solution. Regeneration experiments present the good reusability of PIL gel. This work demonstrated the practical application of EB-radiation technology in the synthesis of PIL gel, which is a promising adsorbent for Re(VII) and U(VI) recovery .

Aminomethylpyridine isomers functionalized cellulose microspheres for TcO4-/ReO4- uptake: Structure-properties relationship and their application in different aquatic systems.

Technetium-99 (99Tc) is a long-lived radioactive nuclide that poses great threat to environment, hence selective removal of 99Tc from aquatic system is always an issue. Aminomethylpyridine (AMP) equipped with pyridine and amino, is a promising receptor for TcO4- and its surrogate ReO4-, thus it is of interest to explore and understand the structure-properties relationship of ReO4- adsorption related to n-AMP structure that differ in amino methyl position. In this work, three n-AMP functionalized cellulose microspheres (n-AMPR, n = 2, 3, 4) were synthesized and employed for TcO4-/ReO4- uptake. The effect of aminomethyl position on adsorption properties of n-AMPR for ReO4- were investigated and compared. Adsorption kinetics and adsorption isotherm showed that adsorption speed and adsorption capacity were in order of 3-AMPR > 2-AMPR > 4-AMPR. DFT calculation verified that the adsorption of ReO4- by n-AMPR was attributed to electrostatic interaction and hydrogen bonding interaction, the order of adsorption abilities of n-AMPR was due to that steric effect and hydrogen bond collaborated in stabilizing n-AMPR-ReO4- complexes. The column experiments demonstrated that 3-AMPR can be selectively remove ReO4- from simulated groundwater. More importantly, 99Tc column experiments showed that 3-AMPR had a better ability for actual radioactive TcO4-.

Recent progress in environmental applications of functional adsorbent prepared by radiation techniques: A review.

Environmental pollution has been accelerated due to fast urbanization and industrialization, and thus hazardous contaminants removal and valuable metal recovery have become urgent. Adsorption has become a promising technology for water treatment because of its advantages of low-cost, good reusability, low energy consumption, high capacity and high selectivity. Particularly, radiation techniques including radiation induced graft copolymerization and radiation crosslinking have been found to be widely utilized to exploit adsorbents for water treatment. In this review, the current status and progress of adsorbents in environmental pollution in the past decade are summarized, including adsorbents (in form of particles, fiber and fabric, membrane, novel nanomaterials) synthesized by radiation induced graft copolymerization and hydrogel-based adsorbents fabricated by radiation crosslinking. Finally, further perspective on the development and challenge of adsorbents by radiation techniques is also suggested.

Facile preparation of L-cysteine-modified cellulose microspheres as a low-cost adsorbent for selective and efficient adsorption of Au(III) from the aqueous solution.

A facile method to synthesize adsorbent based on cellulose modified by amino acid was developed. The novel L-cysteine-functionalized adsorbent for Au(III) recovery was synthesized via radiation grafting technique. Glycidyl methacrylate (GMA) was grafted on the surface of microcrystalline cellulose microsphere (MCC); next, ring-opening reaction was performed to immobilize L-cysteine. The adsorption abilities of the adsorbent (CysR) were tested. Batch experiments suggested that the maximum adsorption capacity of Au(III) is 714.28 mg/g calculated by Langmuir model. The adsorption kinetic data was followed by pseudo-second-order model. CysR showed excellent selectivity for Au(III) even the concentration of competing ions was all ten times than that of Au(III). The column experiments revealed that Au(III) could be efficiently adsorbed by CysR competition with equal amounts of Ni(II) and Zn(II). Moreover, XPS analysis demonstrated that the adsorbed Au(III) was reduced to Au(I) and Au(0). The adsorption performance certified that CysR was a promising adsorbent for Au(III) recovery.

Facile Preparation of EVOH-Based Amphoteric Ion Exchange Membrane Using Radiation Grafting Technique: A Preliminary Investigation on Its Application for Vanadium Redox Flow Battery.

A novel amphoteric ion exchange membrane (AIEM) was successfully prepared by one-step radiation grafting of sodium styrene sulfonate (SSS) and dimethylaminoethyl methacrylate (DMAEMA) onto ethylene-vinylalcohol copolymer (EVOH) powder and sequent transferring into film by casting method. Fourier transform infrared spectrometry (FT-IR), thermal gravimetric analyzer (TGA) and elemental analysis testified SSS and DMAEMA were successfully grafted onto EVOH. The ion exchange capacity, water uptake and proton conductivity of the resulting AIEM increased with grafting yield (GY). At the GY of 40.9%, the permeability of vanadium ions of AIEM was 3.98 × 10-7 cm2 min-1, which was better than Nafion117 membrane. Furthermore, the cost of this AIEM is much lower than that of Nafion117 membrane. This work provided a low cost and simple method for fabrication of the ion exchange membrane for vanadium redox flow battery (VRFB). Meanwhile, it also provided a new direction for the application of EVOH.

One-step radiation synthesis of agarose/polyacrylamide double-network hydrogel with extremely excellent mechanical properties.

A facile one-step radiation method is first developed to synthesize agarose/polyacrylamide (AG/PAM) double-network (DN) hydrogel. Compared to other synthetic methods of DN hydrogels, our synthesis method endows the resultant AG/PAM DN hydrogel with not only top-level tensile properties with a tensile strength of 1263 ± 59 kPa and an elongation at break of 3406 ± 143%, but also highest compression properties with a compression strength of 140 ± 3 MPa and a fracture compression strain of above 99.9%. An expanding-necking phenomenon during compression process of AG/PAM DN hydrogel were observed. We propose a chain pushing-in model to interpret the energy dissipation mechanism accounting for the super-compressibility of AG/PAM DN hydrogel. This novel radiation synthesis strategy provides an insight into the development of DN hydrogels with extremely excellent mechanical properties.

Oxidized multiwall carbon nanotube/silicone foam composites with effective electromagnetic interference shielding and high gamma radiation stability.

Oxidized multiwall carbon nanotubes (o-MWCNTs) were introduced into silicone foam to fabricate an electromagnetic interference (EMI) shielding material with high gamma radiation stability by solution casting followed by foaming and cross-linking reactions. The as-prepared o-MWCNT/silicone foam composites exhibited excellent mechanical strength and effective EMI shielding properties with superior EMI shielding effectiveness (SE) ranging from 26 to 73 dB at a 0.5-6.4 mm thickness with 30 wt% o-MWCNTs in the Ku band. Moreover, the composites have good gamma radiation stability, showing relatively stable EMI shielding properties and an improvement of hardness and pressure resistance after gamma irradiation with the absorbed dose of 500 kGy. These results indicate that the o-MWCNT/silicone foam composite is an attractive candidate for EMI shielding in some ionizing radiation environments.

Tuning the Composition and Structure of Amorphous Molybdenum Sulfide/Carbon Black Nanocomposites by Radiation Technique for Highly Efficient Hydrogen Evolution.

Amorphous molybdenum sulfide/carbon black (MoSx/C) nanocomposites are synthesized by a facile one-step γ-ray radiation induced reduction process. Amorphous MoSx shows better intrinsic activity than crystalline MoS2. And the composition and amorphous structure of MoSx could be expediently tuned by absorbed dose for excellent catalytic activity. Meanwhile, the addition of carbon black leads to a significant decrease of charge transfer resistance and increase of active sites of MoSx/C composite. Consequently, MoSx/C nanocomposite shows Pt-like catalytic activity towards hydrogen evolution reaction (HER), which requires an onset over potential of 40 mV and over potential of 76 mV to achieve a current density of 10 mA cm-2, and the corresponding Tafel slope is 48 mV decade-1. After 6000 CV cycles, the catalytic activity of MoSx/C shows no obvious decrease. However, when platinum (Pt) foil is used as counter electrode, MoSx/C composite show better catalytic activity abnormally after long-term cycling tests. The dissolution of Pt was observed in HER and the Pt dissolution mechanism is elucidated by further analyzing the surface composition of after-cycling electrodes, which offers highly valuable guidelines for using Pt electrode in HER.

Radiation synthesis and performance of novel cellulose-based microsphere adsorbents for efficient removal of boron (III).

A novel cellulose-based microsphere containing glucamine groups, referred as CVN, was successfully synthesized by radiation-induced graft polymerization of 4-vinylbenzyl chloride onto cellulose microspheres and subsequent functionalization with N-methyl-d-glucamine. The adsorption by CVN for boron (III) from aqueous solutions was evaluated systematically by batch adsorption technique. Langmuir models could fit well with the adsorption behavior of CVN. The CVN adsorbents exhibited a high adsorption capacity up to 12.4mgg-1 towards boron (III) over the wide pH range of 5-8. After the addition of chloride salts, the boron uptake of CVN was enhanced that was attributed to the compensation of the surface charge generated by boron (III) adsorption leading to favor the adsorption. At high concentrations of salts, the ionic strength and different salts have no effect on the adsorption of boron(III). This work provides a new sustainable, cost effective material as a promising specific adsorbent for the removal of boron (III) from saline solutions.

Radiation Effect of Carboxyl-Functionalized Task-Specific Ionic Liquids on UO22+ Removal: Experimental Study with DFT Validation.

Experimental study with DFT validation on the effect of radiation on 1-carboxymethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([HOOCCH2MIM][NTf2]) as a solvent and extractant in rapid homogeneous extraction of UO22+ was performed for the first time. The radiolytic products of the anions and cations of [HOOCCH2MIM][NTf2] were identified by 19F NMR and high-resolution ESI-MS, respectively, and they were attributed to a decrease in UO22+ partitioning. Experimental study with DFT validation for complexing reactions between [HOOCCH2MIM][NTf2] and radiolytic products proved that F- competition was one of the main reasons for the decrease in UO22+ partitioning. However, UO22+ partitioning in irradiated [HOOCCH2MIM][NTf2] can largely be recovered after thorough water washing because of the removal of radiolytic products of [NTf2]-.

Comparison with adsorption of Re (VII) by two different γ-radiation synthesized silica-grafting of vinylimidazole/4-vinylpyridine adsorbents.

Two silica gel based adsorbents for Re (VII), i.e. SS-MPTS-VIMH and SS-MPTS-VPQ, were synthesised. Silica gel was used as the matrix for γ-radiation grafting, and the monomer of 1-vinyl imidazole (VIM) and 4-vinylpyridine (4-VP) was grafted onto the silica silanized by methacryloxy propyl trimethoxyl silane, respectively. A VIM concentration of 2molL-1 and an absorbed dose of 30kGy were the optimal grafting conditions for adsorbent SS-MPTS-VIM, and a 4-VP concentration of 4molL-1 and an absorbed dose of 40kGy were the optimal grafting conditions for adsorbent SS-MPTS-VP. At the certain condition, the grafting yield of SS-MPTS-VIM was 30.1% and that of SS-MPTS-VP was 21.0%. The adsorption capacity of adsorbent SS-MPTS-VIMH was 145.99mgg-1 and that of SS-MPTS-VPQ was 71.08mgg-1 according to the Langmuir model. The adsorbent SS-MPTS-VPQ had better adsorption properties of acid resistance and anti-interference than SS-MPTS-VIMH. Dynamic column experiments showed that protonated adsorbent SS-MTPS-VIMH could be recycled with good performance while quaternized adsorbent SS-MPTS-VPQ could not. The adsorbent SS-MPTS-VIMH belongs to weak anion exchange adsorbent and SS-MPTS-VPQ belongs to strong anion exchange adsorbent. This study paves a way to the synthesis and application of a novel silica base adsorbents for Re (VII).

Radiation cross-linked collagen/dextran dermal scaffolds: effects of dextran on cross-linking and degradation.

Ionizing radiation effectively cross-links collagen into network with enhanced anti-degradability and biocompatibility, while radiation-cross-linked collagen scaffold lacks flexibility, satisfactory surface appearance, and performs poor in cell penetration and ingrowth. To make the radiation-cross-linked collagen scaffold to serve as an ideal artificial dermis, dextran was incorporated into collagen. Scaffolds with the collagen/dextran (Col/Dex) ratios of 10/0, 7/3, and 5/5 were fabricated via (60)Co γ-irradiation cross-linking, followed by lyophilization. The morphology, microstructure, physicochemical, and biological properties were investigated. Compared with pure collagen, scaffolds with dextran demonstrated more porous appearance, enhanced hydrophilicity while the cross-linking density was lower with the consequence of larger pore size, higher water uptake, as well as reduced stiffness. Accelerated degradation was observed when dextran was incorporated in both the in vitro and in vivo assays, which led to earlier integration with cell and host tissue. The effect of dextran on degradation was ascribed to the decreased cross-linking density, looser microstructure, more porous and hydrophilic surface. Considering the better appearance, softness, moderate degradation rate due to controllable cross-linking degree and good biocompatibility as well, radiation-cross-linked collagen/dextran scaffolds are expected to serve as promising artificial dermal substitutes.

Radiolysis of crown ether-ionic liquid systems: identification of radiolytic products and their effect on the removal of Sr(2+) from nitric acid.

The quantitative analysis and identification of the radiolytic products of dicyclohexano-18-crown-6 (DCH18C6), 4',4''(5'')-di-tert-butyldicyclohexano-18-crown-6 (DtBuCH18C6) and benzo-18-crown-6 (B18C6) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C4mim][NTf2]) ionic liquid after irradiation were performed for the first time. It was found that the yield for radiolytic destruction of DCH18C6 and DtBuCH18C6 was less than that for B18C6. The main radiolytic products were identified as substituted crown ethers formed between crown ether and active radicals such as methyl, trifluoromethyl, butyl, and [C4mim]˙ radicals generated during the irradiation of the crown ether-[C4mim][NTf2] system. The radiation effect on the Sr(2+) partitioning of the crown ether-[C4mim][NTf2] system shows further that DCH18C6-[C4mim][NTf2] and DtBuCH18C6-[C4mim][NTf2] still have good extractability for Sr(2+) after irradiation. The extraction ability of DCH18C6-[C4mim][NTf2] and DtBuCH18C6-[C4mim][NTf2] system for Sr(2+) decreased by 14.4% and 18.2% even at 500 kGy, respectively.

Stimuli responsive deswelling of radiation synthesized collagen hydrogel in simulated physiological environment.

Collagen hydrogels were prepared via radiation crosslinking. The simulated physiological environmental effects related to their biomedical applications on the volume phase transition of collagen hydrogel were studied, that is stimuli response to ions, temperature, and pH. The deswelling behavior of collagen hydrogel depends on the salt concentration, temperature, pH, and the hydrogel preparation procedure. Meanwhile, hydrogel structure related to the volume phase transition was investigated by FTIR, fluorescence spectrum, and HR-MAS NMR. Deswelling in salt solution caused little change on collagen conformation, and a denser network led to more significant tyrosine-derived fluorescence quenching. Hydrogen bonding between hydrated water and collagen polypeptide chain was dissociated and the activity of hydrophobic side chain increased, inducing a higher extent of contraction with the increasing of salt concentration. Moreover, salt solution treatments weakened the electrostatic interactions, side chains interactions, and hydrogen bonding of collagen hydrogel, which reduced the thermal stability of collagen hydrogel. Comparing with cell-free collagen hydrogel contraction, fibroblasts did not aggravate contraction of collagen hydrogel significantly. This study elucidated the deswelling mechanism of radiation crosslinked collagen hydrogel in simulated physiological environment and provides strategies for controlling the stimuli response of collagen hydrogel in biomedical application.

Selective adsorption of Hg(II) by γ-radiation synthesized silica-graft-vinyl imidazole adsorbent.

Silica-based adsorbent was prepared by γ-radiation induced grafting of vinyl imidazole (VIM) onto the silanized silica, which was silanized by chlorotrimethylsilane (TMCS). The effects of monomer concentration and absorbed dose on the grafting yield were investigated to optimize the reaction conditions. Thermodynamic analysis, FTIR analysis and XPS spectra manifested that VIM was successfully grafted onto the silica surface. The SS-g-VIM adsorbent had excellent selectivity for Hg(II) adsorption in mixture divalent cationic metal solution and a high adsorption capacity of Hg(II). The theoretical maximum adsorption capacity was calculated to be 355.9 mg g(-1) (1.774 mmol g(-1)) in HgCl(2)/HNO(3) solution at pH 5 at room temperature. The adsorption kinetics and adsorption isotherm were investigated. It was found that the Langmuir isotherm model fitted well with the adsorption process and the adsorption of Hg(II) onto SS-g-VIM adsorbent could be considered as a spontaneous, endothermic and chemical sorption process. The comprehensive results suggested that SS-g-VIM adsorbent has potential application for the removal of Hg(II) from wastewater.

Radiation effects on microcrystalline cellulose in 1-butyl-3-methylimidazolium chloride ionic liquid.

The radiation processing of cellulose in ionic liquids (ILs) demands a comprehensive knowledge of radiation effects on cellulose in ILs. Herein, gamma radiation-induced degradation kinetics of microcrystalline cellulose (MCC) in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) was studied by viscometry. The intrinsic viscosity of MCC in [Bmim]Cl decreased slightly with increasing dose; while chemical structure and crystalline state of cellulose has no obvious change up to 300 kGy. The radiation degradation rate constant (k) of MCC in [Bmim]Cl was 2.60×10(-7)/kGy, lower than that of solid cellulose, but higher than that in N-methylmorpholine-N-oxide (NMMO) solvent. Furthermore, k value decreased to 1.12×10(-7)/kGy in dimethyl sulfoxide (DMSO)/[Bmim]Cl system due to the free radicals scavenging of DMSO. The radicals generated during irradiation play main role in the radiation degradation of MCC in [Bmim]Cl. This work provides a new way to control the average molecular weight of cellulose by radiation-induced degradation of cellulose in ILs.

Efficient removal of caesium ions from aqueous solution using a calix crown ether in ionic liquids: mechanism and radiation effect.

The removal of radioactive (137)Cs from nuclear waste is of great importance for both the environment and energy saving. Herein, we report a study on the removal of Cs(+) using a calix crown ether bis(2-propyloxy)calix[4]crown-6 (BPC6) in ionic liquids [C(n)mim][NTf(2)], where [C(n)mim](+) is 1-alkyl-3-methylimidazolium and [NTf(2)](-) is bis(trifluoromethylsulfonyl)imide. The BPC6/[C(n)mim][NTf(2)] system is highly efficient in removing Cs(+) from aqueous solution, even at a low concentration of BPC6. HNO(3) and metal ions such as Na(+), Al(3+) in the aqueous phase interfered with the extraction of Cs(+) by competitive interaction with BPC6 and/or salting-out effect. UV analysis confirmed that the extraction of Cs(+) by the BPC6/[C(n)mim][NTf(2)] system involves a dual extraction mechanism, i.e., via exchange of BPC6.Cs(+) complex or Cs(+) by [C(n)mim](+). Irradiation of [C(4)mim][NTf(2)] dramatically decreases Cs(+) partitioning in the ionic liquid phase by the competitive interaction of radiation-generated H(+) with BPC6, while irradiation of BPC6/[C(4)mim][NTf(2)] decreases Cs(+) partitioning more markedly due to the radiolysis of BPC6.