MOFs基材料用于环境污染控制文献整理（2024.12.29-2025.01.04）

为较全面地展示MOFs材料在环境污染控制领域的研究进展并服务于同行，NMTer课题组每周收集整理“MOFs基材料用于环境污染控制”方面的文献资料，通过“MOFs帮助环境”公众号推送。欢迎各位老师和同学关注！同时，欢迎各位老师将您的相关成果在本公众号做专题推送宣传。“赠人玫瑰，手有余香”！

题目：Floatable artificial leaf to couple oxygen-tolerant CO₂ conversion with water purification

作者：Zhiyong Zhang,  Yang Wang,  Yangen Xie,  Toru Tsukamoto, Qi Zhao, Qing Huang, Xingmiao Huang, Boyang Zhang, Wenjing Song, Chuncheng Chen, Hua Sheng* & Jincai Zhao

摘要：To enable open environment application of artificial photosynthesis, the direct utilization of environmental CO₂ via an oxygen-tolerant reductive procedure is necessary. Herein, we introduce an in situ growth strategy for fabricating two-dimensional heterojunctions between indium porphyrin metal-organic framework (In-MOF) and single-layer graphene oxide (GO). Upon illumination, the In-MOF/GO heterostructure facilitates a tandem CO₂ capture and photocatalytic reduction on its hydroxylated In-node, prioritizing the reduction of dilute CO₂ even in the presence of air-level O₂. The In-MOF/GO heterostructure photocatalyst is integrated with a porous polytetrafluoroethylene (PTFE) membrane to construct a floatable artificial leaf. Through a triphase photocatalytic reaction, the floatable artificial leaf can remove aqueous contaminants from real water while efficiently reducing CO₂ at low concentrations (10%, approximately the CO₂ concentration in combustion flue gases) upon air-level O₂. This study provides a scalable approach for the construction of photocatalytic devices for CO₂ conversion in open environments.

期刊信息：Nat. Commun.

DOI：10.1038/s41467-024-55753-2

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题目：Phase controllable fabrication of MOF-derived iron nickel sulfides as Fenton-like catalysts for peroxymonosulfate activation: The phase transition effect induced variations in the mechanism and performance

作者：Wei Li, Daman Cheng, Xu Yin, Qi Zhang, Siyuan Cao, Hongwei Zhu, Zhifeng Gao, Kajia Wei*, Weiqing Han*

摘要：This study constructed an iron-nickel bimetallic sulfide (FeNiS@C) with a controllable phase to significantly improve PMS activation and durability. The precise phase control and continuous phase transition were achieved by tuning the sulfuration temperature, and the phase transformation from Ni-rich (Fe, Ni)S₂ to Ni-poor (Fe, Ni)S₂ and Fe-doped NiS changed the d-band center and work function of FeNiS@C, which induced variation in the electron-donating ability and Ni charge in each phase further improving the electron-transfer rate and dominating HO•, SO₄^-• and ¹O₂ generation. The Ni-rich (Fe, Ni)S₂ phase exhibited a 21- and 9-fold increased bisphenol A (BPA) removal rate (0.251 min ), excellent structural robustness (> 95 % reactivity maintained after cycling and long-term assays) and satisfactory anti-interference ability over the other two phases, demonstrating promising application prospects in actual wastewater. This work provides new insight into phase-controllable bimetallic sulfide catalyst preparation and phase transition mechanisms for heterogeneous Fenton-like systems.

期刊信息：Appl. Catal. B-Environ.

DOI：10.1016/j.apcatb.2024.124988

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题目：In situ self-grown synthesis of c-MOF@NiO heterostructure anchored to c-MOF/rGA particle electrode: Promoting sustained and efficient degradation of phenol in coking wastewater

作者：Shaojun Gao, Weifeng Liu*, Meiling Wang, Dongju Fu, Zongbin Zhao, Xuguang Liu*

摘要：Herein, we design a high-performance graphene composite aerogel-based particle electrode with superior phenol degradation effect and long-lasting working capability. In situ anchoring c-MOF@NiO heterostructure on c-MOF/rGA surface was realised with a controlled pyrolysis strategy. The three-dimensional electrocatalytic degradation system composed of c-MOF@NiO/rGA particle electrode achieves 100 % phenol degradation rate in 20 min with a degradation rate constant of 0.1323 min⁻¹, and maintains a phenol degradation rate of 95.27 % after 50 consecutive cycles. Density functional theory calculations show that the c-MOF@NiO heterostructure exhibits the most favorable ΔG_OOH*, which effectively promotes the 2e^- ORR process and facilitates the generation of H₂O₂. The defect-induced generation of O₂^•- and •OH together promotes the mineralisation process of phenol. The particle electrode also exhibits good real coking wastewater treatment capability. This work provides a strong motivation for the deep treatment of coking wastewater and the practical process of 3D electrodes.

期刊信息：Appl. Catal. B-Environ.

DOI：10.1016/j.apcatb.2024.124911

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题目：Enhanced defluoridation of neutral and weakly alkaline water using well-dispersed cerium-based metal–organic framework mediated by tannic acid

作者：Liting Wang, Haochen Wang, Hui Qiu*

摘要：

Cerium-based metal–organic frameworks (Ce-MOFs) demonstrate excellent fluoride adsorption capabilities, primarily due to inner-sphere complexation interaction, especially in neutral and weakly alkaline groundwater. However, the potential agglomeration of Ce-MOF particles significantly limits defluoridation efficiency in practical applications. In this work, we present a simple method for synthesizing Ce-MOF with improved dispersibility by using tannic acid (TA) to mediate the formation of TA-Ce-ABDC between Ce ions and 2-aminoterephthalic acid (ABDC). The newly prepared TA-Ce-ABDC had a higher Brunauer–Emmett–Teller (BET) surface area and better stability than original Ce-ABDC. The batch adsorption experiments demonstrated that TA-Ce-ABDC exhibits optimal fluoride adsorption within a broad pH range of 3.0 to 9.0. Notably, TA-Ce-ABDC achieved a maximum adsorption capacity of 206.04 mg·g⁻¹ at pH 7.0 and 194.32 mg·g⁻¹ at pH 9.0. These values significantly surpass those of other synthesized Ce-MOFs and previously reported materials, thereby confirming the superior performance of TA-Ce-ABDC in fluoride adsorption. The equilibrium time of TA-Ce-ABDC was 70 min, which is less than half that of Ce-ABDC. Under conditions with high concentrations of competitive anions, TA-Ce-ABDC exhibited significantly better adsorption selectivity compared to other common adsorbents. The analysis of X-ray photoelectron spectrogram (XPS) and Fourier transform infrared (FTIR) spectra suggested that the defluoridation mechanism of TA-Ce-ABDC involved electrostatic interaction, ion exchange and inner-sphere complexation. In fixed-bed adsorption experiments, impressive working capacities of 462 and 354 bed volumes were observed for TA-Ce-ABDC at pH 7.0 and 9.0, respectively, which were 3.08 and 3.69 times that of commercial activated alumina. TA-Ce-ABDC demonstrated significant potential for reusability and practical application. The findings of this study offer valuable insights into the use of Ce-MOFs for effective groundwater defluoridation.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.159198

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题目：Sustainable solar-driven interfacial evaporation-photocatalytic degradation of Cu-ZIF-67/rGO/PVA aerogel: A multifunctional material for pollutant treatment

作者：Fan Nie, Jihai Cai, Lingxuan Ma, Sheng Gong, Shuangpeng Wang, Wenqian Chen, Shengliang Li*, Jinchao Wei*, Peng Li *

摘要：Simultaneously satisfying recovery and efficient degradation remains a challenge for photocatalysis in pollutant treatment. Hence, Cu-ZIF-67 loaded rGO/PVA aerogel (Cu-ZIF-67/rGO/PVA) is prepared by thermal reduction and surface growth, which boosts photocatalytic rate of recyclable aerogel by utilizing concomitant heat to enhance mass transfer by interfacial evaporation. The Cu ions doping of ZIF-67 advances the overlapping of its absorption band with sunlight and accelerates the separation of the photogenerated hole-electron. PVA based aerogel provides mechanical strength for loading and recycling of Cu-ZIF-67. rGO provides an excellent conductive substrate to extract and transport charge carriers to the reaction site while enhancing solar energy absorption and interfacial evaporation efficiencies. The evaporation rate of Cu-ZIF-67/rGO/PVA could reach 1.95 kg m^-2h⁻¹ under 1 kW m⁻² simulated solar illumination, and the photothermal conversion efficiency could reach 92.1 %. Highly efficient thermal conversion promotes rapid localized warming of the Cu-ZIF-67/rGO/PVA, accelerating the production of reactive oxidants and enhancing their reactivity. Under one solar intensity, the degradation of MB by Cu-ZIF-67/rGO/PVA was significantly improved, increasing from 14.79 % to 78.52 %. Moreover, Cu-ZIF-67/rGO/PVA has excellent salt resistance. Therefore, Cu-ZIF-67/rGO/PVA shows strong potential for synergistic photocatalytic degradation of organic pollutants via interfacial evaporation, providing a novel approach for complex pollutant treatment.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.159130

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题目：Enhanced cesium adsorption and desorption mechanisms in ZnFe Prussian blue analogs: Structural transformation and reusability

作者：Semin Eun, Eunkyung Cho, Jungho Ryu, Hyuncheol Kim, Minsun Kim, Bogyung Kim, Soonhyun Kim*

摘要：The management of radioactive cesium (¹³⁷Cs) is critical due to its long half-life, environmental persistence, and harmful effects on human health and ecosystems. Although Prussian blue analogs (PBAs) have gained attention for their potential in adsorption-based Cs⁺ removal, the structural changes that occur during adsorption and desorption cycling are poorly understood. This study investigates the synthesis of ZnFe-PBAs using various methodologies, including photochemical reduction and the use of different precursors and reducing agents, to achieve diverse oxidation states in their lattice structures. The photochemically synthesized ZnFe-PBAs exhibited significantly enhanced Cs⁺ adsorption capacities compared to those of conventional materials. Comprehensive characterization techniques, including X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, were employed to assess the physicochemical properties of the ZnFe-PBAs and examine their structural changes during Cs⁺ adsorption and desorption. The results revealed that the ZnFe samples exhibited distinct structural transformations, with ZnFe-W showing rapid structural changes that facilitated rapid Cs⁺ adsorption and desorption. In contrast, ZnFe-Y maintained a stable cubic structure throughout the process. Adsorption isotherm and kinetic studies confirmed that ion exchange with K⁺ is the primary mechanism of Cs⁺ adsorption, and it was deduced that the desorption efficiency varied with the choice of desorption solution. This study highlights the importance of understanding structural changes during Cs⁺ removal and provides insights into designing more efficient and reusable adsorbents. These findings suggest that ZnFe-PBAs have strong potential for cesium removal in simulated nuclear waste environments and a promising strategy for radioactive contaminant management.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.159161

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题目：Surface-Engineered 2D Bimetallic FeNi-MOFs Derived from Layered Double Hydroxides for Photocatalytic Membranes with Enhanced Dye Fixation in Wastewater Treatment

作者：Gayathri Karthikeyan, Sakar Mohan, P. Muthu Austeria*, R. Geetha Balakrishna*

摘要：FeNi-based layered double hydroxides (LDHs) are used as precursors to derive bimetallic FeNi-metal organic frameworks (D-FeNi MOFs) with terephthalic acid ligands, offering enhanced properties compared to conventionally prepared FeNi-MOFs (C-FeNi MOFs). D-FeNi MOFs exhibited superior structural, surface, and electrochemical features, confirmed by density functional theory (DFT) studies, which also predicted their catalytic mechanism. Band edge potential calculations through Mott-Schottky analysis revealed their favorable redox potential, enhanced charge transfer, and reduced recombination resistance, explaining their superior photocatalytic efficiency. D-FeNi MOFs degraded 91% of rhodamine B (RhB) and 89% of Congo red (CR), outperforming C-FeNi MOFs, which degraded 84% and 77%, respectively. These MOFs are incorporated (3, 5, and 7 wt%) into polysulfone (PSU) membranes to develop photocatalytic membranes. The 7 wt% membranes (FNM7) exhibited high water flux (54.4 L m⁻²h⁻¹) and dye flux (≈51.1 and 41.6 L m⁻²h⁻¹) with rejection rates of ≈88% and 90% for RhB and CR, significantly surpassing bare membranes. FNM7 demonstrated superior anti-fouling and photocatalytic regeneration (12.9% RhB, 9.6% CR degradation under sunlight) across three cycles. DFT studies showed FeNi centers weaken dye molecule bonds, aiding degradation, while carboxyl groups in MOFs formed robust hydrogen bonds with PSU, ensuring no particle leaching. This highlights D-FeNi MOF-membranes as an efficient system for wastewater treatment.

期刊信息：Small

DOI：10.1002/smll.202409133

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题目：Robust and anti-biofouling bio-based aerogel with Schiff base network stabilized MOFs for efficient removal of tartrazine dye and U(VI) ions

作者：Cuiyun Liu*, Menghui Zhao , Hui Liu , Jun Zhang , Zihao Hu , Yuhan Zhang , Xinchang Pang*

摘要：Tartrazine (TAR), widely used as a synthetic food dye, and U(VI), primarily originating from nuclear industry effluents, pose serious environmental and health risks due to their toxicity and persistence. However, many existing adsorbents suffer from low capacity, poor stability, and limited reusability. Herein, A bio-based aerogel adsorbent (NDC) with a stable three-dimensional porous network structure was prepared through a Schiff base reaction between dialdehyde-functionalized nanocellulose fibrils (DNCFs), chitosan (CS), and aminated metal–organic frameworks (MOFs). The synergistic effect of MOFs, DNCFs, and CS resulted in high adsorption capacities of 689.66 mg/g for TAR and 285.72 mg/g for U(VI) at a temperature of 303 K, respectively. Additionally, the Schiff base chemical bonds firmly anchored the MOFs in the NDC aerogel, providing a compressive strength of 547.4 kPa at 70 % strain. Furthermore, due to the antibacterial properties of the amino groups on CS and MOFs, the NDC aerogel demonstrated excellent anti-biofouling performance. The results suggest that bio-based NDC aerogel is an efficient and prospective for the removal of TAR and U(VI) from wastewater as an adsorbent.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131277

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题目：Strategic tuning of GO ratios in CuBTC-GO nanocomposites for next-generation tetracycline adsorption: A deep dive into isotherms, kinetics, and thermodynamics

作者：Palkaran Sethi , Sanghamitra Barman*, Soumen Basu*

摘要：The increasing environmental persistence of tetracycline antibiotics demands effective removal solutions to safeguard water quality. This study investigates the adsorption of tetracycline hydrochloride using a copper benzene-1,3,5-tricarboxylate (Cu-BTC) hybridized with graphene oxide (GO). The CuBTC-GO composite, synthesized in varying ratios (1:1, 1:3, 3:1), was extensively characterized using field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), thermogravimetric analysis (TGA), zeta potential analysis, and Brunauer-Emmett-Teller (BET) surface area analysis, confirming its robust structure, thermal stability, and high porosity. Adsorption experiments were optimized by systematically varying key parameters, including adsorbent dosage, pollutant concentration, temperature, pH, stirring speed, and time. The composite achieved a remarkable removal efficiency of 97.7 % for 25 ppm tetracycline at pH 10 within 90 min. Reusability tests confirmed consistent performance over six cycles, while real-world medical wastewater treatment demonstrated 65 % removal efficiency. The adsorption process was comprehensively analyzed using six equilibrium isotherm models (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Halsey, and Harkins-Jura). The Langmuir model provided the best fit (R² = 0.99725), indicating monolayer adsorption with chemisorption as the dominant mechanism (adsorption energy:12.121 kJ/mol). Additionally, π-π stacking, hydrogen bonding, electrostatic interactions, and pore filling contributed significantly to adsorption confirmed by post-adsorption characterizations (XRD, FTIR, BET, FESEM-EDS). Kinetics were evaluated using five models (pseudo-first-order, pseudo-second-order, Elovich, intraparticle diffusion, and liquid film model) and the pseudo-second-order model best described the adsorption (R² = 0.99989), with a rate constant of 0.0151 min⁻¹, indicating a chemical reaction-controlled process. Thermodynamic studies revealed the endothermic nature of the process (ΔH = 82.361 kJ/mol), its spontaneity (ΔG = -1.3077 kJ/mol), and less randomness at the solid–liquid interface (ΔS = -0.251 kJ/mol K). This study provides a comprehensive chemical engineering approach to adsorption process design, integrating detailed isotherm, kinetic, and thermodynamic analyses. The CuBTC-GO composite exhibits superior adsorption performance for a very high concentration of tetracycline, faster kinetics, and enhanced reusability, compared to the existing literature positioning it as a promising material for the sustainable remediation of antibiotic-contaminated wastewater.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131311

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本期编辑

郭一辰，男，北京建筑大学2024级环境工程专业硕士研究生。主要研究方向为金属-有机框架及其衍生物材料的设计与制备及其在水环境修复方面的研究。

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