题目: Highly Efficient Hydroxyl Radicals Production Boosted by the Atomically Dispersed Fe and Co Sites for Heterogeneous Electro-Fenton Oxidation

作者: Xin Qin, Peike Cao, Xie Quan*, Kun Zhao, Shuo Chen, Hongtao Yu, and Yan Su

摘要: The heterogeneous electro-Fenton (hetero-e-Fenton)-coupled electrocatalytic oxygen reduction reaction (ORR) is regarded as a promising strategy for ·OH production by simultaneously driving two-electron ORR toward H₂O₂ and stepped activating the as-generated H₂O₂ to ·OH. However, the high-efficiency electrogeneration of ·OH remains challengeable, as it is difficult to synchronously obtain efficient catalysis of both reaction steps above on one catalytic site. In this work, we propose a dual-atomic-site catalyst (CoFe DAC) to cooperatively catalyze ·OH electrogeneration, where the atomically dispersed Co sites are assigned to enhance O₂ reduction to H₂O₂ intermediates and Fe sites are responsible for activation of the as-generated H₂O₂ to ·OH. The CoFe DAC delivers a higher ·OH production rate of 2.4 mmol L^–1 min^–1 g_cat^–1 than the single-site catalyst Co-NC (0.8 mmol L^–1 min^–1 g_cat^–1) and Fe-NC (1.0 mmol L^–1 min^–1 g_cat^–1). Significantly, the CoFe DAC hetero-e-Fenton process is demonstrated to be more energy-efficient for actual coking wastewater treatment with an energy consumption of 19.0 kWh kg^–1 COD^–1 than other electrochemical technologies that reported values of 29.7∼68.0 kW h kg^–1 COD^–1. This study shows the attractive advantages of efficiency and sustainability for ·OH electrogeneration, which should have fresh inspiration for the development of new-generation wastewater treatment technology.

期刊信息: Environ. Sci. Technol.  

DOI: 0.1021/acs.est.2c06981

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题目: Microwave-Assisted Rapid Substitution of Ti for Zr to Produce Bimetallic (Zr/Ti)UiO-66-NH₂ with Congenetic “Shell–Core” Structure for Enhancing Photocatalytic Removal of Nitric Oxide

作者: Jiayou Liu,  Xiaoxiang Huang,  Liuhu Jia,  Linfeng Liu,  Qianqian Nie,  Zhongchao Tan*,  Hesheng Yu*

摘要: Efficient nitric oxide (NO) removal without nitrogen dioxide (NO₂) emission is desired for the control of air pollution. Herein, a series of (Zr/Ti)UiO-66-NH₂ with congenetic shell–core structure, denoted as Ti-UION, are rapidly synthesized by microwave-assisted post-synthetic modification for NO removal. The optimal Ti-UION (i.e., 2.5Ti-UION) exhibits the highest activity of 80.74% without NO₂ emission with moisture, which is 21.65% greater than that of the UiO-66-NH₂. The NO removal efficiency of 2.5Ti-UION further increases to 95.92% without photocatalyst deactivation under an anhydrous condition. This is because selectively produced NO₂ in photocatalysis is completely adsorbed into micropores, refreshing active sites for subsequent reaction. In addition, the enhanced photocatalytic activity after Ti substitution is due to the presence of Ti electron acceptor, the potential difference between the shell and core of Ti-UION crystal, and the high conductivity of Ti-O units. Additionally, the improved adsorption of gas molecules not only favors NO oxidation, but also avoids the emission of NO₂. This work provides a feasible strategy for rapid metal substitution in metal-organic frameworks and insights into enhanced NO photodegradation.

期刊信息: Small  

DOI: 10.1002/smll.202207198

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题目: A novel (Zr/Ce)UiO-66(NH₂)@g-C₃N₄ Z-scheme heterojunction for boosted tetracycline photodegradation via effective electron transfer

作者：Susu Ren, Jiahuan Dong, Xinyu Duan, Tingting Cao, Hongbin Yu, Ying Lu*, Dandan Zhou

摘要: Aiming at efficient tetracycline (TC) removal, a co-modified (Zr/Ce)U(NH₂) was elaborately designed and integrated with thin-layered g-C₃N₄, forming a novel (Zr/Ce)U(NH₂)@CN Z-scheme heterojunction. XRD, XPS, FTIR, ISI-XPS and other analysis cooperatively demonstrated that within this (Zr/Ce)U(NH₂)@CN composite organic linkers H₂BDC was successfully modified by -NH₂, metal Zr in Zr-oxo cluster was partially substituted by Ce, Z-scheme heterojunction was formed by the close interaction between MOFs and g-C₃N₄, as well as the excellent thermal stability and large specific surface area were achieved. Since g-C₃N₄ could serve as carrier skeleton to improve the precursor dispersion, the (Zr/Ce)U(NH₂) with reduced particle size grew densely on it. DRS, PL and TRPL characterization proved more photogenerated carriers with prolonged lifetime were generated. As expected, (Zr/Ce)U(NH₂)@CN composite exhibited high TC degradation rate, whose kinetic constant was 23.73 times greater than that of UiO-66, and 5.89 folds larger than that of CN, respectively. This enhanced photocatalytic performance was ascribed to the effective electron transfer regulated by MOFs unit, where the Zr/Ce improved the electron transfer from photoexcited organic linkers to metal-oxo clusters, as well as the MOFs/g-C₃N₄ Z-scheme heterojunction strengthened interfacial photogenerated carriers transfer. ·OH was the vital species responsible for TC removal using (Zr/Ce)U(NH₂)@CN. Furthermore, intermediate products and degradation pathways were proposed based on HPLC-MS. The toxicity estimation indicated the comprehensive toxicity of TC was significantly alleviated by (Zr/Ce)U(NH₂)@CN photocatalysis.

期刊信息: Chem. Eng. J. 

DOI: 10.1016/j.cej.2023.141884 

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题目: Novel isoreticular UiO-66-NH₂ frameworks by N-cycloalkyl functionalization of the 2-aminoterephtalate linker with enhanced solar photocatalytic degradation of acetaminophen

作者: Almudena Gómez-Avilés, Rafael R. Solís*, Eva M. García-Frutos, Jorge Bedia, Carolina Belver

摘要: This work reports for the first time the functionalization of the 2-aminoterephtalate linker of UiO-66-NH₂ with cyclopentyl or cyclohexyl rings. The resulting materials displayed reduced bandgaps with enhanced separation of the photogenerated charges due to the inductive electron effects of the cycloalkyl substituent. These functionalized materials displayed higher photocatalytic performance towards the solar abatement of acetaminophen than UiO-66-NH₂. The photocatalytic activation mechanism was proposed based on the band alignment and scavenger tests, suggesting the major contribution of holes and superoxide radicals. In particular, UiO-66-NH-C₅ exhibited high stability under reaction with low activity loss after reusing. The acetaminophen degradation pathway was also studied indicating that the ACE molecules were coupled to dimers and trimers that were further oxidized. The small bandgap, the band structure, and the photocatalytic performance resulting from the cycloalkyl functionalization of UiO-66-NH₂ make it a promising approach to designing novel photocatalysts for solar abatement of emerging contaminants.

期刊信息: Chem. Eng. J. 

DOI: 10.1016/j.cej.2023.141889

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题目: Construction of a 0D/3D AgI/MOF-808 photocatalyst with a one-photon excitation pathway for enhancing the degradation of tetracycline hydrochloride: Mechanism, degradation pathway and DFT calculations

作者: Yonghao Dong, Xudong Wang*, Han Sun, Hongmin Zhang, Xiaochen Zhao, Lei Wang*

摘要: One-photon excitation has been demonstrated to be ideal for improving photon utilization effectiveness. We synthesized a unique 0D/3D AgI/MOF-808 composite using a hydrothermal method combined with in situ precipitation. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations indicated the electron migration direction, confirming the presence of a one-photon excitation pathway. The 0D/3D AgI/MOF-808 exhibited both excellent adsorption (189.01 mg/g) and photocatalytic properties for tetracycline hydrochloride (TCH). Electrochemical and photoluminescence (PL) tests showed that 0D/3D AgI (40 wt%)/MOF-808 had the highest photogenerated carrier transport and separation efficiency, with a TCH degradation efficiency of 83.02 % and a degradation rate 14.32 times higher than that of bare AgI. Photon utilization efficiency, carrier separation, and adsorption capacity expansion all contributed to the photocatalytic performance. The effects of pH and inorganic anions on the composite photocatalyst during the photocatalytic reaction were also investigated. The capture experiment demonstrated that ·OH and ·O₂^– were the primary active groups. Additionally, the stability was enhanced because the migration of electrons in AgI effectively limited the reduction of Ag⁺ to Ag⁰. Possible attack sites during TCH degradation were predicted using the condensed FuKui function (CFF), and potential degradation pathways were determined using ultrahigh-performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS). The examination of the biotoxicity of TCH degradation intermediates demonstrated a reduction in their environmental risks.

期刊信息: Chem. Eng. J.      

DOI: 10.1016/j.cej.2023.141842  

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题目: Ultrathin fluorine-doped TiO₂(B) nanosheets-anchored hierarchical cog wheel-shaped NH₂-MIL-53(Al) for boosting photocatalytic activity

作者: Chengzhang Zhu, Haiqian Yao, Tianyu Sun, Shukun Le, Qijie Jin, Chuanxiang Chen, Haitao Xu*, Shaobin Wang

摘要: Developing novel S-scheme systems with highly active solar-driven catalysts are of huge interest in degrading noxious antibiotics in a sustainable manner. Herein, fluorine (F)-doped TiO₂(B) nanosheets-modified gear-shaped NH₂-MIL-53(Al) were first fabricated for tetracycline degradation. Benefiting from the synergy among the incorporated F species, well-matched band structure, and built-in electric field, the optimized nanohybrid attains an impressive degradation rate (94.6 %) and TOC mineralization efficiency (71.4 %). Moreover, the addition of external interferential ions, such as Cu²⁺ or NO₃⁻ nearly have no influence on the photoactivity. A probable degradation pathway was proposed on the basis of the calculated Fuki indexes and prime intermediates identified by a high-performance liquid chromatography-mass spectrometer. On NH₂-MIL-53(Al)/F-TiO₂(B) interfaces, the migration of electrons from F-TiO₂(B) to NH₂-MIL-53(Al) via intense electronic interactions contribute to a S-scheme mode, which is conductive to facilitating rapid spatial charge separation, superior visible light utilization, and populated exposed active sites with high potentials. This study paves new avenues to an atomic-scale interfacial engineering of S-scheme heterojunctions for efficient water purification.

期刊信息: Chem. Eng. J.  

DOI: 10.1016/j.cej.2023.141849  

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题目: Nanoarchitecting a Dual Z-Scheme Zr-MOF/Ti-MOF/g-C₃N₄ Heterojunction for Boosting Gomberg–Buchmann–Hey Reactions under Visible Light Conditions

作者: Hassan Sepehrmansourie, Hassan Alamgholiloo, Mohammad Ali Zolfigol*, Nader Noroozi Pesyan, and Milad Mohammadi Rasooll

摘要: Combining more than two metal–organic frameworks (MOFs) with different structures is an intelligent strategy for the architecture of hybrid MOFs. Herein, well-organized UiO-66(Zr)-on-MIL-125(Ti)-NH₂ growth with g-C₃N₄ nanosheets was developed for the Gomberg–Buchmann–Hey reaction under visible light irradiation (λ > 420 nm). First, UiO-66(Zr) micropores as host MOFs were fabricated by a solvothermal method. Subsequently, MIL-125(Ti)-NH₂ crystals and g-C₃N₄ nanosheets were grown inside UiO-66(Zr) to obtain a new type of the dual Z-scheme Zr-MOF/Ti-MOF/g-C₃N₄ heterojunction photocatalyst. Under visible light irradiation, this dual Z-scheme heterojunction acts as a highly efficient photocatalyst for forming C–C bonds via diazonium salts, which can compete with the best photocatalyst systems. The findings indicated that the presence of Zr and Ti metals in MOF-on-MOF and g-C₃N₄ nanosheets could significantly increase the separation of photogenerated electron–hole pairs and then enhance the photocatalytic performance. The present study not only provides new insights into the architecture of MOFs on other MOFs but also develops Z-scheme heterojunction materials for coupling reactions and other organic reactions under visible light irradiation.

期刊信息: ACS Sustainable Chem. Eng. 

DOI:10.1021/acssuschemeng.2c04810

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题目: 2D Cd-MOF and its mixed-matrix membranes for luminescence sensing antibiotics in various aqueous systems and visible fingerprint identifying

作者: Kexin Ma, Jing Li, Huiyan Ma, Yan Yang, Hua Yang, Jing Lu, Yunwu Li*, Jianmin Dou, Suna Wang*, Suijun Liu*

摘要: The abuse of antibiotics has brought great harm to the human living environment and health, so it is extremely significant to develop an efficient and simple method to detect trace antibiotic residues in various wastewaters. Herein, a new two-dimensional (2D) Cd-based metal−organic framework (Cd-MOF, namely LCU-111) and its mixed matrix membranes (MMMs) is sifted as luminescence sensors for efficient monitoring antibiotic nitrofurazone (NFZ) in various aqueous systems and applied as visible fingerprint identifying. The LCU-111 has good selectivity, sensibility, reproducibility and anti-interference for luminescent quenching NFZ with low detection limits (LODs) of 0.4567, 0.3649 and 0.8071 ppm in aqueous solution, HEPES biological buffer, and real urban Tuhai River water, respectively. Interestingly, the luminescent test papers and MMMs allow the NFZ sensing easier and more rapid by naked eyes, only with a low LOD of 0.8117 ppm for MMMs sensor. Notably, by combining multiple experiments with density functional theory (DFT) calculations, the photo-induced electron transfer (PET) quenching mechanism is further elucidated. More importantly, potential practical applications of LCU-111 for latent fingerprint visualization provide lifelike evidences for effective identification of individuals, which can be applied in criminal investigation.

期刊信息: Chin. Chem. Lett.    

DOI:10.1016/j.cclet.2023.108227 

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题目: Photo-Fenton degradation of tetracycline hydrochloride with Fe₂O₃-on-ZrO₂ polypods derived from MIL-88B-on-UiO-66-NH₂ within full pH range: kinetics, degradation pathway and mechanism insight

作者: Tingting Zhang, Xing Liu, Yanqiu Jiang*, Xiaowei Zheng, Jian Zhang, Yudong Li, Defeng Li*, Kaifeng Lin

摘要: Photo-Fenton reaction has received increasing attention in removing antibiotics in water. Herein, Fe₂O₃-on-ZrO₂ polypods were designed and synthesized via metal organic frameworks (MOFs) derivation strategy combined with reflux heating and baking. The experimental results showed that under Ultraviolet-visible (UV-vis) light irradiation, more than 95% tetracycline hydrochloride (TC-HCl) was degraded by Fe₂O₃-on-ZrO₂ with Fe/Zr mole ratio of 1.3 in 25 minutes within full pH range. Mainly due to the following points, there were abundant Fe₂O₃-on-ZrO₂ heterojunctions, which conduced to transfer photoinduced electrons (e^-) from ZrO₂ to Fe₂O₃, thus accelerating the iron cycle. Besides, OH^- adsorbed was oxidized to hydroxyl radicals (·OH) by holes (h⁺) in the valence band (VB) of ZrO₂, and ZrO₂ also enhanced the stability of the catalyst and reduced the leaching of iron ions. Finally, the reasonable degradation pathway and degradation mechanism were speculated by high performance liquid chromatography-mass spectrometry (HPLC-MS), electron spin resonance technology (ESR), scanning Kelvin probe (SKP), the conduction band (CB) and VB positions of Fe₂O₃-on-ZrO₂, etc. This work exhibited a new structure and degradation mechanism, which would further encourage researchers to study the rational regulation of materials with special morphology and structure.

期刊信息: Appl. Surf. Sci.   

DOI:10.1016/j.apsusc.2023.156715

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      孙雪梓，女，北京建筑大学资源与环境专业2021级硕士研究生，主要从事金属有机骨架材料及衍生物/复合物的设计与可控制备及其环境应用研究。