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SOLAR ENERGY MATERIALS AND SOLAR CELLS · 2024 · IF 6.3

Comparison of UiO-66(Zr) and its derivate in shape stabilized phase change materials: Thermal storage performance and characterizations

Junchi Wang,Hui Li,Ndzondelelo Bingwa,Hao Yu,Guoning Li,Qiangqiang Xiao,Shijie Li,Min Guo,Xiaoling Ma

In this study, UiO-66(Zr) and its derivative (UiO-66-C) are employed as supports to prepare shape stabilized PCM (U/SA-X and UC /SA-X) for resolving the melting leakage and poor thermal conductivity of stearic acid (SA). Thermal storage performance, including phase change enthalpy, supercooling degree, phase change temperature, thermal conductivity, and shape stability of U/SA-X and UC/SA-X, are compared. Preliminary characterization reveals that the physicochemical property evolution of the support impacts the thermal storage performance of SA . UiO-66 with microporous structure is unfavorable to enhance the shape stability of SA. U/SA-X exhibits low thermal storage efficiency and high supercooling degree owing to nanoconfinement and hydrogen bonding. By contrast, UiO-66-C possesses mesopores and graphitic structure that allows for a remarkable thermal storage performance of UC/SA-X. In detail, UC/SA-50 exhibits an ideal thermal storage performance, where the thermal conductivity (0.531 W/(m·K)) increases by 141 % in comparison to SA with a high phase change enthalpy of 93.6 J/g and low supercooling degree of 0.24 °C. It also shows satisfying thermal reliability that the thermal property of UC/SA-50 maintains stability even after 100 thermal cycles. In addition, the photothermal conversion efficiency of UC/SA-50 is up to 83.06 %.

CAS / MDL: 10026-11-6 57-11-4
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CERAMICS INTERNATIONAL · 2017 · IF 2.986

Improvement of the conductivity of sol-gel derived Li-La-Zr-O thin films by the addition of surfactant

Ru-Jun Chen,Yi-Bo Zhang,Ting Liu,Bing-Qing Xu,Yang Shen,Yuan-Hua Lin,Ce-Wen Nan

Li–La–Zr–O thin films were successfully fabricated using the sol-gel spin coating method and the effects of the addition of surfactant in the solution were studied. X-ray diffraction, scanning electron microscopy and Atomic Force Microscope were used to investigate the characteristics of these films and an amorphous structure and smooth surface on the films were revealed. The ionic conductivity of the film was investigated by impedance analysis. The results showed that the room-temperature ionic conductivity of the film increases with the content of surfactant, from 1.8 × 10 −6   S/cm for 0.5   wt% to 3.9 × 10 −6   S/cm for 1.5   wt%. However, further increasing the content of surfactant can deteriorate the property of the thin film on the contrary. The improvement of the property can be attributed to the improvement of the morphology of the film. We propose that this Li–La–Zr–O thin film is a promising solid electrolyte for thin-film lithium-ion batteries.

CAS / MDL: 1907-33-1 23519-77-9
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FUEL · 2024 · IF 6.7

Highly efficient Zr-based coordination polymer for catalytic transfer hydrogenation of 5-hydroxymethylfurfural: Tuning acid strength and enhancing stability

Weizhen Xie,Yue Tang,Yiqiang Liu,Mengyuan Huang,Lu Lin,Xing Tang

In this study, Zr-based coordination polymers were synthesized via solvothermal method for the Meerwein-Ponndorf-Verley reduction of biomass-derived aldehydes and ketones. The morphology and strength of Lewis acid sites could be tuned by using different solvent during catalyst preparation. A 98.5 % yield of 2,5-bis(hydroxymethyl)furan (BHMF) was achieved at 100 °C using Zr-PDC/DMF-DCB, which was synthesized with pyridine-2,6-dicarboxylic acid (PDC) as ligand in a mixed solvent of N, N-dimethylformamide (DMF) and 1,2-dichlorobenzeneisopropanol (DCB) and exhibited moderate Lewis acid sites. Conversely,   while Zr-PDC synthesized in alcohols (Zr-PDC/MeOH and Zr-PDC/EtOH) were used as catalysts, etherification products formed instead of BHMF. Further investigation into the role of solvents during catalyst preparation revealed that coordination between Zr sites and DMF increased the electron cloud density of Zr sites, thus weakening Lewis acidity. In addition, the inclusion of hydrophobic DCB resulted in the formation of spherical morphology, which improved resistance to carbon deposition and enhanced anti-agglomeration properties. This work presents a strategy for controlling acid strength and improving catalytic stability of coordination polymers.

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FUEL · 2024 · IF 6.7

La-doped bimetallic PCN-777 (La-Zr) catalyst synthesized by oil-bath heating for efficient oxidative desulfurization of dibenzothiophene

Mingyu Liao,Miaomiao Zheng,Gexian Li,Xiaolin Pi,Yuanjie Xiao,Linfeng Zhang,Huadong Wu,Jia Guo

The desulfurization of fuels is a crucial step in the production of clean energy. The design of metal–organic frameworks (MOFs) with bimetallic active sites is a new way to achieve deep oxidative desulfurization (ODS). Traditional methods for synthesizing MOFs involve high temperatures and pressures, which can be hazardous. Oil bath heating provides a safer and more convenient way to synthesize catalysts at a slower heating rate with full uniform heating. In this work, a series of La-doped bimetallic PCN-777(La-Zr) catalysts were synthesized by heating in an oil bath. The microstructures of the catalysts were investigated using various techniques, such as XRD, FT-IR, Raman, BET, SEM, TEM, etc. Compared with PCN-777(H) synthesized by hydrothermal method, PCN-777(O) synthesized by oil-bath heating exhibits a higher specific surface area (2017.01 m 2 /g) and a more homogeneous pore size distribution. PCN-777(0.2La-Zr) demonstrated outstanding catalytic performance in ODS of dibenzothiophene (DBT), which could remove 100 % of DBT within 40 min at 60 ℃ and still exhibited high desulfurization efficiency after 12 cycles. The outstanding catalytic ability of PCN-777(0.2La-Zr) should be related to the synergistic effect of its homogeneous pore channels and unsaturated metal sites. The present study exhibits that bimetallic MOFs have possible application potential in the field of ODS, and offers a novel idea for promoting the catalytic ability of ODS by catalyst synthesis in an oil bath.

CAS / MDL: 13520-92-8
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2024 · IF 3.8

One-Step Synthesized Solid Acid Catalyst with High Zr Content for Efficient and Green PET Degradation in Supercritical CO2

Peng Gao,Hui Lv,Shao-Kang Qian,Wen-Huan Qiao,Zhen-Yan Hu,Gui-Ping Cao

Solid acid will be an ecofriendly and efficient catalyst for the hydrolysis of polyethylene terephthalate (PET). Very highly Zr-doped MFI-structured zeolites as catalysts for PET hydrolysis were successfully synthesized for the first time. Comprehensive characterizations confirmed the successful incorporation of Zr into the framework. To comprehend the role of Zr within the framework, density functional calculations were employed to investigate its impact on the surface properties and hydrolysis processes. The results demonstrated that Zr d-orbitals enhance Lewis acidity of the catalyst by contributing to the formation of zeolite’s lowest unoccupied molecular orbitals. The interaction between the model molecule and the catalyst surface was enhanced by doping Zr, leading to electron redistribution toward the surface direction on the carbonyl oxygen of model molecule. Consequently, the carbonyl carbon developed a partial positive charge, and the hydrolysis reaction was promoted. The experimental results validated that the Zr-doped catalyst exhibited a 64% enhancement in the reaction rate.

CAS / MDL: 67-68-5 78-10-4
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Cu/ZnO/Al2O3 sorbent promoted by Zr for the ultra-deep removal of thiophene in simulated coke oven gas

Xiaoxia Zhang,Zhipeng Zhou,Junjie Liao,Liping Chang,Jiancheng Wang,Weiren Bao

The ultra-deep removal of thiophene from coke oven gas (COG) is critical for the conversion of COG to methane. Currently, Cu/ZnO/Al 2 O 3 is considered as a promising sorbent for thiophene removal; however, its desulfurization performance is currently unable to meet the requirements for industrial applications. Here, a zirconium modification strategy is proposed to overcome this problem, allowing zirconium loaded copper-based sorbents (Cu/ZnO/Al 2 O 3 /ZrO 2 ) with significantly improved thiophene removal performance and high activity to be obtained. Characterization results showed that zirconium improved both the dispersion of copper and the concentration of Lewis acid sites on the sorbent surface. A ZrO 2 concentration of 2 % resulted in stronger Cu-Zn interaction, and the dispersion of Cu on the surface of the sorbent reached its maximum value (49.20 %). Additionally, the Lewis acid strength was also maximized, which greatly improved the desulfurization activity and resulted in a breakthrough adsorption capacity of thiophene (Q b-thiophene ) of 36.24 mg/g, which was about 17 % higher than that of the unmodified Cu/ZnO/Al 2 O 3 sorbent. These results demonstrate that the sulfur capacity of the sorbent can be increased by increasing the number of acidic sites on its surface, paving the way for ultra-deep thiophene removal in industrial applications.

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LANGMUIR · 2024 · IF 3.7

Biosensing of Cysteine through the Induction of Oxygen Vacancies in a Cu/Zr Heterostructure Prepared by Supercritical Antisolvent Technique

Wei-Guang Xiong,Chang-Yong Li,Ranjith Kumar Kankala,Ai-Zheng Chen,Shi-Bin Wang

There has been a growing emphasis on facile preparation of binary heterogeneous composite materials. Leveraging the eco-friendly efficiency of supercritical CO2 technology, we achieved precise control over the influencing factors of mass transfer, enabling the accurate modulation of the resulting product morphology and properties. In the current study, CuxO/ZrOy composite materials were prepared using this technology and calcined to obtain electrode materials for the detection of cysteine (Cys). Essential comprehensive characterization techniques were employed to elucidate the heterojunction. The resulting electrode demonstrated a linear response to Cys within a concentration range of 0.5 nM to 1 μM, featuring a high sensitivity of 1035 μA·cm–2·μM–1 and a low detection limit of 97.3 nM. Thus, establishing a novel avenue for nonenzyme-based electrochemical sensors tailored for biologically active Cys detection through the implementation of a heterogeneous structure.

CAS / MDL: 52-90-4
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Adaptive structural modification of Zr-based MOF-808 via solvent and ligand engineering for enhanced fluoride ion adsorption efficiency

Yubo Pan,Linrui Li,Baogang Yang,Guangwei Ji,Zhiren Zhao,Hongling Zhang,Fengyun Wang,Mingzhu Xia,Yu Tao

The rapid development of industries such as new energy and photovoltaic has led to the generation of a large amount of industrial fluorine wastewater, posing serious threats to water environment and human health. To address this issue, MOF-808 adsorbent was synthesized by controlling the synthesis conditions and modifying the ligand structure. Batch adsorption experiments were conducted by varying experimental conditions, including type of adsorbent, pH, wastewater concentration, adsorption time, temperature, and interfering anions. The adsorption behavior of MOF-808-AA towards fluoride ions was well fitted by the Elovich non-linear kinetic model, as well as the Freundlich and Temkin non-linear isotherm models, indicating that the adsorption behavior was influenced by multiple mechanisms other than just intraparticle diffusion. Thermodynamic results suggested a spontaneous exothermic monolayer chemical adsorption process. Under the conditions of pH 6.0 and T = 298 K, MOF-808-AA exhibited a maximum adsorption capacity of 84.65 mg/g for fluoride ions. Characterization techniques, as well as quantum chemical analysis was employed to analyze the adsorption behavior and predict the reaction sites. The potential mechanism can be summarized as the formation of new bonds between MOF-808-AA and the adsorbed fluoride ions, as well as the weak intermolecular interactions such as hydrogen bonding and vdW forces. Furthermore, MOF-808-AA demonstrated satisfactory reusability and excellent chemical stability during the cyclic process. These findings suggest the potential application of MOF-808-AA for removing fluoride ions from wastewater.

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APPLIED CATALYSIS B-ENVIRONMENTAL · 2024 · IF 20.2

A novel hexagonal prism of Zr-based MOF@ZnIn2S4 core−shell nanorod as an efficient photocatalyst for hydrogen evolution

Lijun Liu,Luyang Zuo,Xuejing Zhai,Xiangping Xiao,Huitao Fan,Bo Li,Liya Wang

Photocatalytic water splitting is a commonly used pathway for hydrogen (H 2 ) production, and it is crucial to develop highly active ZnIn 2 S 4 (ZIS)-based photocatalytic systems. In recent years, metal-organic frameworks (MOFs) are also of great interest in the fields of energy production and environmental remediation. Therefore, this study primarily focuses on the fabrication of a series of heterojunction hexagonal prism-shaped Zr-based MOF@ZIS core-shell nanorods through a simple solvothermal method, in which ZIS nanosheets are highly distributed on the surface of the Zr-based MOF (NU-1000). The photocatalytic activities of the resulting materials were evaluated under visible light illumination (λ ≥ 400 nm) by combining different contents of NU-1000 with ZIS. The H 2 evolution results demonstrate that the optimal content of NU-1000 corresponds to a photocatalytic H 2 production rate of 8.53 mmol g −1 h −1 , which is 5.3 times higher than that of pure ZIS. The enhanced photocatalytic activity of the NU-1000@ZIS (NUZ) heterojunction can be attributed to the incorporation of the NU-1000, which provides abundant active sites due to its larger specific surface area. Additionally, the well-matched band structure between the NU-1000 and ZIS is beneficial to efficiently transfer and separate the photogenerated charge carriers. Furthermore, the NUZ core-shell nanorods exhibit excellent stability, offering a new approach for the fabrication of composite photocatalysts by combining MOF-based and ZIS in the field of photocatalytic H 2 production.

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CHEMOSPHERE · 2024 · IF 8.1

Precise manipulation of pore sizes in Zr(IV)-Based metal-organic frameworks for enhanced bisphenol a removal from water

Guangli Yu,Fei Ni,Wenyue Niu,Yu Chen,Feng Zhang,Guo-Dong Li,Xingfei Song,Yajing Zhang,Kangjun Wang

Metal-organic frameworks (MOFs) recently gained immense popularity for the adsorption of organic impurities. In this work, the adsorptive separation of bisphenol A (BPA) from aqueous mixtures was explored utilizing three types of zirconium-based MOFs, namely MOF-808, UiO-66, and hierarchically porous UiO-66 (HP-UiO-66). The HP-UiO-66, which was etched by sodium acetate as the terminal ligand, generated large mesopores ranging from 40 to 300 Å due to the departure of partial linkers and metallic clusters. The adsorption ability for BPA increased significantly with the introduction of numerous mesopores onto the HP-UiO-66 framework, even though the surface area of HP-UiO-66 was lower compared to that of the pristine UiO-66 and MOF-808. The study revealed that the maximum adsorption capacities ( q ) for BPA by HP-UiO-66 reached up to 295.04 mg g −1 , which was about 88.5% and 17.4% higher in comparison to UiO-66 and MOF-808, respectively. Furthermore, the q value of HP-UiO-66 was also better than many other previously reported MOF adsorbents. The analysis of possible adsorption mechanisms indicated that physical pore-filling was anticipated as the principal mechanism, attributed to the larger window size and high mesopore surface area of HP-UiO-66. Furthermore, X-ray photoelectron and Fourier transform infrared spectroscopic measurements inferred that the synergetic effects of H-bonding and π-π interactions played crucial roles in BPA capture as well. Overall, this study revealed a structure–property relationship in the Zr-MOFs-based adsorbents and opened up a new avenue to exploit unique MOF platforms for the efficient removal of emerging contaminations in the future.

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REACTIVE & FUNCTIONAL POLYMERS · 2025 · IF 5.1

The effect of coordination state on the activity of TA-Zr supramolecular networks for heavy metals removal from water

Shuxin Chen,Liting Wang,Wenxiang Ni,Hui Qiu

The self-assembly behavior of the MPNs-based adsorbent is substantially influenced by changes in solution pH. In this study, a highly negatively charged tannic acid‑zirconium (TA-Zr) macromolecular network has been successfully synthesized. As pH increases from 3 to 11, the coordination structure of TA with Zr(IV) changes from mono- to tri-complexation state, resulting in enhanced electronegativity and increased structural stability of tri-complex TA-Zr(9) due to its higher charge density. The TA dissolution experiments and zeta potential measurements confirm this conclusion. The tri-complex TA-Zr(11) underwent structural changes in its macromolecular network due to partial zirconium hydroxide formation under strongly alkaline conditions, as confirmed by X-ray photoelectron spectroscopy analysis, which in turn impacted its stability. Meanwhile, the adsorption capacity of TA-Zr materials for Pb(II) ion increases with the pH of the synthesis solution. XPS analysis suggested that the underlying adsorption mechanism involved ligand exchange between Pb(II) ion and phenolic hydroxyl groups on TA-Zr(9). After batch adsorption-regeneration cycles, TA-Zr(9) could be regenerated with an acidic solution while maintaining consistent Pb(II) ion removal efficiency. Furthermore, TA-Zr(9) effectively treated 12,150 bed volumes (BV) of synthetic water at pH 5.6, which is 18 times more than commercial D001. These results confirm that TA-Zr(9) shows great potential as an effective adsorbentfor Pb(II) removal in practical wastewater treatment, making it a promising candidate for water remediation.

CAS / MDL: 13520-92-8 1401-55-4
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AICHE JOURNAL · 2024 · IF 3.5

Production of jet fuel cycloalkanes from 5-(hydroxymethyl)furfural via cascade catalysis on Mg(Al)(Zr)O supported CuCo

Yanru Zhu,Zhen Zhang,Yunfei Zou,Jian Zhang,Zhe An,Xin Shu,Hongyan Song,Jing He

Catalytic conversion of biomass-derived 5-(hydroxymethyl)furfural (5-HMF) into carbon-increased hydrocarbons as drop-in energy-rich biofuels has received a great deal of concern for the development of sustainable chemical industry. Here, we demonstrate a one-pot conversion of 5-HMF into C 9 -alkanes on one single catalyst, acidic–basic layered double oxides (Mg(Al)(Zr)O) supported CuCo alloy. The well-defined multifunctional catalytic sites with harmonious combination carry out cascade catalysis, affording C 9 -alkanes (including 30% of more value-added branched-cycloalkanes) in 83% yield. The basic–acidic sites on Mg(Al)(Zr)O show high activity for aldol condensation of 5-HMF and acetone, producing 4-[5-(hydroxymethyl)-2-furanyl]-3-buten-2-one (HAc) in a yield of >99%. The engineered Co–Cu–Co linkages on supported CuCo perform efficient hydrodeoxygenation, affording C 9 -alkanes in a selectivity of 96% from HAc. C 9 -cycloalkanes are generated from the cyclization of the corresponding monohydric alcohol intermediates by the synergy of acidic and CuCo sites in the hydrodeoxygenation reaction.

CAS / MDL: 14985-18-3
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