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Materials Today Energy · 2022 · IF 9.257

Lead-free perovskite Cs2XCl6 (X = Hf, Zr, Te) microcrystals for photocatalytic CO2 reduction

Changqing Tian,Qiang Huang,Daofu Wu,Junan Lai,Fei Qi,Nan Zhang,Wenxia Zhang,Xiaosheng Tang

The lead halide perovskites have broad application prospects in the fields of optoelectronics and photocatalysis . However, their toxicity and limited stability are the main obstacles restricting their large-scale photocatalytic applications. In order to solve these problems, a set of lead-free stable Cs 2 XCl 6 (X = Hf, Zr, Te) perovskite microcrystals were synthesized via a solvothermal solution. For the first time, the Cs 2 XCl 6 (X = Hf, Zr, Te) perovskite microcrystals were employed as efficient photocatalysts for the conversion of CO 2 into CO and CH 4 . Among them, the Cs 2 TeCl 6 microcrystals showed the best photocatalytic performance under light irradiation for 3 h, while the yields of CO and CH 4 were 284.4 μmol/g and 48.96 μmol/g respectively. Our strategy may provide a new idea for the CO 2 photoreduction based on lead-free halide perovskites.

研究领域: 材料科学 · 光催化 · 环境科学
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Journal of Environmental Sciences · 2020 · IF 4.302

Zr-MOFs loaded on polyurethane foam by polydopamine for enhanced dye adsorption

Jingjing Zhao,Linqiong Xu,Yaozhuo Su,Hongwei Yu,Hui Liu,Shaoping Qian,Wenge Zheng,Yongqing Zhao

ABSTRACT Zirconium-based metal-organic frameworks (Zr-MOFs) have attracted widespread attention due to their high specific surface area, high porosity, abundant metal active sites and excellent hydrothermal stability. However, Zr-MOFs materials are mostly powdery in nature and thus difficult to separate from aqueous media, which limits their application in wastewater treatment . In this study, PDA/Zr-MOFs/PU foam was constructed by growing Zr-MOFs nanoparticles on a dopamine-modified polyurethane foam substrate by in-situ hydrothermal synthesis as an adsorbent for removing dyes from wastewater. The results demonstrated that the polydopamine coating improves the dispersion of the Zr-MOFs nanoparticles on the substrate and enhances the interaction between the Zr-MOFs nanoparticles and the PU foam substrate. As a result, compared with Zr-MOFs/PU foam, the prepared PDA/Zr-MOFs/PU foam exhibits higher adsorption capacity for crystal violet (CV) (63.38 mg/g) and rhodamine B (RB) (67.73 mg/g), with maximum adsorption efficiencies of CV and RB of 98.4% (pH=11) and 93.5% (pH=7), respectively, at a concentration of 10 mg/L. The PDA/Zr-MOFs/PU foam can simultaneously remove CV and RB from the mixed solution. Moreover, the PDA/Zr-MOFs/PU foam still exhibits high stability and reusability after five cycles.

CAS / MDL: 62-31-7 77-86-1
研究领域: 环境科学 · 材料科学 · 化学工程
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2024 · IF 8.1

Coal-based carbon quantum dots modified Ni-MOF and Co/Zr-MOF heterojunctions for efficient photocatalytic hydrogen evolution

Shiyong Xu,Mei Li,Ziyu Li,Meijuan Ding,Yijun Wang,Zhiliang Jin

NS-CQDs were synthesized by a hydrothermal method using high-sulfur lignite as the carbon source. Modification of Ni-MOF and Co/Zr-MOF using NS-CQDs to explore the performance of composite photocatalysts for hydrogen production . It was found that NS-CQDs significantly enhanced the hydrogen precipitation performance of the composite photocatalysts compared with the MOFs catalysts alone, and the highest hydrogen precipitation rate of the novel composite photocatalyst 5%NS-CQDs/NCZ2 reached 3662.68 μmol g −1  h −1 . It can be inferred from the conduction band and valence band positions of Ni-MOF, Co/Zr-MOF and NS-CQDs that a double S-type heterojunction is formed. The presence of thiophene and pyrrole nitrogen in NS-CQDs can promote electron transport , reduce the rate of electron-hole pair complexation, and improve the hydrogen evolution activity of the 5%NS-CQDs/NCZ2.

研究领域: 材料科学 · 能源化学
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Inorganic Chemistry Frontiers · 2020 ·Vol. 7 ·期 14 ·2629-2636 · IF 5.958

Zr modified SrNbO2N as an active photocatalyst for water oxidation under visible light illumination

Guoan Lin,Ran Wang,Tongcheng Cao,Liangxi Yuan,Xiaoxiang Xu

With an absorption edge as far as 690 nm, SrNbO2N holds great promise for solar energy conversion. However, very poor photocatalytic activity is generally seen for SrNbO2N, limiting its practical applications as a photocatalyst. In this work, SrNbO2N is modified by introducing Zr at B sites, i.e. SrNb1−xZrxO2+yN1−y (0 ≤ x ≤ 1), which are then investigated as photocatalysts for water oxidation reactions. Zr modification not only induces porous microstructures and inhibits the formation of Nb4+ defects, but it also ameliorates the surface hydrophilicity of SrNbO2N. Clear improvements in photocatalytic water oxidation have been realized after Zr modification and an apparent quantum efficiency of as high as 1.44% has been achieved. Further analysis of the band edge alignments suggests that Zr modification positively shifts the valence band edge of SrNbO2N, which favors water oxidation reactions.

研究领域: 材料科学 · 光催化 · 太阳能转换
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JOURNAL OF HAZARDOUS MATERIALS · 2020 · IF 9.038

Electric field assisted benzene oxidation over Pt-Ce-Zr nano-catalysts at low temperature

Xuteng Zhao,Dejun Xu,Yinan Wang,Zuwei Zheng,Ke Li,Yiran Zhang,Reggie Zhan,He Lin

A novel catalytic system for benzene oxidation at low temperature is constructed by combining electric field with Pt-Ce-Zr nano-catalyst. The 1 wt% Pt/Ce 0.75 Zr 0.25 O 2 catalyst assisted by electric field shows the best catalytic performance with 90% benzene conversion at 96.5 °C and excellent water resistance. The effect of electric field on catalysts and catalytic process is comprehensively investigated. The results of XRD, TEM, XPS and H 2 -TPR reveal that the electric field show negligible influence on the crystal structure and surface morphology of the catalyst, but it can lead to more oxygen vacancies. Therefore, more adsorbed oxygen with higher activity will be produced on the catalyst surface. The redox performance is improved due to the fact that valence distribution of Pt is changed in forms of more active sites composed of high valence oxides (PtO) generated in electric field. In situ DRIFTS is used to investigate the oxidation process of benzene and the results prove that electric field could accelerate the production and consumption of intermediate products, and produce new intermediate products such as carboxylic acid species, indicating that the introduction of electric field may open up a new rapid reaction path and promote the activation of benzene at low temperature.

研究领域: 催化化学 · 环境科学
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FUEL · 2022 · IF 8.035

Synergetic effect of Ce/Zr for ethanol synthesis from syngas over Rh-based catalyst

Caixia Zhu,Kaizhuang Xu,Yuan Fang,Qian Lv,Kun Jiang,Huibo Zhao,Yang Chen,Peng Wang,Hua Yang,Lizhi Wu,Yu Tang,Li Tan

The direct synthesis of ethanol from syngas is a promising way in the field of clean and efficient use of fossil fuel, but it still suffers from insufficient ethanol selectivity and understanding of active sites. In this work, the Rh-based catalyst with Ce as promoter and ZrO 2 as carrier exhibits excellent catalytic performance, showing the selectivity of ethanol toward 24.3 %. Moreover, the yield of methane decreases to 4.8 %, and the formation of CO 2 is inhibited to a certain degree by tuning the active sites. The carrier is changed by doping Ce into the ZrO 2 lattice, which assists to form the Rh δ+ active sites. The synergetic effect of Ce and Zr is important to influence the state of Rh species in the catalysts, leading to the differences in the CO hydrogenation process. On the other hand, the Rh δ+ active sites are also stabilized by promoted surface oxygen vacancies in the 2.0Rh5.0Ce-ZrO 2 catalyst. The high-activity catalyst with Rh δ+ active sites will be helpful to understand the real active sites of Rh-based catalysts for ethanol synthesis from syngas, thereby guiding further design of the related catalyst with high performance to meet the industrial demand in syngas converting to ethanol.

研究领域: 催化化学 · 能源化学
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Frontiers in Chemistry · 2022 · IF 5.545

Green Photocatalysis of Organic Pollutants by Bimetallic Zn-Zr Metal-Organic Framework Catalyst

Zhang Xiaojuan,Yu Rongfei,Wang Dandan,Li Weihua,Zhang Yutao

A series of bimetallic Zn-Zr metal-organic frameworks (Zn-Zr MOFs) with different Zn:Zr molar ratios has been synthesized via a green hydrothermal method. The structures and morphologies of these photocatalysts have been characterized and analyzed by FTIR, XRD, SEM, and nitrogen adsorption-desorption. The prepared Zn-Zr MOFs had large specific surface areas and pore volumes, favoring the adsorption of pollutant molecules, which in turn led to an improved photocatalytic effect. The photocatalytic activities of the Zn-Zr MOFs under visible light irradiation have been studied towards rhodamine B (RhB) as a target pollutant. The extent of degradation of RhB in a 40 mg/L aqueous solution reached 97.4%. The optimal photocatalyst could also degrade other dyes, suggesting a certain degree of universality.

研究领域: 材料科学 · 环境科学
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JOURNAL OF MOLECULAR STRUCTURE · 2023 · IF 3.8

Simple preparation and high activity for cancer therapy via Zr(IO3)4 nanozyme

Jiayin Li,Runze Liu,Pengfei Liu,Hu Zhou

The reactive oxygen species (ROS) level as an hopeful strategy for cancer therapy, mainly including photodynamic therapy (PDT) and chemodynamic therapy (CDT). It is well known both PDT and CDT greatly rely on oxygen reliance, inherent flaws of traditional photosensitizers, and lowly selectivity between normal cells and tumor cells. Herein, we reported Zr(IO 3)4 nanoparticles as a biocompatible nanozyme with effective ROS supply by Feton-like reaction and Brady reaction. The Zr(IO 3 ) 4 exhibiting a remarkable selectivity between normal cells and tumor cells. Importantly, the Zr(IO 3 ) 4 , H 2 O 2 -responsive and GSH-depleted nanozymes, were explored for tumor therapy. Nanozyme is highly important from the deep cancer therapy point of view. In this work, we prepared Zr(IO 3 ) 4 by a simple method. The obtained Zr(IO 3 ) 4 samples showed obvious performance in treatment of cancer. It was confirmed by the electron spin resonance (ESR) as well as the fluorescence probe results of Zr(IO 3 ) 4 that the treatment of cancer due to the reactive oxygen species.

研究领域: 生物医学工程 · 肿瘤学 · 纳米医学
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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2024 · IF 11.2

One-step in situ preparation of Zr(Ti)-MOFs on titanium alloys at a low temperature of 80°C and atmospheric pressure

Rong Liu,Yan Gao

Preparing metal-organic frameworks (MOFs) film in situ on the surface of the Ti-6Al-4V (TC4) titanium alloy is challenging owing to the dense and stable surface TiO 2 passive film. In this study, titanium-doped zirconium-based MOFs (Zr(Ti)-MOFs) film was constructed in situ on the TC4 alloy in one step at a low temperature and atmospheric pressure, with ZrCl 4 as the source of Zr metal ions. ZrCl 4 attacked and dissolved the TiO 2 film to form Zr-O-Ti bonds on the surface of TC4 to provide nucleation sites for further reactions. At the same time, Zr 4+ and dissolved Ti 4+ combined in solution to form Ti containing Zr-O cluster nodes, which aggregated and grafted to the Zr-O-Ti bonds on the substrate surface, and reacted with organic ligands (terephthalic acid) to form Zr(Ti)-MOFs film. The Ti 4+ dissolved from the TC4 participate in the Zr-MOFs formation, thereby changing the high temperature and high-pressure conditions required for the traditional preparation of Zr-MOFs (UiO-66). The in situ preparation of Zr(Ti)-MOFs on TC4 was achieved at 80°C under atmospheric pressure conditions. This study elucidated the growth mechanism of Zr(Ti)-MOFs on the TC4 surface, providing a reference for the design and in-situ preparation of multifunctional MOFs on the TC4 titanium alloy.

CAS / MDL: 10026-11-6 100-21-0
研究领域: 材料科学 · 表面工程 · 化学工程
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Removal of aqueous pharmaceuticals by magnetically functionalized Zr-MOFs: Adsorption Kinetics, Isotherms, and regeneration

Fankang Zhao,Shengqiong Fang,Yanxin Gao,Jinhong Bi

The functionalization of metal–organic frameworks (MOFs) is imperative and challenging for the development of practical MOF-based materials. Herein, a magnetically functionalized Zr-MOF (Fe 3 O 4 @MOF-525) was synthesized via secondary-growth approach to obtain an easily-separated and recyclable adsorbent for the removal of pharmaceuticals (tetracycline (TC) and diclofenac sodium (DF)). After loading Fe 3 O 4 nanoparticles (NPs), due to the increase of micropore volume and specific surface area caused by defects, the adsorption performance of Fe 3 O 4 @MOF-525 was improved. The kinetics could be described by the pseudo-second-order kinetic model. The different adsorption capacity and initial rate were attributed to the properties of the pharmaceuticals, including the molecular size and hydrophobicity/hydrophilicity. In isotherm experiments, the maximum adsorption capacities of DF and TC on Fe 3 O 4 @MOF-525 calculated by Sips model reached 745 and 277 mg·g −1 , respectively. The thermodynamic studies indicated the adsorption was endothermic and spontaneous. The effect of pH suggested that electrostatic interaction, π-π interaction, anion-π interaction, and H-bonding were possibly involved in the adsorption process. The adsorbent was separated by magnetic and regenerated. Washed with ethanol, Fe 3 O 4 @MOF-525 remained about 80% adsorption capacity after four cycles. In-situ photo-regeneration under visible-light irradiation was another attractive method, where > 95% TC was degraded in 4 h. The reaction with scavengers revealed that 1 O 2 was the dominant reactive species in our system, indicating the occurrence of Type II photosensitization. The separability, excellent adsorption performance, and recyclability of Fe 3 O 4 @MOF-525 may lead to its beneficial applications in water treatment.

研究领域: 环境科学 · 材料科学 · 药学
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Journal of Environmental Chemical Engineering · 2025 · IF 7.2

Co(II) porphyrin-integrated Zr-MOF containing imidazolium-based ionic liquid for boosting cocatalyst-free CO2 cycloaddition

Fangfang Li,Xiaofang Hou,Wei Fu,Jinjin Wang,Ying-Hua Zhou

The efficient transformation of CO 2 into high-value chemicals remains a significant challenge, particularly in the design of heterocatalysts capable of simultaneous multi-site activation towards the substrate. In this work, we develop the novel Zr-MOF catalysts incorporating both cobalt(II) meso-tetra(4-carboxyphenyl)porphine (CoTCPP) complex and the imidazolium bromide-based ionic liquid (IL) containing different alkyl chain (RImBr), where R = Et, Pr, Bu, and Pe), denoted as CoTCPP-UiO-66-IL(RImBr). The catalysts were synthesized through a solvothermal method followed by a post-synthetic modification. Among the prepared catalysts, CoTCPP-UiO-66-IL(BuImBr) demonstrated exceptional performance on the solventless and cocatalyst-free conversion of epichlorohydrin into chloropropene carbonate, achieving a remarkable 99% yield under mild conditions (90 °C and 1.0   bar CO 2 ). This outstanding catalytic efficiency was attributed to the synergistic effects of the dual Lewis-acid active sites offered by Zr-MOF node and the integrated CoTCPP complex, the strong nucleophilicity resulting from the incorporated imidazolium bromide-type IL, and the improved CO 2 adsorption capacity. Additionally, the CoTCPP-UiO-66-IL(BuImBr) catalyst exhibited excellent recyclability and broad substrate versatility in epoxide cycloaddition. These findings provide valuable insights into the development of multifunctional MOF-based heterogeneous catalysts with high activity and sustainability for CO 2 conversion applications.

CAS / MDL: 10026-11-6 610-92-4
研究领域: 材料科学 · 催化化学 · 环境科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Heating-induced adsorption promoting the efficient removal of toluene by the metal-organic framework UiO-66 (Zr) under visible light

Jiajun Yu,Xiao Wang,Yan Wang,Xiaofeng Xie,Haijiao Xie,Nat Vorayos,Jing Sun

The removal of indoor/outdoor toluene by photocatalysis has drawn much attention due to its low energy consumption and easy availability. However, light inevitably generates heat, and pollutants desorb from catalysts as the temperature rises, which is not beneficial to degradation. Contrast to the frequently occurred phenomena, we firstly found that the adsorption capacity of UiO-66 (Zr) on toluene increased with increasing temperature as adsorption isotherms and in-situ Fourier transform infrared spectra (in-situ FTIR) showed. The optimum temperature was 30 °C. This stage in which adsorption capacity was positively correlated with temperature was called heating-induced adsorption, which achieved a toluene removal efficiency of 69.6 %. By density functional theory (DFT) calculations and changing the metal centers and organic ligands of UiO-66 (Zr) respectively, we disclosed that the heating-induced adsorption was mainly related to the π-π stacking interaction of MOF ligands and toluene. The analysis of samples before and after adsorption showed that the interaction between UiO-66 (Zr) and adsorbed toluene facilitated the charge transfer and prolonged the carrier lifetime, leading to the increase of hydroxyl radicals (•OH) in photocatalysis. Therefore, a synergistic effect between heating-induced adsorption and photocatalysis was proposed by analyzing the adsorption of toluene on UiO-66 (Zr) in detail. This work provided new viewpoint to understand the role of concomitant heat contributed to the adsorption and degradation of toluene during photocatalysis.

研究领域: 环境科学 · 材料科学
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