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题目：Chemical transformations of highly toxic H₂S to promising clean energy in MOFs

作者：Juan L. Obeso, Daniel R. Amaro, Catalina V. Flores, Aída Gutiérrez-Alejandre, Ricardo A. Peralta, Carolina Leyva*, Ilich A. Ibarra*

摘要：Metal-Organic Frameworks (MOFs) are one of the most attractive and promising candidates for sequestering toxic H₂S. Furthermore, the chemical transformation of H₂S within their pores to form polysulfides is one of the most exciting discoveries for the development of new technologies for future applications in lithium-sulfur batteries. Herein, we discuss how a group of selected MOFs have been used in the field of the adsorption and oxidation of H₂S. Mainly, it is presented the main pathway in the conversion mechanism to understand the relevance of the metal center and the linker, emphasizing the relevant role of open metal sites (OMS) and hemilabile (non-permanent) sites for the generation of polysulfides. Finally, we expect that this review article can provide relevant insights on re-utilizing MOFs, previously used for capturing toxic H₂S, to investigate a new fascinating environmental-remediation application which is the generation of clean energy. 

期刊信息：Coord. Chem. Rev.

DOI：10.1016/j.ccr.2023.215135

论文链接：

题目：Ligand-Assistant Iced Photocatalytic Reduction to Synthesize Atomically Dispersed Cu Implanted Metal-Organic Frameworks for Photo-Enhanced Uranium Extraction from Seawater

作者：Tao Liu, Anping Gu, Tao Wei, Mengwei Chen, Xi Guo,  Shuai Tang,  Yihui Yuan,  Ning Wang*

摘要：Uranium extraction from natural seawater is one of the most promising routes to address the shortage of uranium resources. By combination of ligand complexation and photocatalytic reduction, porous framework-based photocatalysts have been widely applied to uranium enrichment. However, their practical applicability is limited by poor photocatalytic activity and low adsorption capacity. Herein, atomically dispersed Cu implanted UiO-66-NH₂ (Cu SA@UiO-66-NH₂) photocatalysts are prepared via ligand-assistant iced photocatalytic reduction route. N—Cu–N moiety acts as an effective electron acceptor to potentially facilitate charge transfer kinetics. By contrast, there exist Cu sub-nanometer clusters by the typical liquid phase photoreduction, resulting in a relatively low photocatalytic activity. Cu SA@UiO-66-NH₂ adsorbents exhibit superior antibacterial ability and improved photoreduction conversion of the adsorbed U(VI) to insoluble U(IV), leading to a high uranium sorption capacity of 9.16 mg-U/g-Ads from natural seawater. This study provides new insight for enhancing uranium uptake by designing SA-mediated MOF photocatalysts.

期刊信息：Small.

DOI：10.1002/smll.202208002

论文链接：

题目：Multifunctional Fe-doped carbon dots and metal-organic frameworks nanoreactor for cascade degradation and detection of organophosphorus pesticides 

作者：Xuejuan Ma, Qi Ou, Jiajia Yuan, Jiaojiao Yang, Shuxia Xu*, Xinfeng Zhang*

摘要：Organophosphorus pesticides (OPs) are the most widely used pesticides, hence it is crucial to effectively prevent and control OPs residues for agricultural product safety and ecological development. In this work, the nanoreactor consisting of Fe-doped carbon dots (Fe-CDs) and metal-Organic frameworks (MOF-808) were developed for selective degradation as well as sensitive detection of paraoxon and parathion. MOF-808 was selected as the host and used to rapidly degrade paraoxon due to its excellent organophosphorus hydrolase activity. Fe-CDs were severed as guest molecules not only for photocatalytic degradation of parathion, but also for sensing to detect OPs. Through host-guest interaction, Fe-CDs/MOF-808 and Fe-CDs@MOF-808 were synthesized for cascade degradation and detection of paraoxon and parathion, respectively. Paraoxon and parathion were detoxified by catalytic hydrolysis and photocatalytic degradation by Fe-CDs/MOF-808 and Fe-CDs@MOF-808, respectively. Meanwhile, the fluorescence of the nanocomposites was quenched by the internal filtering effect with 4-nitrophenol (4-NP), the degradation product of OPs. Fe-CDs/MOF-808 has a wide linear range for detection of paraoxon from 0.001 to 360 μM, with a limit of detection (LOD) as low as 0.3 nM. Fe-CDs@MOF-808 exhibited a linear range of 0.01-100 μM for parathion, with an LOD about 3.3 nM. The reliability of the nanoreactor was verified by testing the recovery rate of OPs spiked in water sample. Meanwhile, the nanoreactors were applied for degradation and detection of OPs in pakchoi. The OPs in pakchoi can be fully degraded within 5 min, and the analytical results are consistent with those by standard method (HPLC). Therefore, the proposed nanoreactor provides a feasible alternative for effective degradation and timely detection of OPs during agricultural production. 

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2023.142480

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题目：Boosting Solar-Driven Volatile Organic Compounds Desorption via the Synergy of NH₂-UiO-66 with Hollow Polypyrrole Nanotube 

作者：Mengying Feng, Sijia Chen, Guiying Li, Yingxin Yu, Weiping Zhang, Jiangyao Chen, Hongli Liu*, Taicheng An 

摘要：Metal-organic frameworks (MOFs) are witnessing rapid development in the adsorption removal of volatile organic compounds (VOCs) from polluted air due to their remarkable adsorption capacity. However, their intrinsic poor thermal conductivities often make their regeneration processes suffer from high energy consumption. Herein, a novel photodynamic NH₂-UiO-66@PPy adsorbent was constructed by in-situ growth of NH₂-UiO-66 particles onto hollow PPy nanotubes via a facile solvothermal method. This adsorbent was able to extend the light response range of NH₂-UiO-66 from UV-vis to near-infrared region. Benefitting from the superior photothermal conversion ability of PPy and well contact interface between PPy nanotube and its surface-loaded NH₂-UiO-66 particles, higher surface temperature of PPy nanotubes would be obtained upon exposure to UV-vis-NIR light and further transferred to its surrounding MOF nanoparticles. Eventually, the surface temperature of the optimal NH₂-UiO-66@PPy-2 adsorbent can be as high as 245 °C, and almost 100% of the adsorbed ethyl acetate was able to be released within 30 min of UV-vis-NIR irradiation. Distinct from the conventional heating whole adsorbent bed, this photothermal desorption strategy would significantly reduce the heat-transfer among adsorbent particles and become less dependent on the heat-transfer rate, thus efficiently alleviating the intrinsic thermal conductivity shortcoming of MOF.

期刊信息：Chem. Eng. J. 

DOI：10.1016/j.cej.2023.142503

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题目：Constructing Liquid Metal/Metal-Organic Framework Nanohybrid with Strong Sonochemical Energy Storage Performance for Enhanced Pollutants Removal

作者：Junjie Yan*, Chen Su, Kequan Lou, Min Gu, Xinyu Wang, Donghui Pan, Lizhen Wang, Yuping Xu, Chongyang Chen, Yu Chen, Daozhen Chen*, Min Yang*.

摘要：With endogenous redox systems and multiple enzymes, the storage and utilization of external energy is general in living cells, especially through photo/ultrasonic synthesis/catalysis due to in-situ generation of abundant reactive oxygen species (ROS). However, in artificial systems, because of extreme cavitation surroundings, ultrashort lifetime and increased diffusion distance, sonochemical energy is rapidly dissipated via electron-hole pairs recombination and ROS termination. Here, we integrate zeolitic imidazolate framework-90 (ZIF-90) and liquid metal (LM) with opposite charges by convenient sonosynthesis, and the resultant nanohybrid (LMND@ZIF-90) can efficiently scavenge sonogenerated holes and electrons, and thus suppress electron-hole pairs recombination. Unexpectedly, LMND@ZIF-90 can store the ultrasonic energy for over ten days and exhibit acid-responsive release to trigger persistent generation of various ROS including superoxide (O₂•⁻), hydroxyl radicals (•OH), and singlet oxygen (¹O₂), presenting significantly faster dye degradation rate (short to seconds) than previously reported sonocatalysts. Moreover, unique properties of gallium could additionally facilitate heavy metals removal through galvanic replacement and alloying. In summary, the LM/MOF nanohybrid constructed here demonstrates strong capacity for storing sonochemical energy as long-lived ROS, enabling enhanced water decontamination without energy input.

期刊信息：J. Hazard. Mater.

DOI：10.1016/j.jhazmat.2023.131285

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题目：Mercury Clathration-Driven Phase Transition in a Luminescent Bipyrazolate Metal–Organic Framework: A Multitechnique Investigation

作者：Marco Moroni, Luca Nardo*, Angelo Maspero, Guglielmo Vesco, Marco Lamperti, Luca Scapinello, Rebecca Vismara, Jorge A. R. Navarro, Damiano Monticelli, Andrea Penoni, Massimo Mella, and Simona Galli*

摘要：Mercury is one of the most toxic heavy metals. By virtue of its triple bond, the novel ligand 1,2-bis(1H-pyrazol-4-yl)ethyne (H₂BPE) was expressly designed and synthesized to devise metal–organic frameworks (MOFs) exhibiting high chemical affinity for mercury. Two MOFs, Zn(BPE) and Zn(BPE)·nDMF [interpenetrated i-Zn and noninterpenetrated ni-Zn·S, respectively; DMF = dimethylformamide], were isolated as microcrystalline powders. While i-Zn is stable in water for at least 15 days, its suspension in HgCl₂ aqueous solutions prompts its conversion into HgCl₂@ni-Zn. A multitechnique approach allowed us to shed light onto the observed HgCl₂-triggered i-Zn-to-HgCl₂@ni-Zn transformation at the molecular level. Density functional theory calculations on model systems suggested that HgCl₂ interacts via the mercury atom with the carbon–carbon triple bond exclusively in ni-Zn. Powder X-ray diffraction enabled us to quantify the extent of the i-Zn-to-HgCl₂@ni-Zn transition in 100–5000 ppm HgCl₂ (aq) solutions, while X-ray fluorescence and inductively coupled plasma-mass spectrometry allowed us to demonstrate that HgCl₂ is quantitatively sequestered from the aqueous phase. Irradiating at 365 nm, an intense fluorescence is observed at 470 nm for ni-Zn·S, which is partially quenched for i-Zn. This spectral benchmark was exploited to monitor in real time the i-Zn-to-HgCl₂@ni-Zn conversion kinetics at different HgCl₂ (aq) concentrations. A sizeable fluorescence increase was observed, within a 1 h time lapse, even at a concentration of 5 ppb. Overall, this comprehensive investigation unraveled an intriguing molecular mechanism, featuring the disaggregation of a water-stable MOF in the presence of HgCl₂ and the self-assembly of a different crystalline phase around the pollutant, which is sequestered and simultaneously quantified by means of a luminescence change. Such a case study might open the way to new-conception strategies to achieve real-time sensing of mercury-containing pollutants in wastewaters and, eventually, pursue their straightforward and cost-effective purification.

期刊信息：Chem. Mater.

DOI：10.1021/acs.chemmater.2c03801

论文链接：

题目：Difunctional MOF-wrapped graphene membranes for efficient photothermal membrane distillation and VOCs interception

作者：Mengmeng Lou, Jingzi Li, Xiaowei Zhu, Jingchao Chen, Xingran Zhang, Xiaofeng Fang, Fang Li *

摘要：Photothermal membrane distillation (PMD) has the potential to address freshwater scarcity, but heat loss during heat transfer from the photothermal surface to the feed bulk inevitably lower the photothermal-vapor conversion efficiency of this process. The permeation of VOCs during PMD also threatens the recycling of distilled water. Herein, a zeolitic imidazolate framework-67 (ZIF-67) wrapped graphene membrane (ZGM) was developed and used for the PMD process. The results demonstrated that the hierarchical porous structure and low heat conductivity of ZIF-67 endowed the ZGM with improved light absorbance and heat localization, thus sustaining a high cross-membrane temperature gradient. Under simulated sunlight illumination, the ZGM attained an additional flux of 0.91 kg m⁻² h⁻¹, corresponding to a photothermal efficiency of 62.1%, which was 183.2% higher than that of the pristine membrane. The temperature change near the photothermal coating was simulated, which showed that ZGM had slower heat conduction into the feed, demonstrating a confined heat effect. Meanwhile, the ZGM exhibited a good interception for phenol when peroxymonosulfate (PMS) was added to the hot feed. The distilled phenol concentration was 88.0% lower than that of the PMD without PS. Electron paramagnetic resonance (EPR) and radical quenching experiments verified that singlet oxygen (¹O₂) was the dominant reactive oxygen species during in-situ phenol degradation. This work provides a new strategy to develop advanced photothermal membranes to simultaneously promote the photothermal performance and VOC interception.       

期刊信息：J. Membr. Sci.

DOI：10.1016/j.memsci.2023.121592

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题目：Temperature-regulated formation of hierarchical pores and defective sites in MIL-121 for enhanced adsorption of cationic and anionic dyes

作者：Na Hu, Fangxue Hang, Kai Li, Ting Liao, Darryn Rackemann, Zhanying Zhang, Changrong Shi, Caifeng Xie*

摘要：The micropore range of typical MOFs limits the accessibility of substances e.g., dyes have larger sizes. In this work, MIL-121 was transformed into hierarchically porous MOF variants through temperature-regulated linker thermolysis, of which hierarchical porosity (increased average pore size of up to 61.8 Å) and increased specific surface area of up to 346.2 m/g were achieved. Surface functionality of -COOH and anhydride groups were also improved together with the formation of defective sites and graphite carbon with π-conjugated layers. Improved adsorption of CR and MB were observed with the thermally treated variants, in particular for MIL-121-500 (597.9 and 246.0 mg/g, respectively), when compared with pristine MIL-121 (69.7 and 27.8 mg/g, respectively). Pseudo-second order and Langmuir models were used to explain the adsorption mechanisms. Thermodynamic studies revealed the adsorption of CR and MB on MIL-121-500 were spontaneous, and were endothermic and exothermic, respectively. Characterization of the adsorbents and the DFT calculations demonstrated the synergetic effect of the improved textural and functional properties (especially the oxygen defective sites) of MIL-121-500 was responsible for the enhanced adsorption of dyes. This work sheds light on improving the adsorption performance of MOFs to organic dyes through linker thermolysis and offering a systematic approach to designing custom-built MOFs for targeted applications.

期刊信息：Sep. Purif. Technol.

DOI：10.1016/j.seppur.2023.123650

论文链接：

题目：Fabrication of novel thin-film composite membrane based on ultrathin metal-organic framework interlayer for enhancing forward osmosis performance

作者：Hao Liu, Bo Li, Pin Zhao*, Rongming Xu, Chuyang Y. Tang, Weilong Song, Zunaira Habib, Xinhua Wang*

摘要：To improve operation efficiency, an interlayered thin-film composite forward osmosis (iTFC-FO) membrane was designed by introducing an ultrathin and porous interlayer based on aluminum tetra-(4-carboxyphenyl)porphyrin (a stable metal−organic framework nanosheet, Al-MOF). Surface characterization results revealed that Al-MOF spread evenly in the macro-porous substrate, and provided a flat and smooth reaction interface with moderate hydrophilicity and uniform small aperture. The resultant polyamide (PA) layer had a thin base (without intrusion into substrate) and crumpled surface (with abundant leaves). The leaves size and cross-linking degree of PA layer firstly increased and then decreased with the Al-MOF loading. Compared to the original membrane, the iTFC-FO showed an enhanced water permeability and a reduced reverse sodium flux in both modes of active layer facing feed solution (AL-FS) and active layer facing draw solution (AL-DS). To be specific, the specific reverse sodium flux (reverse sodium flux/pure water flux) decreased from 0.27 g/L to 0.04 g/L in the AL-FS mode, while from 1.36 g/L to 0.23 g/L in the AL-DS mode with 2 mol/L NaCl as DS. Moreover, the iTFC-FO maintained high stability and high permeability under high-salinity and contaminated environment. This study offers a new possibility for the rational fabrication of high-performance TFC-FO membranes.

期刊信息：Chin. Chem. Lett.

DOI：10.1016/j.cclet.2023.108369

论文链接：

题目：Hierarchical Cu-MOF Hollow Nanowires Modified Copper Mesh for Efficient Antibacterial PM Filtration

作者：Haiyan Li, Tao Wang, YULONG YING, Zhiqi Wang, Lianjun Pan and Sheng Wang*

摘要：The filtration of fine particulate matter (PM) particles poses a significant threat to public health, with potentially adverse effects on the lungs and blood. Metal mesh filters have shown promise as multifunctional PM filters, as the released metal ions can eliminate pathogens. However, filtration of fine PM particles is still challenging due to the large processing mesh size. In this study, we developed a hierarchical metal-organic-framework-based structure (Cu-MOF hollow nanowires) on copper mesh for PM filtration. The in-situ grown three-dimensional (3D) Cu-MOF hollow nanowires effectively reduced the pore size and provided an enhanced electrostatic surface with maximum MOF exposure. This Cu-MOF coated metal (CMM) demonstrated excellent filtration efficiencies in small-size PM regime (89.1% for PM0.3, 90.4% for PM0.5, 93.8% for PM1.0, and 98.1% for PM2.5). Furthermore, the CMM filter exhibited good antibacterial performance against both S. aureus and E. coli. These attractive metal-based materials show potential in developing energy-saving and high-efficient metal-based filters for various applications.

期刊信息：Inorg. Chem. Front.

DOI：10.1039/D3QI00349C

论文链接：

题目：In₂O₃/ZnO S-scheme heterojunction nanocomposite hollow microtubes with highly sensitive response to formaldehyde

作者：Yu Peng, Bei Cheng, Liuyang Zhang*, Jingjing Liu*, Jiaguo Yu*

摘要：As we all know, formaldehyde (HCHO) is extremely harmful to human health and has been identified as a primary carcinogen by the World Health Organization. Therefore, there is an urgent need to design efficient formaldehyde-sensing materials. In this work, a highly responsive formaldehyde sensor of In₂O₃@ZnO derived from MIL-68(In)@ZIF-8 precursor was successfully prepared. By adjusting the ratio of In₂O₃ and ZnO, it can be found that the performance of the resulting sensor has greatly improved under 100 ppm HCHO at an operating temperature of 220 °C and the detection limit can be as low as 4 ppb. Additionally, it also has excellent selectivity (Q≥10), anti-interference (the deviation value≤3.5%), and long-lasting stability (the variation value≤4%). Such distinguished sensing performance can be attributed to the metal-organic framework (MOF) derived step-scheme (S-scheme) heterojunction, which ultimately increases the adsorption of oxygen and HCHO. This work verifies that ingenious heterojunction construction can significantly improve gas sensing performance.

期刊信息：Sens. Actuators, B

DOI：10.1016/j.snb.2023.133700

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题目：Assembling a bifunctional BiOCl/Bi-MOF catalyst via sharing Bi-Cl bond: Achieving ultra-efficient CO₂ capture and photoreduction

作者：Lan Ding, Yuning Li, Yongping Ding, Fenghua Bai, Ben Jia, Huiqin Li*, Xiaojing Wang*

摘要：Recently, capturing and photocatalytically converting CO₂ to carbon fuels has been demonstrated as a sustainable and green approach to solve the issue of greenhouse gas with good efficiency and low cost. However, the most photocatalysts suffer from low solar light harvest and poor CO₂ adsorption capacity. Here, the BiOCl nanoflowers have been in situ planted on Bi-MOF nanosheets to form BiOCl/Bi-MOF hybrids, in which BiOCl flowers contribute to harvest solar light and Bi-MOF nanosheets response to capture CO₂. Moreover, by the shared Bi-Cl bonding linkage, the smoothly tunnels is constructed to quickly transport photo-generated carriers. Hence, the assembly presents excellent CO₂ capture and light-driven CO₂-conversion activity, reaching up to 456.7 μmol⋅g⁻¹⋅h⁻¹. Furthermore, different from the quickly decreased activity of the pristine BiOCl during the reaction proceeding, the CO₂ photoreduction performance of BiOCl/Bi-MOF hybrid does not change much under wet air with consecutive eight hours recycle. The present investigation may provide a new strategy to prepare highly effective photocatalysts by in situ constructing bifunctional heterojunctions in the application of CO₂ capture and visible-light-driven conversion.

期刊信息：Appl. Surf. Sci.

DOI：10.1016/j.apsusc.2023.157100

论文链接：

本期编辑

  孟令辉，男，北京建筑大学环境工程专业2021级硕士研究生。主要研究方向为金属-有机骨架材料的设计、制备及其在水环境修复领域的应用。目前以第一作者身份在Separation and Purification Technology上发表SCI论文1篇，以导师一作、本人二作在Applied Catalysis B: Environmental发表论文1篇，以其他作者发表论文1篇。

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