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Linker-driven tuning of pore structure and acidity in Zr-MOFs for paraoxon-methyl hydrolysis and efficient oxidative desulfurization 链接器驱动的zr - mof的孔结构和酸度调节对氧氧甲基的水解和高效氧化脱硫
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-05-01 Epub Date: 2025-12-26 DOI: 10.1016/j.jtice.2025.106588
Manh B Nguyen , Le Van Dung , Tan Le Hoang Doan , Pham Tung Son , Sanjit Nayak , Thi Hai Yen Pham , Valeska P. Ting , Huan V. Doan

Background

Zirconium-based metal-organic frameworks are promising candidates for catalytic applications due to their high structural stability, tunable porosity, and acidity. However, the influence of organic linkers on their acid site distribution, pore structure, and catalytic activity, particularly in hydrolysis and oxidative desulfurization reactions, has not been fully explored.

Methods

A series of Zr-MOFs was synthesized using a microwave-assisted solvothermal method at 100 °C for 30 minutes, reducing reaction times by 20–50 times compared to conventional solvothermal approaches. Structural, textural properties, acidity and defect content were characterized using TEM, BET, NH3-TPD, FTIR-CD3CN, ESR and XPS. The catalytic activity was evaluated for the hydrolysis of paraoxon-methyl (PM) and the oxidative desulfurization of dibenzothiophene (DBT) under mild conditions. The ODS mechanism of DBT and hydrolysis mechanism of PM are proposed based on the identified degradation products by GC–MS/LC-MC, nuclear magnetic resonance and the role of the Lewis acid sites.

Significant findings

Organic linker variation significantly affected the pore size (0.83–3.68 nm), surface area (1332–1762 m2 g-1), and acid site distribution. Zr-BTC exhibited the highest Lewis acidity (0.311 mmol g-1) and defect content, achieving complete PM hydrolysis in 2.5 min and 100 % DBT removal within 30 min. Catalytic efficiency strongly correlated with Lewis acid site density modulated by the choice of linker.
锆基金属有机骨架由于其高结构稳定性、可调节的孔隙度和酸度而成为催化应用的有希望的候选者。然而,有机连接剂对其酸位分布、孔结构和催化活性的影响,特别是在水解和氧化脱硫反应中,尚未得到充分的探讨。方法采用微波辅助溶剂热法,在100℃条件下反应30 min,合成一系列zr - mof,反应时间比传统溶剂热法缩短20 ~ 50倍。采用TEM、BET、NH3-TPD、FTIR-CD3CN、ESR和XPS表征了其结构、织构性能、酸度和缺陷含量。在温和条件下考察了对氧磷-甲基(PM)水解和二苯并噻吩(DBT)氧化脱硫的催化活性。基于GC-MS /LC-MC、核磁共振鉴定的降解产物和Lewis酸位点的作用,提出了DBT的ODS机理和PM的水解机理。有机连接剂的变化显著影响了孔隙大小(0.83-3.68 nm)、表面积(1332-1762 m2 g-1)和酸位点分布。Zr-BTC具有最高的Lewis酸度(0.311 mmol g-1)和缺陷含量,在2.5 min内完全水解PM,在30 min内100%去除DBT。催化效率与通过选择连接剂调节的路易斯酸位点密度密切相关。
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引用次数: 0
Alkali modification and nitrogen doping synergistically regulate sludge-derived biochar for persulfate activation and organic pollutant degradation 碱改性和氮掺杂协同调节污泥源生物炭的过硫酸盐活化和有机污染物降解
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-05-01 Epub Date: 2025-12-08 DOI: 10.1016/j.jtice.2025.106569
Yujie Zhang, Shoulong Peng, Siyu Zhang, Jiani Li
Given the increasing organic pollution in industrial wastewater and the disposal risks of municipal sludge, developing advanced oxidation technology based on sludge-derived biochar-activated peroxymonosulfate (PMS) is highly promising. In this study, a series of sludge-derived biochars (SSB) were prepared via alkali modification and nitrogen doping, and their performance and mechanism in activating PMS for the degradation of organic pollutants were systematically investigated. After alkali modification, the surface of biochar becomes much rougher, and meanwhile the functional group C=O appears. After urea doping, the biochar exhibits a more porous characteristic, and the increased nitrogen species can enhance the electron transfer ability. Experimental results demonstrated that the 0.5-SSB-3/PMS reaction system could rapidly oxidize and degrade multiple organic pollutants. Characterization via SEM and BET revealed that the modified biochar has a rough surface and a relatively distinct pore structure, while both its pore size and pore volume are increased. Mechanistic investigations revealed that non-radical singlet oxygen (1O2) served as the dominant reactive species. On the one hand, it is generated by the self-decomposition of PMS; on the other hand, it is generated by the activation of PMS by special structures such as C=O, pyridinic N, and graphitic N. The catalyst maintained high efficiency across a wide pH range (3–9), and the 0.5-SSB-3/PMS system still achieved 90.7% pollutant degradation after five reuse cycles. This study provides valuable insights into the resource utilization of sludge and the degradation of organic pollutants.
鉴于工业废水中有机污染的日益增加和城市污泥的处置风险,开发基于污泥源生物炭活化过氧单硫酸根(PMS)的高级氧化技术是非常有前景的。本研究通过碱改性和氮掺杂制备了一系列污泥源生物炭(SSB),并对其激活PMS降解有机污染物的性能和机理进行了系统研究。碱改性后的生物炭表面变得更加粗糙,同时出现了官能团C=O。尿素掺杂后的生物炭表现出更多孔的特性,增加的氮种可以增强电子传递能力。实验结果表明,0.5-SSB-3/PMS反应体系能够快速氧化降解多种有机污染物。SEM和BET表征表明,改性后的生物炭表面粗糙,孔隙结构相对清晰,孔径和孔体积均有所增大。机理研究表明,非自由基单线态氧(1O2)是主要的反应物质。它一方面是由PMS自分解产生的;另一方面,它是由C=O、吡啶N和石墨N等特殊结构对PMS的活化产生的。催化剂在较宽的pH范围(3-9)内保持了较高的效率,0.5-SSB-3/PMS体系在重复使用5次后仍能达到90.7%的污染物降解率。本研究为污泥资源化利用和有机污染物的降解提供了有价值的见解。
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引用次数: 0
Synergistic adsorption and degradation of flumetsulam residue by agricultural waste-derived biochar: Performance and mechanism 农业废弃物生物炭协同吸附和降解氟metsulam残留物:性能和机理
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-05-01 Epub Date: 2025-12-13 DOI: 10.1016/j.jtice.2025.106581
Jianji Zhao , Xiangyu Zhang , Xiaoqiang Wang , Deyi Ou , Kecheng Huang , Chenglan Liu

Background

Engineered waste-derived biochar can simultaneously remediate polluted aquatic and soil environments, but a comprehensive and mechanistic assessment of efficacy is required, particularly concerning emerging herbicide residues in complex agricultural environments.

Methods

We engineered four types of biochar derived from different waste, including tobacco straw (TBC), rice husk (RBC), cattle feces (FBC), and cattle bone (BBC), and evaluated their potential as a multifunctional strategy for regulating herbicide flumetsulam (FLM) adsorption, degradation, and microbial interaction mechanisms.

Significant findings

The adsorption capacity of these biochars for FLM followed the order: RBC > BBC > TBC > FBC. Among them, RBC demonstrated a high specific surface area (611.24 m²/g) and the largest sorption quantity (39.39 mg/g). This remarkable performance benefited from the surface adsorption and hydrophobic distribution, primarily controlled by the pore filling, hydrogen bonding, π-π stacking, and hydrophobic interaction. Notably, both RBC and FBC accelerated the degradation of FLM in soil, with degradation rate constants increasing by 138.6-213.1% and 22.2-58.5%, respectively. 16S rRNA sequencing revealed feedstock-specific microbiome remodeling, enriching keystone taxa linked to FLM degradation, including Ellin6067 (RBC) and Lysobacter (FBC). Moreover, two degradation products of FLM were identified by a Q Exactive combined quadrupole-Orbitrap mass spectrometer (Q-TOF), and toxicity tests showed that the toxicity of the degradation intermediates was reduced. Overall, this work provides new insights for using agricultural waste to produce low-cost remediation materials with high adsorption capacity and enhanced biodegradation efficiency, positioning them as highly effective in reducing the risk of herbicide residues in agricultural environments.
工程废物衍生的生物炭可以同时修复被污染的水生和土壤环境,但需要对其功效进行全面和机械的评估,特别是在复杂的农业环境中出现的除草剂残留。方法利用烟草秸秆(TBC)、稻壳(RBC)、牛粪(FBC)和牛骨(BBC)等4种不同的废弃物制备生物炭,评价其作为调节除草剂氟美舒兰(FLM)吸附、降解和微生物相互作用机制的多功能策略的潜力。这些生物炭对FLM的吸附量顺序为:RBC >; BBC > TBC >; FBC。其中,RBC比表面积最高(611.24 m²/g),吸附量最大(39.39 mg/g)。这种优异的性能得益于表面吸附和疏水分布,主要由孔隙填充、氢键、π-π堆积和疏水相互作用控制。RBC和FBC均加速了土壤中FLM的降解,降解速率常数分别提高了138.6 ~ 213.1%和22.2 ~ 58.5%。16S rRNA测序揭示了原料特异性微生物群的重塑,丰富了与FLM降解相关的关键分类群,包括Ellin6067 (RBC)和Lysobacter (FBC)。利用Q- Exactive联合四极轨道阱质谱仪(Q- tof)鉴定了两种降解产物,毒性试验表明降解中间体的毒性降低。综上所述,本研究为利用农业废弃物生产低成本、高吸附能力、高生物降解效率的修复材料提供了新的见解,使其在降低农业环境中除草剂残留风险方面非常有效。
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引用次数: 0
Development and characterization of biodegradable packaging films based on sodium alginate, Iota-carrageenan and latex blends for packaging applications 以海藻酸钠、角叉胶和乳胶为基础的可生物降解包装薄膜的研制与表征
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-05-01 Epub Date: 2025-12-19 DOI: 10.1016/j.jtice.2025.106567
Sandhiya Mohan, Gokul Sreekumar, Keerthi Praveen

Background

The goal of this work is to create a biopolymer packaging film that is made of Sodium alginate and I-Carrageenan and reinforced with different amounts of natural rubber latex (NRL). The objective is to enhance the film's mechanical and physicochemical characteristics for possible use in the packaging sector.

Method

Solvent casting was the method used to create the films. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to examine the physicochemical properties of the films. The impact of varying quantities of NRL on the performance of the film was evaluated.

Significant Findings

When NRL was added, the moisture content decreased from 6.98% to 3.87% and the water solubility drastically decreased from 9.55% to 5.61%, resulting in a decrease in moisture retention. On the other hand, with 20% NRL content, mechanical characteristics significantly improved, with tensile strength rising from 18.63 MPa to 45.45 MPa. Furthermore, films containing NRL demonstrated exceptional optical transparency and improved UV resistance. According to these results, NRL functions as a powerful reinforcing agent, improving the biopolymer films' capacity for packaging applications.
这项工作的目标是创造一种生物聚合物包装薄膜,该薄膜由海藻酸钠和i -卡拉胶制成,并用不同量的天然胶乳(NRL)增强。目的是提高薄膜的机械和物理化学特性,以便在包装部门中使用。方法采用溶剂铸造法制备膜。利用扫描电镜(SEM)和傅里叶变换红外光谱(FTIR)对膜的理化性质进行了表征。评估了不同数量的NRL对薄膜性能的影响。结果表明:添加NRL后,水杨浆含水率由6.98%下降到3.87%,水溶性由9.55%急剧下降到5.61%,保水性能下降。另一方面,当NRL含量为20%时,材料的力学特性显著改善,抗拉强度由18.63 MPa提高到45.45 MPa。此外,含有NRL的薄膜表现出优异的光学透明度和增强的抗紫外线能力。根据这些结果,NRL作为一种强大的补强剂,提高了生物聚合物薄膜的包装应用能力。
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引用次数: 0
Synergistic surface plasmon resonance and S-scheme charge migration in oxygen vacancy rich TiO2/Bi19Br3S27/Bi nanostructures enabling outstanding photocatalytic degradation of pollutants 富氧空位TiO2/Bi19Br3S27/Bi纳米结构的协同表面等离子体共振和s方案电荷迁移使污染物具有出色的光催化降解能力
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-05-01 Epub Date: 2025-12-20 DOI: 10.1016/j.jtice.2025.106591
Zahra Salmanzadeh-Jamadi , Aziz Habibi-Yangjeh , Alireza Khataee

Background

Dye and pharmaceutical pollution in water bodies poses a serious worldwide challenge, endangering both aquatic ecosystems and human health because of their durability, harmful effects, and potential to cause cancer, making urgent intervention.

Methods

In this study, plasmonic TiO2-X/Bi19Br3S27/Bi photocatalysts were successfully formulated through a two-step hydrothermal method using sodium borohydride as a reducing agent. The synthesized photocatalyst exhibited greatly improved photocatalytic performance in the degradation of various pollutants, including azithromycin (AZM), tetracycline hydrochloride (TCH), and cephalexin (CPN), and three dyes, including methyl orange (MO), methylene blue (MB), and rhodamine B (RhB). Key improvements are superior redox efficiency resulting from the highly negative conduction potential of Bi19Br3S27, improved visible-light response induced by bismuth nanoparticles and defects formed in TiO2 (abbreviated as TiO2-x), efficient separation rate and photoinduced charge carrier transport, creation of active sites and species, development of S-scheme mechanism between the photocatalyst counterparts, and quantum size of the synthesized photocatalysts.

Significant findings

The impact of Bi19Br3S27 nanoparticles (5, 10, and 20 wt%) on the performance of TiO2-X was investigated to determine the optimal photocatalyst composition. The highest photocatalytic degradation of TCH was achieved by the TiO2-X/Bi19Br3S27 (10 %) nanocomposite (98 % in 180 min). The optimized TiO2-X/Bi19Br3S27/Bi-2 nanocomposite achieved a TCH degradation rate of 99.7 % within 60 min with a reaction rate constant of 1002 × 10‒4 min‒1, which was 4.81 times of TiO2-X/Bi19Br3S27 (10 %), 16.6 folds of Bi19Br3S27, 14.6 times of TiO2, and 4.41 as high as TiO2-x under the identical conditions. The TiO2-X/Bi19Br3S27/Bi-2 nanocomposite exhibited stability across four reuse cycles, while its compatibility with biological systems was shown by successful lentil seed growth in the treated solution. This work introduces an innovative nanocomposite designed for the degradation of dyes and the elimination of antibiotics with usability in plant irrigation applications.
水体中的染料和药物污染因其持久性、有害影响和致癌潜力而危及水生生态系统和人类健康,是一项严重的全球性挑战,迫切需要进行干预。方法以硼氢化钠为还原剂,通过两步水热法制备了等离子体TiO2-X/Bi19Br3S27/Bi光催化剂。合成的光催化剂在降解阿奇霉素(AZM)、盐酸四环素(TCH)、头孢氨苄(CPN)等多种污染物以及甲基橙(MO)、亚甲基蓝(MB)、罗丹明B (RhB)等3种染料方面表现出了较好的光催化性能。关键的改进是由于Bi19Br3S27的高负传导电位而产生的优越的氧化还原效率,铋纳米粒子诱导的可见光响应和TiO2(简称TiO2-x)中形成的缺陷的改善,高效的分离速率和光诱导的载流子传输,活性位点和物质的产生,光催化剂对偶物之间S-scheme机制的发展,以及合成的光催化剂的量子尺寸。研究了Bi19Br3S27纳米颗粒(5%、10%和20% wt%)对TiO2-X性能的影响,以确定最佳光催化剂组成。TiO2-X/Bi19Br3S27(10%)纳米复合材料对TCH的光催化降解效果最好,在180 min内达到98%。优化后的TiO2-x /Bi19Br3S27/Bi-2纳米复合材料在60 min内的TCH降解率为99.7%,反应速率常数为1002 × 10 - 4 min - 1,是相同条件下TiO2-x /Bi19Br3S27的4.81倍(10%),Bi19Br3S27的16.6倍,TiO2的14.6倍,TiO2-x的4.41倍。TiO2-X/Bi19Br3S27/Bi-2纳米复合材料在4个重复使用循环中表现出稳定性,而其与生物系统的相容性通过在处理过的溶液中成功的小扁豆种子生长来证明。这项工作介绍了一种创新的纳米复合材料,用于降解染料和消除抗生素,在植物灌溉应用中具有可用性。
{"title":"Synergistic surface plasmon resonance and S-scheme charge migration in oxygen vacancy rich TiO2/Bi19Br3S27/Bi nanostructures enabling outstanding photocatalytic degradation of pollutants","authors":"Zahra Salmanzadeh-Jamadi ,&nbsp;Aziz Habibi-Yangjeh ,&nbsp;Alireza Khataee","doi":"10.1016/j.jtice.2025.106591","DOIUrl":"10.1016/j.jtice.2025.106591","url":null,"abstract":"<div><h3>Background</h3><div>Dye and pharmaceutical pollution in water bodies poses a serious worldwide challenge, endangering both aquatic ecosystems and human health because of their durability, harmful effects, and potential to cause cancer, making urgent intervention.</div></div><div><h3>Methods</h3><div>In this study, plasmonic TiO<sub>2-X</sub>/Bi<sub>19</sub>Br<sub>3</sub>S<sub>27</sub>/Bi photocatalysts were successfully formulated through a two-step hydrothermal method using sodium borohydride as a reducing agent. The synthesized photocatalyst exhibited greatly improved photocatalytic performance in the degradation of various pollutants, including azithromycin (AZM), tetracycline hydrochloride (TCH), and cephalexin (CPN), and three dyes, including methyl orange (MO), methylene blue (MB), and rhodamine B (RhB). Key improvements are superior redox efficiency resulting from the highly negative conduction potential of Bi<sub>19</sub>Br<sub>3</sub>S<sub>27</sub>, improved visible-light response induced by bismuth nanoparticles and defects formed in TiO<sub>2</sub> (abbreviated as TiO<sub>2-x</sub>), efficient separation rate and photoinduced charge carrier transport, creation of active sites and species, development of S-scheme mechanism between the photocatalyst counterparts, and quantum size of the synthesized photocatalysts.</div></div><div><h3>Significant findings</h3><div>The impact of Bi<sub>19</sub>Br<sub>3</sub>S<sub>27</sub> nanoparticles (5, 10, and 20 wt%) on the performance of TiO<sub>2-X</sub> was investigated to determine the optimal photocatalyst composition. The highest photocatalytic degradation of TCH was achieved by the TiO<sub>2-X</sub>/Bi<sub>19</sub>Br<sub>3</sub>S<sub>27</sub> (10 %) nanocomposite (98 % in 180 min). The optimized TiO<sub>2-X</sub>/Bi<sub>19</sub>Br<sub>3</sub>S<sub>27</sub>/Bi-2 nanocomposite achieved a TCH degradation rate of 99.7 % within 60 min with a reaction rate constant of 1002 × 10<sup>‒4</sup> min<sup>‒1</sup>, which was 4.81 times of TiO<sub>2-X</sub>/Bi<sub>19</sub>Br<sub>3</sub>S<sub>27</sub> (10 %), 16.6 folds of Bi<sub>19</sub>Br<sub>3</sub>S<sub>27</sub>, 14.6 times of TiO<sub>2,</sub> and 4.41 as high as TiO<sub>2-x</sub> under the identical conditions. The TiO<sub>2-X</sub>/Bi<sub>19</sub>Br<sub>3</sub>S<sub>27</sub>/Bi-2 nanocomposite exhibited stability across four reuse cycles, while its compatibility with biological systems was shown by successful lentil seed growth in the treated solution. This work introduces an innovative nanocomposite designed for the degradation of dyes and the elimination of antibiotics with usability in plant irrigation applications.</div></div>","PeriodicalId":381,"journal":{"name":"Journal of the Taiwan Institute of Chemical Engineers","volume":"182 ","pages":"Article 106591"},"PeriodicalIF":6.3,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837753","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A photo-driven iodate–iron synergistic advanced oxidation process for efficient Orange II degradation in water treatment 光驱动碘-铁协同深度氧化工艺在水处理中的高效降解
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-05-01 Epub Date: 2025-12-31 DOI: 10.1016/j.jtice.2025.106604
Jianing Shi , Siru Huang , Xunfa Yu , Wanying Zhai , Guochao Xie , Li Guo , Tiancui Li

Background

Azo dyes such as Orange II are highly toxic, structurally stable, and resistant to biodegradation, posing serious risks to aquatic environments. Conventional treatment methods are often ineffective, necessitating the development of efficient and sustainable degradation strategies.

Methods

This study investigated a Fe²⁺/IO₃⁻/UV system for Orange II degradation. Key operational factors were systematically examined, while radical quenching and EPR were applied to identify reactive species. LC–MS and frontier molecular orbital analysis were used to propose degradation pathways, and ECOSAR assessed the toxicity of intermediates. Process optimization was conducted using response surface methodology.

Results

Hydroxyl radicals, superoxide radicals, and iodine-centered radicals were identified as the dominant oxidants. Under optimal conditions (pH 11, Fe²⁺ = 0.05 mM, IO₃⁻ = 3 mM, UV = 32 W), Orange II removal reached 99.26 %, surpassing the conventional Fenton-like process. Simulated natural water tests achieved >90 % removal, with low energy consumption and reduced toxicity of byproducts, confirming both environmental compatibility and economic feasibility.
偶氮染料如橙ⅱ具有剧毒、结构稳定、抗生物降解等特点,对水生环境构成严重威胁。传统的处理方法往往是无效的,因此必须制定有效和可持续的降解战略。方法研究了Fe 2 + /IO₃⁻/UV体系对橙II的降解作用。系统考察了关键操作因素,并应用自由基猝灭和EPR技术鉴定了反应物质。采用LC-MS和前沿分子轨道分析提出了降解途径,ECOSAR评估了中间体的毒性。采用响应面法进行工艺优化。结果羟基自由基、超氧自由基和碘中心自由基是主要的氧化剂。在最佳条件下(pH 11, Fe 2⁺= 0.05 mM, IO₃⁻= 3 mM, UV = 32 W), Orange II的去除率达到99.26%,超过了传统的类芬顿法。模拟天然水试验达到了90%的去除率,能耗低,副产品毒性降低,证实了环境兼容性和经济可行性。
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引用次数: 0
Efficient Ge(IV) CAPTURE by hydroxyl-functionalized Zr-MOF via inner-sphere complexation 球内络合羟基功能化Zr-MOF高效捕获Ge(IV)
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-05-01 Epub Date: 2025-12-17 DOI: 10.1016/j.jtice.2025.106587
Xinni Tang , Manying Zhu , Yihui Wu , Jiaxin Luo , Xinrui Yang , Shixing Wang , Libo Zhang

Background

Germanium (Ge) is a rare strategic element, with its content in industrial wastewater far exceeding the Earth's crustal average, necessitating efficient recovery.

Methods

This study synthesized a zirconium-based metal-organic framework (UiO-66–2OH) with hydroxyl groups via solvothermal method using 2,5-dihydroxyterephthalic acid as a linker. Characterization by SEM, EDS, XRD, FT-IR, BET, and XPS confirmed high crystallinity and abundant oxygen-containing groups. Batch adsorption experiments assessed performance.

Significant Findings

UiO-66–2OH showed excellent adsorption capacity and selectivity under alkaline conditions, due to its porous structure, high surface area, and rich hydroxyl/carboxyl sites. Spectroscopic analysis and DFT calculations indicated a strong coordination between Ge(IV) and hydroxyl groups on 2,5-dihydroxyterephthalic acid, enabling efficient Ge capture. At pH 10, it achieved a 253.87 mg/g capacity at room temperature. Kinetics followed a pseudo-n-order model, and isotherms fit the Langmuir model, suggesting chemisorption-driven monolayer adsorption. Robust Zr-O clusters ensured stability across multiple cycles. These findings position UiO-66–2OH as a promising adsorbent for sustainable Ge recovery from complex solutions.
锗(Ge)是一种稀有的战略元素,其在工业废水中的含量远远超过地球地壳的平均含量,需要有效的回收。方法以2,5-二羟基对苯二甲酸为连接剂,采用溶剂热法合成了含羟基的锆基金属有机骨架(UiO-66-2OH)。通过SEM、EDS、XRD、FT-IR、BET、XPS等表征,证实其结晶度高,含氧基团丰富。批量吸附实验评估性能。suio -66 - 2oh由于其多孔结构、高比表面积和丰富的羟基/羧基位点,在碱性条件下表现出优异的吸附能力和选择性。光谱分析和DFT计算表明,2,5-二羟基对苯二甲酸上的Ge(IV)和羟基之间有很强的配位,能够有效地捕获Ge。在pH值为10时,其室温容量为253.87 mg/g。动力学遵循伪n阶模型,等温线符合Langmuir模型,表明化学吸附驱动的单层吸附。稳健的Zr-O簇确保了跨多个周期的稳定性。这些发现表明UiO-66-2OH是一种很有前途的吸附剂,可以从复杂溶液中持续回收锗。
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引用次数: 0
Unraveling the role of oxygen species in Pt/MnO2 catalysts for low-temperature HCHO abatement: A precursor-dependent study 揭示氧在Pt/MnO2催化剂中用于低温HCHO减排的作用:前体依赖研究
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-04-01 Epub Date: 2025-12-08 DOI: 10.1016/j.jtice.2025.106541
Wei Tong , Jie Yang , Yaxiong Ji , Hongli Wu

Backgrounds

Formaldehyde (HCHO) is a hazardous indoor pollutant requiring efficient low-temperature abatement. Catalytic oxidation effectiveness hinges on active oxygen species generation.

Methods

Pt/δ-MnO2 catalysts were synthesized using five manganese precursors (acetate, sulfate, carbonate, chloride, nitrate) via impregnation-reduction. Catalytic performance was assessed for HCHO oxidation (200–460 ppm, 80,000 mL/(g·h)), with mechanisms probed via in situ DRIFTS, DFT, XPS, EPR, Raman, H2-TPR, SEM, TEM and N2 adsorption-desorption.

Significant findings

Pt/MnO2-S (sulfate-derived) achieved 100 % HCHO conversion at 50 °C (200 ppm, 80,000 mL/(g·h)), outperforming other precursors due to its abundant oxygen vacancies (EPR/XPS) and high metallic Pt° content (55 %, XPS). In situ DRIFTS and DFT calculations revealed that Pt nanoparticles and oxygen vacancies synergistically generate active oxygen species, enabling a dual-path "butterfly mechanism": Under O2-rich conditions, surface radicals (O, OH) dominate oxidation to CO2/H2O; in O2-deficient environments, lattice oxygen participates, accumulating formate intermediates. Pt/MnO2-S exhibited exceptional stability (100 % conversion at 460 ppm for >4 h) and recyclability. The work establishes oxygen vacancy engineering as critical for enhancing Pt-MnO2 interfacial reactivity.
甲醛(HCHO)是一种有害的室内污染物,需要有效的低温减排。催化氧化的效果取决于活性氧的生成。方法以五种锰前驱体(乙酸、硫酸盐、碳酸盐、氯化物、硝酸盐)为原料,通过浸渍还原法制备spt /δ-MnO2催化剂。考察了HCHO氧化(200-460 ppm, 80000 mL/(g·h))的催化性能,并通过原位漂移、DFT、XPS、EPR、拉曼、H2-TPR、SEM、TEM和N2吸附-解吸探讨了机理。spt /MnO2-S(硫酸盐衍生)在50°C (200 ppm, 80,000 mL/(g·h))下实现了100%的HCHO转化,由于其丰富的氧空位(EPR/XPS)和高金属Pt°含量(55%,XPS),优于其他前驱体。原位漂移和DFT计算表明,Pt纳米颗粒和氧空位协同产生活性氧,实现了双程“蝴蝶机制”:在富氧条件下,表面自由基(O, OH)主导氧化生成CO2/H2O;在缺乏o2的环境中,晶格氧参与,积累甲酸酯中间体。Pt/MnO2-S表现出优异的稳定性(在460ppm下4小时转化率100%)和可回收性。这项工作建立了氧空位工程是提高Pt-MnO2界面反应性的关键。
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引用次数: 0
Z-Scheme g-C3N4/BiVO4 photocatalysts via hydrothermal tuning: charge transfer mechanism and machine learning optimization 水热调谐Z-Scheme g-C3N4/BiVO4光催化剂:电荷转移机制和机器学习优化
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-04-01 Epub Date: 2025-11-08 DOI: 10.1016/j.jtice.2025.106514
Zili Liang , Jianan Dai , Meiting Zhao , Jing Ma , Jiaxing Zhang , Tengyue Zhang , Rui Liu

Background

Escalating global water pollution from intensified industrial and agricultural activities has highlighted the urgent need for sustainable wastewater treatment. Semiconductor photocatalysis is a promising solution, yet conventional type-II heterojunctions often suffer from sluggish charge separation and weak redox capacity, limiting their practical application.

Methods

To address these challenges, a series of Z-scheme g-C3N4/BiVO4 (CN/BV) heterojunctions were rationally engineered via hydrothermal temperature modulation (100-180 °C), enabling precise control of crystallinity, morphology, and band alignment. Advanced characterizations (XRD, TEM, UV-vis DRS, and XPS) were combined with EPR analysis, DFT calculations, and XPS valence band studies to elucidate the structure–property–activity relationship. Furthermore, machine learning models were integrated with experimental data to predict norfloxacin (NOR) degradation performance under diverse operational conditions.

Significant Findings

The optimized CN/BV composite synthesized at 120°C exhibited outstanding photocatalytic activity, achieving 94.41 % degradation of norfloxacin (10 mg/L) within 120 min under visible light (λ > 420 nm), with an apparent rate constant (k = 0.02618 min⁻¹), 4.83 times higher than BiVO4 and 2.44 times higher than g-C3N4. EPR and radical trapping analyses identified •OH and •O₂⁻ as the dominant reactive species, while mechanistic evidence confirmed a direct Z-scheme charge transfer pathway enabling efficient carrier separation and strong redox capability. Integrating this rationally designed photocatalyst with machine-learning prediction (R2 = 0.8558, RMSE = 0.0510) establishes a data-driven framework for performance optimization. This study provides both a mechanistic insight and an intelligent design paradigm for next-generation photocatalysts targeting efficient degradation of emerging contaminants.
工业和农业活动加剧造成的全球水污染不断升级,凸显了对可持续废水处理的迫切需要。半导体光催化是一种很有前途的解决方案,但传统的ii型异质结往往存在电荷分离缓慢和氧化还原能力弱的问题,限制了它们的实际应用。方法为了解决这些问题,通过水热温度调制(100-180℃)合理地设计了一系列Z-scheme g-C3N4/BiVO4 (CN/BV)异质结,实现了对结晶度、形貌和能带取向的精确控制。先进的表征(XRD, TEM, UV-vis DRS和XPS)结合EPR分析,DFT计算和XPS价带研究来阐明结构-性能-活性关系。此外,将机器学习模型与实验数据相结合,预测诺氟沙星(NOR)在不同操作条件下的降解性能。在120℃下合成的优化后的CN/BV复合材料具有良好的光催化活性,在可见光(λ > 420 nm)下,在120 min内对诺氟沙星(10 mg/L)的降解率达到94.41%,表观速率常数(k = 0.02618 min⁻¹)比BiVO4高4.83倍,比g-C3N4高2.44倍。EPR和自由基捕获分析确定•OH和•O₂⁻作为主要的反应物质,而机制证据证实了直接的Z-scheme电荷转移途径能够有效地分离载流子和增强氧化还原能力。将这种合理设计的光催化剂与机器学习预测(R2 = 0.8558, RMSE = 0.0510)相结合,建立了一个数据驱动的性能优化框架。这项研究为下一代光催化剂高效降解新出现的污染物提供了机理见解和智能设计范例。
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引用次数: 0
Boron-enriched edge-nitrogen doped porous carbon nanosheets as cathode for zinc-ion hybrid capacitors 富硼边氮掺杂多孔碳纳米片作为锌离子杂化电容器的阴极
IF 6.3 3区 工程技术 Q1 ENGINEERING, CHEMICAL Pub Date : 2026-04-01 Epub Date: 2025-11-07 DOI: 10.1016/j.jtice.2025.106511
Hui Xu , Jun Ni , Meng Liu , Dongxue Han , Lichao Tan , Wenli Zhang , Xiaoliang Wu , Xin Wang

Background

Developing porous carbon materials with abundant accessible active sites and fast charge-transfer kinetics still remains a significant challenge.

Methods

Herein, boron-enriched edge-nitrogen doped porous carbon nanosheets (BNPC) were prepared by electrostatic self-assembly of chitin and graphene oxide using boric acid as a boron source followed by carbonization. Boron-enriched edge-type N functional groups with porous nanosheet-like structure and high specific surface area ensure more accessible active sites and rapid charge-transfer kinetics.

Significant Findings

The obtained BNPC-900 shows a specific capacity of 367.0 F g−1 at 0.5 A g−1, outstanding rate characteristics, and superior electrochemical stability. Furthermore, the constructed BNPC-900//BNPC-900 symmetric supercapacitor displays an energy density of 28.6 Wh kg−1 and superior electrochemical steadiness. More interestingly, the Zn//ZnSO4//BNPC-900 hybrid capacitor achieves an energy density of 106.9 Wh kg−1 and outstanding electrochemical stability.
开发具有丰富活性位点和快速电荷转移动力学的多孔碳材料仍然是一个重大挑战。方法以硼酸为硼源,通过静电自组装甲壳素和氧化石墨烯制备富硼边氮掺杂多孔碳纳米片(BNPC)。富硼的边缘型N官能团具有多孔纳米片状结构和高比表面积,确保了更容易接近的活性位点和快速的电荷转移动力学。在0.5 a g−1下,BNPC-900的比容量为367.0 F g−1,具有出色的速率特性和优异的电化学稳定性。此外,所构建的BNPC-900//BNPC-900对称超级电容器具有28.6 Wh kg−1的能量密度和优异的电化学稳定性。更有趣的是,Zn//ZnSO4//BNPC-900混合电容器的能量密度达到106.9 Wh kg−1,具有出色的电化学稳定性。
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引用次数: 0
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Journal of the Taiwan Institute of Chemical Engineers
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