Journal of Materials Chemistry C
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2020
·Vol. 8
·期 39
·13612-13620
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IF 7.059
Majid Basharat,Yasir Abbas,Djebar Hadji,Zahid Ali,Shuangkun Zhang,Hanlin Ma,Zhanpeng Wu,Wei Liu
Covalent inorganic–organic hybrid frameworks (CIOFs) composed of inorganic heterocycles covalently linked to organic building blocks are a relatively unexplored and fertile area of research compared to the covalent organic frameworks. Herein, we report the selective light responsive CIOFs prepared by considering energy gaps (Egs) of the inorganic heterocycle (P3N3Cl6) (Eg 5.745 eV), organic building block (4,4-sulfonyldiphenol) (Eg 4.05 eV), and triazine heterocycle (1,3,5-triazine-2,4,6-triamine) (Eg 4.79 eV) under mild reaction conditions (by P–O–C and P–NH–C bond formation). The morphology of CIOF-I (prepared from hexachlorocyclotriphosphazene and 4,4-sulfonyldiphenol) is micro-spherical (diameter, ca. 0.6–1 μm), whereas that of CIOF-II (prepared from hexachlorocyclotriphosphazene and 1,3,5-triazine-2,4,6-triamine) is micro-spherical (diameter, ca. 0.5–1 μm) as well as tubular. The X-ray diffraction (XRD) analysis showed that these CIOFs are amorphous in nature. The luminescence studies of both CIOFs have shown a selective response to different lights; when excited under UV light at a wavelength of 365 nm, the CIOFs showed cyan emission, while under visible region 420 nm and 546 nm excitations, the emission shifts to green and red, respectively. CIOF-I demonstrated maximum emission at 454 nm (Ex. 365 nm), 487 nm (Ex. 420 nm), and 708 nm (Ex. 546 nm), while CIOF-II exhibited maximum emission at 460 nm (Ex. 365 nm), 478 nm (Ex. 420 nm), and 604 nm (Ex. 546 nm). The density functional theory (DFT) studies were performed based on Gaussian 09 (B3LYP/6-311+G (d,p)) for the core structure of CIOFs’ HOMO and LUMO levels (CIOF-I −6.54 eV, −2.62 eV and CIOF-II −6.44 eV, −2.55 eV), and Egs (3.92 eV and 3.84 eV) which are in good agreement with the experimental values. The mechanism behind the demonstration of similar emission colors by two different chemical structures is also underpinned. The selective response towards different lights is ascribed to the aggregation/clustering-induced/triggered emission (AIE/CTE) and restricted rotation emission (RRE) due to the crosslinking of the wider energy gap inorganic heterocycle and organic linkers. This study may grab the attention of researchers to study the inorganic heterocycle centered selective light responsive materials due to their extensive application prospects.
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Analytical Methods
·
2020
·Vol. 12
·期 7
·943-950
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IF 2.596
Dandan Li,Lihua Gong,Zhenyang Qiao,Congcong Zhu,Qiaojuan Jia,Huajie Kong,Shuyan Jiao
A novel highly selective colorimetric fluorescence probe, POPH, has been successfully synthesized and it shows remarkable selective and sensitive response to Cu2+ in aqueous media (HEPES buffer, pH = 7.4). The fluorescence of probe POPH immediately decreased when 1.1 equiv. of Cu2+ was added to a solution of probe POPH, accompanied by color change from wathet blue to colorless under 365 nm UV lamp illumination. The possible bonding model of probe POPH with Cu2+ was examined through HRMS, FESEM, TEM, FTIR spectroscopy and DFT calculations. Moreover, the probe POPH could be used for monitoring Cu2+ in living cells using laser scanning confocal microscopy.
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CARBOHYDRATE POLYMERS
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2019
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IF 6.044
Chunfu Shao,Qiang Shao,Xiaoyi Wang,Jun Ling,Xiao Guo,Yulin Ning,Yujie Dai,Shiru Jia,Yuanyuan Qiao,Changwen Li,Kai Zhao
The OH induced cellulose degradation was examined by analyzing the reaction products of Fenton’s regents with cellobiose. Many degradation products including C2-C5 compounds such as oxaldehyde, malonaldehyde and 2-hydroxysuccinaldehyde were detected by GC MS analysis. Four reaction pathways for the formation of some degradation products were obtained from ReaxFF kinetics simulation and validated by the DFT quantum chemistry calculation at B3LYP/6-31+g(d,p) level. It was found that the H-abstraction from OH of the glucose unit by OH can cause saccharide ring open and breakage of the glycosidic bond. Pathways 1–4 showed that the glucose unit can react with OH consecutively to produce small molecular products with carbon atoms less than 6. This study indicated that ReaxFF reaction kinetics is a powerful tool for the exploration of the degradation mechanism of cellulose induced by OH at room temperature, which correlated well with the experimental results and was validated by DFT calculation.
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Journal of Water Process Engineering
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2024
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IF 6.3
Fengyang Liu,Wenjie Zou,Wei Zhao
Chitosan-based flocculants represent a highly promising alternative to industrial synthetic organic flocculants, offering exceptional environmental friendliness and efficiency. The carboxymethyl chitosan- graft -poly (acrylamide-dimethyl diallyl ammonium chloride) (CMCPD) and chitosan- graft -poly (acrylamide-dimethyl diallyl ammonium chloride) (CPD) were successful synthesized using UV-induced graft polymerization. The flocculation behavior and mechanism of these two chitosan-graft-copolymers on kaolinite suspension were investigated employing settling test and density functional theory calculation of the structural units of CMCPD and CPD on the kaolinite (00–1) surface. Experimental results indicated that the CMCPD had a greater settling rate of 19.47 m/h at the dosage of 80 g/t than CPD (12.96 m/h). The simulation results revealed distinct adsorption conformations of CMCPD and CPD units on the kaolinite (00–1) surface, characterized by an inclined posture and a horizontal posture, respectively. The stable adsorption of CPD can be attributed to the electrostatic attraction, which is evidenced by its higher adsorption energy (−4.74 eV) on the kaolinite (00–1) surface compared to CMCPD (−3.63 eV). It should be noted that both the adsorption energy and conformation play crucial roles in determining the flocculation efficiency of a flocculant. The inclined adsorption of CMCPD not only displayed electrostatic attraction but also enhanced its bridging ability, leading to a rapid increase in floc size and settling rate. The settling performance was significantly influenced by the bridging effect exerted by flocculants. This study holds great significance for the advancement of novel and efficient flocculant development.
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SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Xiaonuo Xu,Yueli Wen,Yuxuan Zhao,Bin Wang,Maohong Fan,Zhiju Chen,Shiyun Guo,Wei Huang
As the primary byproduct of paper making industry, alkali lignin can lead to biological anoxia and disrupt aquatic ecosystems. Application of it in wastewater treatment can not only realize its high value utilization, but realizing reduction of carbon emission. In this study, a renewable alkali lignin-modified MOFs adsorbent AL@PCN-250 was prepared by in-situ synthesis strategy and was used to adsorb and remove Methylene blue (MB) and Rhodamine B (RhB) from textile wastewater. The effects of adsorbent dosage, pH, contact time, and initial concentration on the adsorption behavior of RhB and MB by AL@PCN-250 were investigated to evaluate its adsorption capacity and reusability. The results showed that the maximum adsorption capacities of AL@PCN-250 for RhB and MB were 299.292 mg g −1 and 209.260 mg g −1 , respectively. The Sips models fitted the adsorption isotherms well, indicating that the adsorption sites on the surface of AL@PCN-250 are heterogeneous, with varying affinities for the adsorbates. Notably, after six cycles, the removal efficiency of AL@PCN-250 for the two dyes remained above 80 %. Experimental and theoretical calculations revealed that adsorption mainly involved hydrogen bonding, Van der Waals’ force, π-π interactions, and electrostatic interactions. This study provides new insights into the high-value utilization of lignin and the synthesis of efficient adsorbents.
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Journal of Water Process Engineering
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2024
·
IF 6.3
Xinxin Shi,Yinxia Nian,Yixing Wang,Junjie Zheng,Xufeng Dong,Hao Huang,Julian Shi,Yang Liu,Weihuang Zhu,Pengfei Guo,Tinglin Huang
Recovery of nitrogen from industrial wastewater through electrochemically reducing nitrate to ammonia attracts increasing research interest. However, conventional two-dimensional (2D) planar substrates limit the catalyst activity. Loading catalysts on three-dimensional (3D) electrodes with high specific surface area is an effective way to enhance electrode catalytic activity. In this work, we fabricated a 3D carbon brush electrode loaded with CuNi nano-alloy (CuNi/CB). The CuNi/CB achieved ammonia yield rate (NH 3 -N yr ) of 479.1 ± 5.3 μg h −1 cm −2 within 0.5 h, with a Faraday efficiency of 73.4 %. Compared with CuNi supported on carbon paper (CP), carbon felt (CF) and carbon cloth (CC), the NH 3 -N yr of CuNi/CB were higher by 114.7, 35.2, and 26.8 times, respectively. The outstanding performance of CuNi/CB benefited from the higher specific surface area of the 3D carbon brush. Additionally, Ni doping in the CuNi catalyst reduced the accumulation of NO 2 − by 39.7 % and increased the NH 3 -N yr by 82.9 %. Density functional theory (DFT) revealed that a shift of the d-band center toward Fermi level was likely the fundamental reason for the enhanced activity of the CuNi catalyst, comparing with single Cu catalyst. These findings offer broad prospects of efficient nitrate electroreduction to ammonia by the novel 3D electrode.
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Surfaces and Interfaces
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2024
·
IF 5.7
Yuling Lu,Yuxing Peng,Dejun Kong
A NiAlCrZrMo medium–entropy alloy (MEA) coating with solid solution was fabricated by laser cladding , which was evolved to high–entropy alloy (HEA) structure by tempering treatment for the improvement of corrosion resistance . The effects of tempering treatment on the structural evolution and electrochemical properties of obtained MEA coatings were comparatively investigated, and the corrosion mechanism was discussed with the density functional theory (DFT) calculation. The results show that the MEA structure of original MEA coating is evolved to HEA structure of tempered MEA coating by tempering treatment, which is composed of AlNi 2 Ti and Cr phases. The charge transfer resistance of tempered MEA coating is increased by ∼140 times compared with the original MEA coating, in which the diffusion of electrons is held back by its HEA structure. Moreover, the tempered MEA coating possesses higher electrochemical resistance compared with the original MEA coating, which is attributed to the AlNi 2 Ti phase of tempered MEA coating decreasing the corrosion tendency by the effect of high–entropy evolution.
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JOURNAL OF MOLECULAR LIQUIDS
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2024
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IF 5.3
Hang Yao,Jialei Huang,Yuqing Ni,Gang Fu,Lei Ni,Juncheng Jiang,Yong Pan
Selection of appropriate solvents is of great significance for achieving efficient and safe m-xylene nitration . In this study, the exothermic behavior of m-xylene nitration under twelve organic solvents were studied by reaction calorimetry. The process hazards were assessed by calculation of thermal safety parameters. The reaction selectivity was quantified. The anhydrides exhibited the prominent promotion as water absorbent and active reagent in nitration, followed by selected aliphatic hydrocarbons, chlorinated hydrocarbons. While acetic acid, propionic acid and ethyl acetate had negative effects. The maximum yield of 95.6 % was achieved in nitric acid-acetic anhydride (HNO 3 -Ac 2 O) system. The thermal weight loss of the products appeared at around 150−230 °C by thermogravimetry experiments. The activation energy was determined to be 192.9 kJ/mol through adiabatic kinetic calculations. Furthermore, the solvent effects were analyzed by calculating the solvent polarity and its interaction energy with HNO 3 . The different action mechanisms of Ac 2 O and Pc 2 O on NO 2 + generation were revealed. The density functional theory calculations were in agreement with the experimental results. These findings can provide guidance for understanding of the solvent effect on the reaction hazards and selectivity of m-xylene nitration, and provide experimental and theoretical basis for solvent screening for the nitration of similar aromatic compounds.
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FUEL
·
2024
·
IF 6.7
Ranlei Shao,Lu Zhang,Luyuan Wang,Jianmei Wang,Xingyu Zhang,Shiwang Han,Xingxing Cheng,Zhiqiang Wang
In this study, Ru catalysts supported on Ce-Al composite carriers were prepared using the precipitation-hydrothermal method, significantly enhancing ammonia decomposition efficiency. The test results show that the Ru/3Ce-Al catalyst, with a Ru loading of only 0.8 wt%, achieves a reaction rate of 14.17 mmol g cat −1 min −1 at 500 °C, and reaches a 95 % conversion rate at 525 °C. No decline in efficiency was observed after 48 h of durability testing, which significantly reduces the usage of Ru. The RuO 2 particle size in the samples was only 2–4 nm. Ce-Al composite increased the specific surface area and pore volume of the catalyst, facilitating the uniform distribution of Ru. Additionally, it increased the number of surface acidic sites and strengthened the metal-support interaction. The unique low redox potential and oxygen vacancies of CeO 2 allowed for faster electron transfer to the Ru surface. DFT calculations revealed that bridge site adsorption was more stable, with the rate-determining step of the ammonia decomposition reaction being the formation of N 2 . Ce-Al composite catalysts enhanced NH 3 adsorption strength and lowered the reaction energy barrier.
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JOURNAL OF HAZARDOUS MATERIALS
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2025
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IF 11.3
Guanqing Hu,Qingguo Zhang,Yongde Yan,Yun Xue,Fuqiu Ma,Yuelin Wang,Xin Liu,Jinlong Song
With the rapid development of the global nuclear industry, substantial amounts of radioactive tributyl phosphate (TBP) have accumulated during the PUREX process. Prolonged accumulation poses significant environmental risks. Therefore, this study proposes an efficient molten salt oxidation (MSO) method for the treatment of gelled TBP. Comprehensive thermal analysis data indicate that the oxidation process of gelled TBP primarily consists of three stages. The composition of the waste salts after the MSO process was analyzed using X-ray diffraction spectroscopy. Fourier transform infrared spectroscopy revealed that the primary functional groups in gelled TBP were progressively degraded with increasing temperature. Scanning electron microscopy clearly illustrated the decomposition process of gelled TBP. X-ray photoelectron spectroscopy results identified the predominant forms of residual substances. The generated exhaust gas was analyzed using gas mass spectrometry and chromatography. Additionally, through DFT calculations of TBP, the possible reaction mechanism of TBP in the molten salts was deduced. In the molten state, carbonate can effectively absorb P 2 O 5 and eventually form stable NaPO 3 , which is the reason for the 94.90 % retention rate of phosphorus element. During the experimental process, the degradation rate of gelled TBP reached as high as 99.99 %. The MSO method proposed in this study shows great potential for the treatment of liquid organic waste.
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Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Qian Liu,Kangping Cui,Minshu Cui,Shijie Sun,Haiyang Li
As a green photocatalyst with simple synthesis method, excellent electronic structure, and metal-free properties, the deficiencies of pristine graphitic carbon nitride, such as high electron transfer resistance and narrow energy band gap, inhibit its photocatalytic activity to some extent. In this paper, we synthesized a sulfur and chlorine co-doped g-C 3 N 4 (SCl-CN) capable of efficient photocatalytic activation of peroxymonosulfate (PMS) by calcining a mixture of ammonium chloride and thiourea. By means of DFT calculation, the contribution of sulfur and chlorine to photogenic electron hole separation was discussed. The electrostatic potential of SCl-CN and the adsorption model between SCl-CN and PMS were deduced, and the activation mechanism of PMS was further analyzed. According to the calculated results, the incorporation of sulfur and chlorine tuned the electronic configuration of the material and intensified the interactions between SCl-CN and PMS. It is shown that free and non-free radicals act simultaneously in the SCl-CN/PMS/Vis system. This study provides a new idea for the study of photocatalytic activation of PMS by non-metallic co-doped carbon nitride.
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Molecular Catalysis
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2024
·
IF 3.9
Qinglei Wu,Chenyang Shen,Chang-jun Liu
Molybdenum carbide is a promising support to tune the metal reactivity, which originates from the interaction between metal and support. In this work, Pd/β-Mo 2 C was prepared using a deposition-precipitation method for selective hydrogenation of acetylene. The high temperature calcination is employed to modulate the interaction between Pd and β-Mo 2 C. The Pd/β-Mo 2 C catalyst calcined at 600 °C exhibits significant promotion in selective hydrogenation, which shows 100 % acetylene conversion and 81.4 % ethylene selectivity at 160 °C. The activity promotion originates from the enhanced electronic metal-support interaction, which induces a shift of Pd 3d to higher binding energy. Besides, the Pd species become atomically dispersed after calcination. The changes in geometric and electronic structure suppress the formation of Pd hydrides, which consequently inhibits the excessive hydrogenation capacity of Pd. The structure variation also affects the adsorption of ethylene. No strong adsorbed ethylene (di-σ bonded ethylene) can be identified, which is conducive to the improvement of ethylene selectivity. Density functional theoretical (DFT) calculations confirm that Pd on β-Mo 2 C is positively charged. The desorption energy of C 2 H 4 * (0.78 eV) is significantly lower than that of further hydrogenation (1.45 eV), which explains the improved ethylene selectivity of the calcinated catalyst. The present study indicates calcination is an effective method to tune the activity of Pd/β-Mo 2 C for reactions beyond selective hydrogenation of acetylene.
研究领域:
催化
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化学工程
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材料科学
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理论化学
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