FUEL
·
2024
·
IF 6.7
Faraz Ahmad,Yueli Wen,Muhammad Zeeshan,Bin Wang,Awais Ashraf,Bai Hui,Zheng Cui,Chengda Li,Samia Kausar,Wei Huang
The balance of acid-base property is crucial for the catalytic performance of Side-Chain Alkylation of Toluene with Methanol (SATM). In this work, Na 3 PO 4 modified NaX catalysts with suitable middle base strength and feasible acid-base center distance were prepared by direct solvent-evaporation and exhibited the best styrene selectivity of 45.4 % and the total yield of side chain alkylation products of 71.7 %, respectively at methanol conversion up to 99.9 % in NaX-P (0.075) . Notably, the selectivity exhibits surprising stability in the evaluated 15 days, which might owe to the uniform dispersion of active species and constant acid base property. Combined the comprehensive characterizations of solid-state NMR, FTIR, SEM, and XPS, etc., with Density Functional Theory (DFT) calculation results, it is revealed that O-1264 are affected mostly by loading Na + or both of Na + and PO 4 3- , which exhibits the least adsorption energy and the highest electronic cloud density in the four kinds of oxygen atoms according to the calculated Bader charge. Therefore, the structure S4 (O-1264) was considered to be the most stable and meet the basicity requirements for SATM.
研究领域:
催化化学
·
材料科学
·
理论化学
✓ 已验证
产品关联
DOI
高影响因子
Nanomaterials
·
2022
·Vol. 12
·期 16
·2856
·
IF 5.719
Anis Ur Rahman,Nighat Zarshad,Wu Jianghua,Muslim Shah,Sana Ullah,Guigen Li,Muhammad Tariq,Asad Ali
Electrochemical energy storage devices are ubiquitous for personal electronics, electric vehicles, smart grids, and future clean energy demand. SCs are EES devices with excellent power density and superior cycling ability. Herein, we focused on the fabrication and DFT calculations of Na3-δ-MnO2nanocomposite, which has layered MnO2redox-active sites, supported on carbon cloth. MnO2has two-dimensional diffusion channels and is not labile to structural changes during intercalation; therefore, it is considered the best substrate for intercalation. Cation pre-intercalation has proven to be an effective way of increasing inter-layered spacing, optimizing the crystal structure, and improving the relevant electrochemical behavior of asymmetric aqueous supercapacitors. We successfully established Na+pre-intercalated δ-MnO2nanosheets on carbon cloth via one-pot hydrothermal synthesis. As a cathode, our prepared material exhibited an extended potential window of 0–1.4 V with a remarkable specific capacitance of 546 F g−1(300 F g−1at 50 A g−1). Moreover, when this cathode was accompanied by an N-AC anode in an asymmetric aqueous supercapacitor, it illustrated exceptional performance (64 Wh kg−1at a power density of 1225 W kg−1) and incomparable potential window of 2.4 V and 83% capacitance retention over 10,000 cycles with a great Columbic efficiency.Keywords:manganese oxide;pre-intercalation;specific capacitance;wide potential window;asymmetric aqueous supercapacitor;DFT calculation
研究领域:
材料科学
·
电化学
·
理论计算
✓ 已验证
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Pin Hou,Xinyu Sun,Jianhui Guo,Chunrong Wang,Cesar Nieto-Delgado,Jianbing Wang
The study developed a novel adsorbent for improving perchlorate removal efficiency by anchoring Poly (ionic liquid) (PIL) onto granular activated carbons (GACs) via radical polymerization. The authors characterized the physical–chemical properties of GAC modified by PIL (PIL-GAC), and investigated its performance and mechanism for perchlorate adsorption. The results show that the introduction of dicationic ionic liquids dramatically increases the positively charged nitrogen (12.59 %) and point of zero charge (pH pzc = 9.79) of GAC, resulting in a higher attraction for perchlorate. Density Functional Theory (DFT) calculations reveal a better adsorption energy (−162.58 kJ/mol) of perchlorate on imidazole N, highlighting its potential selectivity over other N and O functional groups. PIL-GAC exhibits a maximum adsorption capacity (Q m ) of 300.05 mg/g at 25 °C, which is 12 times higher than that of pristine GAC and better than previously reported adsorbents. Additionally, this Q m is pH independent within pH 4 to 10. The perchlorate adsorption on PIL-GAC fits the Langmuir (R 2 ≥ 0.98) and pseudo second order kinetic (R 2 > 0.99) models, indicating a spontaneous process primarily driven by chemisorption. Remarkably, PIL-GAC also exhibits sustainable regeneration and greater selectivity for perchlorate with a lower hydration energy (−214 kJ/mol), over nitrate, chloride, and sulfate with higher hydration energy (−306, −347, and −1090 kJ/mol). After adsorption, PIL-GAC demonstrates a decrease of N + and an increase in Cl - , indicating that perchlorate adsorption of PIL-GAC mainly involves electrostatic interaction and ion exchange. Therefore, this study offers a promising method for efficient and selective removal of perchlorate from water.
研究领域:
环境科学
·
水处理
·
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Yuhang He,Jing Lao,Hua Ke,Yangcheng Lu
The alcoholysis process of ethylene–vinyl acetate copolymer (EVA) is both important and complex. In this work, we conduct experimental and computational investigations to examine the alcoholysis kinetics and mechanism of EVA with an ethylene content if less than 50 mol%. Our findings indicate that the overall structure of EVA polymer chain has little effect on the alcoholysis rate. However, the local structure of the acetate group, particularly its association with the ethylene content, significantly affects the overall alcloholysis. To predict the influence of ethylene content on the overall rate constant, we propose an empirical model based on detailed kinetic studies of triads. Additionally, we discover a self-acceleration phenomenon in EVA alcoholysis, although it is less pronounced compared to polyvinyl acetate. Furthermore, we employed quantum chemical calculation using density functional theory (DFT) to confirm the effect of structure on EVA alcoholysis. Notably, we investigate, for the first time, the influence of neighboring hydroxyl group on self-acceleration phenomenon through theoretical calculations. This work offers valuable insight into EVA alcoholysis and may serve as a guide for exploring its mechanism and designing processes for producing EVA related polymer materials.
研究领域:
聚合物化学
·
材料科学
·
计算化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Zhengwen Wei,Liuqing Li,Wei Wang,Wankui Ni,Xiang-fei Lü,Giuseppe Mele,Zhen-Yi Jiang
The widespread presence of harmful and stubborn amine organic contaminants in aquatic environments motivated the exploration of efficient technologies for alleviating their serious environmental crisis. Herein, the recyclable magnetic Schiff base polymer (Fe 3 O 4 -TENE) with satisfactory and promising capacity in treating aniline and 3,4-diaminotoluene as representative amine organic contaminants was fabricated via a simple in-situ polymerization method, which combined the magnetic separability advantage of magnetic oxides with the abundant aromatic carbon content properties of Schiff base polymer. Multiple characterization methods verified the effectiveness of the in-situ polycondensation coating reaction and analyzed the physicochemical properties of Fe 3 O 4 -TENE. The Fe 3 O 4 -TENE possessed abundant homogeneous reaction sites and excellent regeneration performance, multiple diffusion driving forces and micro-mechanisms co-participated in the removal reaction. The adsorption pathway, underlying reaction mechanism and the most probable bonding system were identified based on the statistical modelling and DFT quantitative calculations. Especially, the visible electrostatic potential molecular and molecular orbitals verified the π-π interaction and electrostatic forces greatly contributed to the removal reaction. The Driving forces – Challenges – Breakthrough – Application framework was proposed for comprehensively assessing the possible environmental application of Fe 3 O 4 -TENE. Overall, this work not only provides important insights into the utilization of magnetic polymer composite to alleviate ecological and environmental risks caused by amine organic pollutants, but also contributes to an in-depth excavation of the bonding types and removal mechanisms from both micro and macro perspectives.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2015
·
IF 1.602
Xue-Jie Tan,Xiu-Qi Hao,Qing-Zhe Zhao,Shuang-Shuang Cheng,Wen-Long Xie,Dian-Xiang Xing,Yun Liu,Lai-Zhou Song
A series of mono- and di-Schiff-bases based on Benzil Dihydrazone ( BDH ) were designed and synthesized to be set as the model compounds to explain which one should be the advanced product and which parameters will determine the end-product. As the first step of a series of investigations, this article presents the syntheses and characterization of five new Schiff-bases plus one preliminary reported Schiff-base, all derived from BDH . The compounds were characterized by single crystal (or conventional powder) X-ray diffractometry, elemental analysis , m.p., 1 H NMR, 13 C NMR, IR and UV–Vis. Structural features of the five new Schiff-bases are similar. For instance, all molecules are nonsymmetrical/symmetrical double helix with the torsion angle of two “half-parts” about 72–97°. The Ph-C N–N C-Ph moiety all exists in planar and anti form, indicating significant conjugation. The crystal structures appear to be stabilized by π-stacking between the aromatic rings , as well as by intermolecular hydrogen bonds and C–H … π stacking interactions. DFT calculations have been performed to explain the trend of the experimentally measured reaction yields. In the case of the studied systems by us, the type of Schiff-bases exhibits a clear dependence on the molar ratio of reactants if the products have similar stabilities. Otherwise the importance of reaction conditions will be weakened and the most stable product will be favored.
研究领域:
有机化学
·
理论化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Zhixin Liu,Yongdi Liu,Xianbo Sun,Haodong Ji,Wen Liu,Zhengqing Cai
A novel Z-scheme Ag/AgVO 3 /carbon-rich g-C 3 N 4 heterojunction with excellent solar-light-driven photocatalytic activity was constructed via a facile hydrothermal-calcining method. The Ag/AgVO 3 /carbon-rich g-C 3 N 4 composites displayed superior performance for the photocatalytic degradation of sulfamethiadiazole (SFZ) under solar irradiation. The optimal composite with a 10 wt% Ag/AgVO 3 content showed the highest photocatalytic activity, its degradation rate constant ( k ) for SFZ degradation was ∼13 and 30 times than that of carbon-rich g-C 3 N 4 (CCN) and Ag/AgVO 3 , respectively. Furthermore, •O 2 – was identified as the most crucial reactive species in the Z-scheme photocatalysis system. The greatly improved photocatalytic activities are derived from the built-in electric field (BIEF) of CCN and efficient Z-scheme charge transfer with Ag nanoparticles as charge transmission-bridge. The possible photocatalytic degradation mechanism and pathway over Ag/AgVO 3 /carbon-rich g-C 3 N 4 were proposed based on LC-MS analysis and density functional theory (DFT) calculation, and the toxicity of intermediates was evaluated by Quantitative structure–activity relationship (QSAR) based prediction. In summary, this work provides new insight into constructing highly efficient Z-scheme photocatalyst, which is promising for implementation in surface water remediation.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
高影响因子
BIOMASS & BIOENERGY
·
2025
·
IF 5.8
Chun Chang,Xin Liu,Shuo Zang,Kai Fu,Zhen Ma,Xiaoyang Zheng,Huijuan Tian,Zhining Li
Xylose residue (XR), a waste product from the xylose industry, is currently primarily used for incineration, animal feed, and cultivation substrates, representing a significant waste of resources. Due to its rich cellulose content, this study demonstrates the valorization of XR into methyl/ethyl levulinate (ML/EL) under high-solid conditions catalyzed by sulfate, through an integrated approach combining experimental and DFT investigations. Under the same optimized conditions (catalyst loading: 6 g/200 mL, 180 °C, 2 h), an increase in the solid content of XR from 15 % to 30 % in methanol, catalyzed by CuSO 4 , enhanced the ML concentration by 58 % (46.73 → 74.06 g/L), though at the expense of a 20 % yield reduction (24.89 → 19.84 wt%). Analogous trends were observed in ethanol systems catalyzed by Al 2 (SO 4 ) 3 under identical conditions (EL: concentration +60 % (26.0 → 41.59 g/L), yield −19 % (22.96 → 18.64 wt%)). DFT simulations revealed that Brønsted-Lewis acid synergy (e.g., Cu(CH 3 OH) 2 + , Al(CH 3 OH) 4 3+ , and Fe(CH 3 OH) 3 3+ ) governed catalytic performance. The Brønsted-to-Lewis acidity hierarchy (Al 3+ > Fe 3+ > Cu 2+ ) correlated with metal electronegativity but was predominantly modulated by ligand electron transfer. Fukui function analysis highlighted distinct electronic behaviors of H + and Cu 2+ , enabling cooperative catalysis that shifted the rate-limiting step from initial dehydration (39.87 and 39.13 kcal/mol) to glucoside-fructoside isomerization (33.87 and 35.87 kcal/mol). These insights underscore the superiority of bifunctional catalysts in reducing energy barriers and optimizing reaction pathways. By integrating process intensification with acid-site engineering, this work establishes a strategy to reconcile yield-concentration trade-offs in high-solid biomass conversion, offering a scalable route for sustainable levulinate production.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Qianyun Tan,Shuying Pu,Guangyu Zhu,Chunxiao Yin,Gege Zhang,Zhongyao Zhang,Min Wu,Yong Tan,Fa-Qian Liu
Marine biofouling is one of the biggest problems for titanium alloys and rutile TiO 2 coatings in marine engineering applications. Hydrogel materials are a novel and environmentally benign antifouling strategy, but they cannot be stabilized on alloy surfaces to provide long-term protection. Focusing on the challenges of bonding at the hydrogel-alloy interface, a PAA/PHEMA composite hydrogel containing Cu 2 O@PEG powder was strongly bonded to the titanium alloy by forming chemical bonds with APTES. The composite hydrogel still achieves an adhesion strength of 60–70 kPa after 7 days of immersion. The samples maintained a stable copper ion leaching rate of 2.61–3.76 μg·cm −2 ·d −1 after 21 days of immersion. The coating-modified titanium alloys showed a 100 % bactericidal rate within three hours of contact with different bacteria and exhibited a high anti-algal adhesion rate of up to 99 %. In addition, the attachment mode of APTES on rutile TiO 2 was clarified for the first time by Density Functional Theory (DFT) calculations. According to DFT calculations, the adsorption energy of APTES on Ti-TiO 2 is −747.025 kJ/mol, and the adsorption energy of acrylic acid on TiO 2 -APTES is −535.152 kJ/mol. The chemical bonding connection between the hydrogel-alloy interface, as a novel interface bonding strategy, would be expected to broaden the application of titanium alloy in marine engineering.
研究领域:
材料科学
·
海洋工程
·
表面化学
·
计算化学
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL RESEARCH
·
2025
·
IF 7.7
Qianqian Ni,Huiping Shao,Yun Zhang,Xin Ke,Wengang Liu
Oxygen vacancies could be induced into the heterojunction structure of BiOI/BiOBr via high-temperature calcination. Light absorption, charge transfer efficiency, photocatalytic activity, and mechanism are all intimately connected to oxygen vacancies. Density-functional theory simulations demonstrate that surface oxygen vacancies adsorb oxygen to active sites, whereas bulk oxygen vacancies activate oxygen adsorbed to the surface to reactive radicals. Meanwhile, the addition of oxygen vacancies efficiently reduces the effects of background ions and pH on tetracycline breakdown in the real aquatic environment. The experimental results are consistent with the DFT calculations. This paper presents a straightforward approach for creating heterojunction surface and bulk-phase oxygen vacancies, as well as an understanding of the many roles that different types of oxygen vacancies play in the photocatalytic degradation process.
研究领域:
环境科学
·
材料科学
·
光催化化学
·
水污染治理
·
计算化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Yi Zhang,Gesheng Li,Zunhua Zhang,Yong Huang,Minghao Li,Jian Li,Mengni Zhou
Highly active catalysts suitable for ammonia reforming reactions have been comprehensively investigated by density functional theory (DFT) calculations and experimental tests. Non-precious metal Ni, precious metal Ru and Ru-Ni composite metal are selected as catalytic activity surfaces, and a series of three-dimensional metal-packed catalyst models are constructed parallelly. Then, to elucidate the rate-determining step of reforming reaction, in-depth analysis of microscopic reaction mechanisms for amino groups (including H and NH x , x =0–3) adsorption, dissociation, recombination and desorption are carried out by simulation parameters and experimental data. The results indicate that NH 3 exhibits highly stable adsorption configurations (Bridge site) on both Ni, Ru-based catalyst surfaces , with the adsorption position having a relatively minor effect on adsorption energy . It is worth noting that Ni-based catalyst exhibits better adsorption behaviors towards NH 3 compared to Ru. Whereas, during stepwise dehydrogenation of NH 3 and subsequent N 2 and H 2 recombination and desorption processes, the reaction energy barriers confirm experimental observations of higher activity displayed by Ru-based catalyst in low-temperature range of 400–500 °C. Interestingly, N 2 synthesis behavior of innovative Ru-Ni bimetallic tandem catalyst surface possesses the lowest reaction energy barrier than other models, which is attributed to the adsorption capability of Ni layers and the catalytic activity of Ru atoms. The experimental results also demonstrate that under typical engine exhaust conditions, the H 2 production efficiency of 1 %Ru-3 %Ni/Al 2 O 3 surpasses that of 1 %Ru/Al 2 O 3 by 6.2 %, showcasing exceptional stability.
研究领域:
催化化学
·
能源材料
·
理论计算化学
✓ 已验证
产品关联
DOI
高影响因子
MOLECULES
·
2023
·Vol. 28
·期 14
·5459
·
IF 4.6
Guangyuan Hu,Zhiwei Wang,Weiye Zhang,Hongxing He,Yi Zhang,Xiujun Deng,Weili Li
The recovery of precious metals from secondary resources is significant economically and environmentally. However, their separation is still challenging because they often occur in complex metal ion mixtures. The poor selectivity of adsorbents for gold in complicated solutions prevents further application of adsorption technology. In this study, a Zr-based MOF adsorbent, MIL-161, was synthesized using s-tetrazine dicarboxylic acid (H2STz) as an organic ligand. MIL-161 demonstrated a high adsorption capacity of up to 446.49 mg/g and outstanding selectivity for gold(III) in a simulated electronic waste solution as a result of the presence of sulfur- and nitrogen-containing groups. In addition, the MIL-161 adsorbents were characterized using Fourier transform infrared (FT-IR), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TG), Brunner–Emment–Teller (BET), and X-ray photoelectron spectroscopy (XPS). Additionally, the adsorption kinetics, isotherms, and thermodynamics of the MOF adsorbents were also thoroughly examined. More importantly, the experimental results and DFT calculations indicate that chelation and electrostatic interactions are the main adsorption mechanisms.Keywords:selectivity;e-wastes;metal–organic framework;gold;adsorption;DFT calculations
研究领域:
材料科学
·
环境工程
·
化学工程
·
可持续化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）