RSC Advances

Ren, Gangli; Zhao, Ke; Zhao, Lang

doi: 10.1039/d0ra08076dpmid: 35520870

MIL-88A with different sizes was prepared by hydrothermal method by changing the content of ZnO. The samples were characterized by SEM, TEM, XRD, XPS and FT-IR. The synthesized material was used for the removal of methylene blue dye in a Fenton-like reaction, and the optimal reaction conditions were studied through single factor experiments. The experimental results show that when the molar ratio of the amount of ZnO introduced to FeCl3·6H2O is 1 : 1, the obtained materials have better catalytic performance than others. Under the optimal conditions, MIL-88A(Fe1Zn1) has the best catalytic performance for 300 mg L−1 methylene blue. The removal rate can reach 96.15% within 40 minutes.

Zheng, Ju-Gong; Ren, Guang-Yuan; Shi, Jun; Yang, Ting; Tang, Yue-Feng; Chen, Yan-Feng

doi: 10.1039/d0ra08274kpmid: 35520846

In this study, a facile yet efficient interfacial hydrothermal process was successfully developed to fabricate LiMnPO4/C composites. In this strategy, the walls of carbon nanotubes were employed as heterogeneous nucleation interfaces and biomass of phytic acid (PA) as an eco-friendly phosphorus source. By comparing the experimental results, a reasonable nucleation-growth mechanism was proposed, suggesting the advantages of interfacial effects. Meanwhile, the as-synthesized LiMnPO4/C samples exhibited superior rate performances with discharge capacities reaching 161 mA h g−1 at C/20, 134 mA h g−1 at 1C, and 100 mA h g−1 at 5C. The composites also displayed excellent cycling stabilities by maintaining 95% of the initial capacity over 100 continuous cycles at 1C. Electrochemical impedance spectroscopy showed that the superior electrochemical performances were attributed to the low charge-transfer resistance and elevated diffusion coefficient of lithium ions. In sum, the proposed approach for the preparation of LiMnPO4/C composites looks promising for future production of composite electrode materials for high-performance lithium-ion batteries.

Jin, Zongzi; Peng, Ranran; Xia, Yunpeng; Wang, Zhenbin; Liu, Wei

doi: 10.1039/d0ra08097gpmid: 35520833

Understanding the electrode properties at the atomistic level is of great benefit to the evaluation of electrode performance and design of better electrode materials in solid oxide fuel cells. In this work, density functional theory (DFT) calculations are employed to investigate the formation and conducting behaviors of oxygen vacancies and proton defects in Ruddlesden–Popper oxide SrEu2Fe2O7 (SEFO), which has been experimentally characterized as a promising cathode. The calculation results suggest both oxygen vacancies and proton defects can be formed in SEFO, and especially, the formation of these defects is largely dependent on oxygen sites in the special crystal structure with alternative stacking of rock-salt layers and double-layered perovskite slabs. The oxygen vacancies within the perovskite slabs have very low formation energies, but demonstrate high energy barriers for migration and low hydration properties; while in the case of those in the rock salt layers, it’s contrary. Interestingly, protons have similar migration abilities in the perovskite slabs and rock salt layers. And therefore, increasing the vacancy concentration of the rock salt layer is beneficial to increase the concentration of proton defects and to improve the proton conductivity. DFT calculations also indicate that substituting Zn for Fe in SEFO can largely depress the oxygen vacancy formation energy, which helps to increase the concentration of both defects. Importantly, the energy barriers for migration of both oxygen ions and protons are barely enhanced, implying a negligible trapping effect of the Zn dopant.

More, Sagar A.; Halor, Rajendra G.; Shaikh, Raees; Bisen, Gauri G.; Tarkas, Hemant S.; Tak, Swapnil R.; Bade, Bharat R.; Jadkar, Sandesh R.; Sali, Jaydeep V.; Ghosh, Sanjay S.

doi: 10.1039/d0ra07926jpmid: 35520837

A comprehensive study regarding the effect of different solvent vapours on organolead halide perovskite properties is lacking. In the present work, the impact of exposing CH3NH3PbI3 films to the vapours of commonly available solvents has been studied. The interaction with perovskite has been correlated to solvent properties like dielectric constant, molecular dipole moment, Gutmann donor number and boiling point. Changes in the crystallinity, phase, optical absorption, morphologies at both nanometer and micrometer scale, functional groups and structures were studied using X-ray diffraction, UV-visible absorption, FE-SEM, FTIR and Raman spectroscopies. Among the aprotic solvents DMSO and DMF vapours deteriorate the crystallinity, phase, and optical, morphological and structural properties of the perovskite films in a very short time, but due to the difference in solvent property values acetone affects the perovskite properties differently. Polar protic 2-propanol and water vapours moderately affect the perovskite properties. However 2-propanol can solvate the organic cation CH3NH3+ more efficiently as compared to water and a considerable difference was found in the film properties especially the morphology at the nanoscale. Nonpolar chlorobenzene vapour minutely affects the perovskite morphology but toluene was found to enhance perovskite crystallinity. Solvent properties can be effectively used to interpret the coordination ability of a solvent. The present study can be immensely useful in understanding the effects of different solvent vapours and also their use for post-deposition processing (like solvent vapour annealing) to improve their properties.

Hoseini, Akram-Alsadat; Farhadi, Saeed; Zabardasti, Abedin; Siadatnasab, Firouzeh

doi: 10.1039/d0ra07042dpmid: 35520823

In this work, an inorganic–organic hybrid nanomaterial, P2Mo18/MIL-101(Cr), based on Wells–Dawson-type (NH4)6P2Mo18O62 polyoxometalate (abbreviated as P2Mo18) and the MIL-101(Cr) metal–organic framework was fabricated by the reaction of (NH4)6P2Mo18O62, Cr(NO3)3·9H2O and terephthalic acid under hydrothermal conditions. The as-prepared recyclable nanohybrid was fully characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR) equipped with energy dispersive X-ray microanalysis (EDX), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy and Brunauer–Emmett–Teller (BET) specific surface area studies. All the analyses confirmed the successful insertion of P2Mo18O626− heteropolyanion within the cavities of MIL-101(Cr). The encapsulated MIL-101(Cr) showed a considerable decrease in both pore volume and surface area compared with MIL-101(Cr) due to incorporation of the very large Dowson-type polyoxometalate into the three-dimensional porous MIL-101(Cr). The nanohybrid had a specific surface area of 800.42 m2 g−1. The adsorption efficiency of this nanohybrid for removal of methylene blue (MB), rhodamine B (RhB), and methyl orange (MO) from aqueous solutions was evaluated. Surprisingly, the composite not only presented a high adsorption capacity of 312.5 mg g−1 for MB, but also has the ability to rapidly remove 100% MB from a dye solution of 50 mg L−1 within 3 min. These results confirmed that this adsorbent is applicable in a wide pH range of 2–10. The nanohybrid showed rapid and selective adsorption for cationic MB and RhB dyes from MB/MO, MB/RhB, MO/RhB and MB/MO/RhB mixed dye solutions. The equilibrium adsorption data were better fitted by the Langmuir isotherm. Kinetics data indicate that the adsorption of the dye follows a pseudo-second order kinetics model. Also, this material could be effortlessly separated and recycled without any structural modification. Accordingly, it is an efficient adsorbent for removing cationic dyes.

Abdi, Gisya; Filip, Anna; Krajewski, Michał; Kazimierczuk, Krzysztof; Strawski, Marcin; Szarek, Paweł; Hamankiewicz, Bartosz; Mazej, Zoran; Cichowicz, Grzegorz; Leszczyński, Piotr J.; Fijałkowski, Karol J.; Szczurek, Andrzej

doi: 10.1039/d0ra08143dpmid: 35520861

The discovery of properties and applications of unknown materials is one of the hottest research areas in materials science. In this work, we navigate a route towards these goals by the development of a new type of graphyne nanostructure. It is synthesised by a Sonogashira cross-coupling reaction of 1,3,5-triethynylbenzene with cyanuric chloride resulting in an extended carbon-based material called TCC. Also, we modify the obtained TCC via fluorination using XeF2 at various concentrations to investigate the effect of fluorination on the triple bonds and the conjugated structure of graphyne. In this study, we put special emphasis on the determination of the impact of the fluorine content and the type of CF functionalities on the morphology, chemical and electronic structure, biocompatibility, electrical conductivity and possible applicability as anode materials for Li-ion batteries. The obtained results indicate that the character of C–F bonds influences the final properties of fluorinated materials. The polar C–F bonds are preferable for cell proliferation while CF2 groups are most suitable for battery devices, however, the appearance of PTFE-like units may have a negative impact on battery specific capacitance as well as on cell viability.

Li, Hua; Huang, Lumei; Jiang, Hailong; Fang, Jianyang; Guo, Zhide; Gao, Fei; Chen, Mei; Xu, Duo; Li, Zijing; Zhang, Xianzhong

doi: 10.1039/d0ra07186bpmid: 35520872

A novel “turn-off” strategy for controllable radionuclide clearance is established. 1,4-dihydropyridine (DHP) is used as a conditional linker to connect a radioisotope labeled moiety and nano-agent. A highly specific, sensitive and effective C–C bond cleavage of DHP happens in vivo when treated with nitric oxide which is provided by glyceryl trinitrate (GTN). The radioactive cut-off part from the nanoparticle is observed to be cleared quickly by microSPECT-CT. 3–5 times decreases of radioactivity in the blood, kidneys, intestine, heart and lungs are observed after GTN treatment in a biodistribution assay. The radioactivity redistribution indicates that the radioactive leaving part is indeed cut off and the radionuclide metabolism accelerated. Organ level internal dose assessment reveals the GTN treated groups carry only ½ the radiation dose of the control group. Collectively, a feasible pathway for controllable radionuclide clearance is for the first time provided for high contrast and low radiation nuclear imaging.

Wang, Zhipeng; Zhang, Yixiang; Liu, Jingjing; Song, Lianjun; Wang, Xueyu; Yang, Xiuying; Xu, Chao; Li, Jun; Ding, Songdong

doi: 10.1039/d0ra08841bpmid: 35520876

Dithiophosphinic acids (DPAHs, expressed as R1R2PSSH) are a type of sulfur-donor ligand that have been vastly applied in hydrometallurgy. In particular, DPAHs have shown great potential in highly efficient trivalent actinide/lanthanide separation, which is one of the most challenging tasks in separation science and is of great importance for the development of an advanced fuel cycle in nuclear industry. However, DPAHs have been found liable to undergo oxidative degradation in the air, leading to significant reduction in the selectivity of actinide/lanthanide separation. In this work, the atmospheric degradation of five representative DPAH ligands was investigated for the first time over a sufficiently long period (180 days). The oxidative degradation process of DPAHs elucidated by ESI-MS, 31P NMR, and FT-IR analyses is R1R2PSSH → R1R2PSOH → R1R2POOH → R1R2POO–OOPR1R2, R1R2PSSH → R1R2PSS–SSPR1R2, and R1R2PSSH → R1R2PSOH → R1R2POS–SOPR1R2. Meanwhile, the determination of pKa values through pH titration and oxidation product by PXRD further confirms the S → O transformation in the process of DPAH deterioration. DFT calculations suggest that the hydroxyl radical plays the dominant role in the oxidation process of DPAHs and the order in which the oxidation products formed is closely related to the reaction energy barrier. Moreover, nickel salts of DPAHs have shown much higher chemical stability than DPAHs, which was also elaborated through molecular orbital (MO) and adaptive natural density portioning (AdNDP) analyses. This work unambiguously reveals the atmospheric degradation mechanism of DPAHs through both experimental and theoretical approaches. At the application level, the results not only provide an effective way to preserve DPAHs but could also guide the design of more stable sulfur-donor ligands in the future.

Kang, Gil-Seon; Baek, Youngbin; Yoo, Ji-Beom

doi: 10.1039/d0ra07262apmid: 35520838

Surface hydrophobicity of anodic aluminum oxide (AAO) membranes was controlled via carbon coating using the CVD method or O2 plasma treatment with insignificant changes of pore diameter. This study first demonstrated that a larger hydrophobic pore surface and hydrophilic membrane surface are favorable for developing high performance membranes.

Chen, Qizhi; Yang, Yong; Luo, Hang; Liu, Zuohua; Tong, Zhangfa; Tao, Changyuan; Du, Jun

doi: 10.1039/d0ra06639gpmid: 35520869

Ce modified MnOx/SAPO-34 was prepared and investigated for low-temperature selective catalytic reduction of NOx with ammonia (NH3-SCR). The 0.3Ce–Mn/SAPO-34 catalyst had nearly 95% NO conversion at 200–350 °C at a space velocity of 10 000 h−1. Microporous SAPO-34 as the support provided the catalyst with increased hydrothermal stability. XPS and H2-TPR results proved that the Mn4+ and Oα content increased after incorporation of Ce, this promoted the conversion of NO at low temperature via a ‘fast SCR’ route. NH3-TPD measurements combined oxidation experiments of NO, NH3 indicated the reduction of both the surface acidity and the amount of acid sites, which effectively decreased the NH3 oxditaion to NO or N2O at elevated temperature and promoted the catalytic selectivity for nitrogen. A redox cycle between manganese oxide and Ce was assumed for the active oxygen transfer and facilitated the catalyst durability.