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ENERGY CONVERSION AND MANAGEMENT · 2019 · IF 7.181

Hydrogen production through steam reforming of toluene over Ce, Zr or Fe promoted Ni-Mg-Al hydrotalcite-derived catalysts at low temperature

Fan Zhou,Ningyi Pan,Hongyu Chen,Xiang Xu,Chunhao Wang,Yankun Du,Yang Guo,Zheng Zeng,Liqing Li

Ni-Mg-Al hydrotalcite-derived materials promoted with Ce, Zr or Fe were prepared by the co-precipitation method, which exhibited excellent performance in steam reforming of toluene (SRT) at low temperature. Especially, Fe-doped catalyst had higher catalytic activity and stability at 400 °C, which maintained almost 100% toluene conversion during the SRT reaction (3 h). Moreover, it also had higher hydrogen production and better selectivity for hydrogen production. The physico-chemical characterizations and model simulation indicate its high dispersion of active sites and accessibility of reactants to active sites: uniform dispersion of active sites (SEM, TEM and EDX), large specific surface area (151 m 2 /g), pore volume (0.84 cm 3 /g) and average pore diameter (22.1 nm), small crystallite size (34.9 nm), desirable Ni species reducibility (TPR), high basicity (TPD), low metal carbide formation (XPS), and good adsorption affinity with toluene (−18.391 kJ mol −1 , DFT). Moreover, less carbon was deposited on the Fe-containing catalyst through measuring the amorphous carbon and CNTs by the TG-MS method, which was due to the tip-growth mechanism of CNTs. Considering lower toluene conversion temperature, higher hydrogen yield, and better resistance to carbon deposition, this study may be meaningful in development of SRT at low temperature.

CAS / MDL: 497-19-8
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ENERGY & FUELS · 2018 · IF 3.024

Facile and High-Yield Synthesis of Alkyl Levulinate Directly from Furfural by Combining Zr-MCM-41 and Amberlyst-15 without External H2

Lincai Peng,Xueying Gao,Xin Yu,Hui Li,Junhua Zhang,Liang He

An integrated multistep catalytic process in a one-pot cascade model to realize conversion is preferred in terms of process economics and energy efficiency. Here, we present the noble-metal-free but highly effective catalytic transfer hydrogenation and acid-catalyzed conversion of biomass-derived furfural for direct production of biofuel alkyl levulinate using alcohols as the hydrogen donor and reaction medium. With optimization of the process variables, a high yield of alkyl levulinate at up to 85.3% could be captured under mild conditions in isopropanol medium with the combination of Zr-MCM-41 and Amberlyst-15 catalysts. The reaction proceeds via the catalytic transfer hydrogenation of furfural to furfuryl alcohol over Zr-MCM-41, which is then converted to alkyl levulinate by an Amberlyst-15 acid catalyst. The spent hybrid catalysts could be effectively recovered from the resulting reaction mixture and reused 5 times with little deactivation after plain regeneration treatment.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Carboxylic acid modulated in situ growth of Zr-based MOFs on carboxylated cotton fabrics for removal of Cr(VI) from aqueous solutions

Jinshan Xie,Xiaoxiang He,Kexin Liu,Wulong Li,Zhanxiong Li

In this paper, carboxylated cotton fabric (CF-Ph-COOH) were obtained as active substrate by diazonium radical polymerization modification of cotton fibers. Then the MOF fabric composites were prepared by in situ growth of metal zirconium ions (Zr) and organic ligands on the surface of carboxylated cotton fabrics under carboxylic acid modifier. MOF fabric composites with controllable morphologies structures were achieved by regulating organic ligands, reaction time the type and dosage of regulator (formic acid and acetic acid). The prepared acetic acid regulated MOF fabric composites were designated as CF-HAc1-UiO-66, CF-HAc2-UiO-66, CF-HAc1-UiO-66-NH 2 , and CF-HAc2-UiO-66-NH 2 , respectively, and the formic acid regulated as CF-FA-UiO-66 and CF-FA-UiO-66-NH 2 . The fabricated carboxylic acid modulated MOF fabric composites were well characterized using SEM, TGA, XRD, FTIR, and XPS spectra. The adsorption experiment results show that carboxylic acid modulated Zr based MOF fabric composites can serve as adsorbent for effective removal of Cr(VI) from water, in which the CF-FA-UiO-66-NH 2 was prepared under the ratio of ZrCl 4 and BDC-NH 2 is 1.006 and with 5.47 M formic acid regulator exhibits that the optimal adsorption efficiency and the removal efficiency is 79.5 %. In addition, the adsorption of Cr(VI) in water by CFA-UiO-66-NH 2 showed a quasi-secondary kinetic model following the Langmuir adsorption model, showing a a typical of chemisorption. What’s more, the Cr(VI) removal efficiency and saturated adsorption capacity of CF-FA-UiO-66-NH 2 was up to 80 % and 318.85 mg/g, respectively. The prepared CF-FA-UiO-66-NH 2 MOF fabric composite was recyclable for removal of Cr(VI), and could be used as the potential adsorbent membrane for waste water treatment.

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International Journal of Electrochemical Science · 2024 · IF 1.3

Fabrication of highly conductive VXC-72R carbon nanoparticles decorated Zr (IV)-based metal-organic framework for highly sensitive detection of methyl parathion

Mengyuan Zhao,Yunhang Liu,Fang Li,Jiale Han,Volodymyr Dubovyk,Hongyuan Zhao

A simple and efficient ultrasonic-assisted strategy was used to prepare the nanocomposite of Vulcan XC-72R carbon (VXC-72R) nanoparticles and Zr(IV)-based metal-organic framework (UIO-66) nanoparticles. For the multifunctional VXC-72R@UIO-66 nanocomposite, VXC-72R nanoparticles possessed good conductivity property and good dispersion, which were conductive to form the interconnected carbon conductive channels; UIO-66 nanoparticles could improve the accumulation ability of methyl parathion (MP) because of the high affinity of Zr-O groups with phosphoric groups. Moreover, the introduction of VXC-72R nanoparticles could effectively make up the conductivity property of UIO-66 nanoparticles. The VXC-72R@UIO-66/GCE sensor presented good MP detection performance with limit of detection (LOD) of 1.35 nM (Linear MP concentration range: 0.01–10 μM). When used for the detection of MP in juice samples, the VXC-72R@UIO-66/GCE sensor showed acceptable recoveries of 96.00–104.67 %.

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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
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Nano Zr/Cu oxide modified poly-β-cyclodextrin peroxidase mimic for potable discrimination of aminophenol isomers and catalytic degradation of methyl red

Shuo Sun,Xingyu Fu,Xu Yang,Shuhui Zhao,Huitian Zhi,Ruhui Shang,Xujie Wang,Yingchao Yang,Zhengquan Yan,Lei Hu

To high-performance recognize or degrade o/p -aminophenol and methyl red, nano Zr/Cu oxide decorated poly-β-cyclodextrin (CuO/ZrO 2 @p-β-CD) was developed under microwave-assisted conditions. Fibrous CuO/ZrO 2 @p-β-CD expressed synergistic peroxidase-like activity to degrade >90.4 % methyl red in the air. When applied to accelerate the oxidization of 2,2′-azinobis (3-ethyl benzothiazoline-6-sulfonic acid) ammonium salt (ABTS), K m / V max could be 0.053 mM/2.92 × 10 −8  M/s. Trace aminophenol isomers ( o -AP and m -AP) could exclusively alter CuO/ZrO 2 @p-β-CD-ABTS from green to colorless or to purple-red with remarkable time-resolved effect. Under the optimized conditions, CuO/ZrO 2 @p-β-CD was successfully applied for intelligent monitoring or degradation o -AP, m -AP or methyl red in practice with the help of a smartphone. The recoveries for UV–vis spectral/RGB detection of o -AP and m -AP could reach 100.0 % ~ 102.9 %/98.0 % ~ 102.5 % and 97.8 % ~ 101.1 %/96.8 % ~ 103.33 %. The catalytic detection or quantitative degradation mechanisms were investigated in detail. This work will provide a potential for quantitative monitoring or degradation of organic pollutions.

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ACS Applied Materials & Interfaces · 2018 · IF 8.097

Composites of Layered M(HPO4)2 (M = Zr, Sn, and Ti) with Reduced Graphene Oxide as Anode Materials for Lithium Ion Batteries

Mei Ma,Shouwu Guo,Wenzhuo Shen

Tetravalent metal phosphates (M(HPO4)2, M = Zr, Sn, and Ti) have robust layered structures with interlayer d spacings over 7.5 Å, but show poor electrical conductivity. On the other hand, single-atomic-layered reduced graphene oxide (rGO) sheets exhibit a high electrical conductivity. In this work, the combination of rGO and M(HPO4)2 is explored for their potential as anode materials for lithium ion batteries (LIBs). Specifically, rGO/M(HPO4)2 composites are prepared, and their electrochemical performances are investigated systematically. In comparison with bare M(HPO4)2, the rGO/M(HPO4)2 composites exhibit larger specific capacity, higher rate capability, better cyclic stability, lower voltage for lithium ion insertion and extraction, and improved first Coulombic efficiency. We propose that the superior electrochemical performances of the composites are primarily contributed to the large interlayer space of M(HPO4)2 and the rGO sheets cladded on the surfaces of the layered M(HPO4)2. The attached rGO sheets bridge the layers together forming a network that is beneficial for the electron and ion diffusion within the composites, thus enhancing the discharge/charge rate capability of the composites. In addition, the attached rGO sheets provide extra anchoring sites for Li+; the specific capacity of the composites as anode materials is thus enhanced.

CAS / MDL: 13520-92-8
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

A modulator-induced defect strategy to construct different mesopore ratios Zr-based metal-organic frameworks for ultrafast adsorption of heterocyclic aromatic amines

Qiyue Zhao,Hong-Man Hou,Gong-Liang Zhang,Hongshun Hao,Bei-wei Zhu,Jingran Bi

The platform of isostructural crystalline metal-organic frameworks (MOFs) with structural defects and additional pores is an emerging technology for rapidly removing hazardous small molecules. Herein, this paper designed a series of Zr-based MOFs (UiO-66) with different mesopore ratios by inducing linker/cluster missing through monocarboxylic acid modulators; besides their adsorption capacity and mechanism for heterocyclic aromatic amines (HAAs) were investigated. The UiO-66 defected with lauric acid (UiO-66-12A) showed the best adsorption performance and its adsorption capacity and rate for HAAs were 1.25–5.63 and 1.74–5.82 times higher than UiO-66, respectively. The zeta potentials of adsorbents in the presence of HAAs aqueous solutions underscore the pivotal role of electrostatic interactions during adsorption. Fourier Transform Infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) demonstrated that π-π stacking, coordination and hydrogen bonding interactions were also critical factors in promoting adsorption. Moreover, simulation calculations revealed that UiO-66 with missing clusters can provide more active sites and stronger interactions. These findings provided a novel and feasible strategy for the rapid removal of hazardous small molecules from complex food environments, which could improve the adsorption capacity and convenient processes of MOFs through building appropriate inherent microporous structures. The comprehensive and systematic understanding of the adsorption mechanism in this paper is conducive to the future advancement of nanomaterials.

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JOURNAL OF APPLIED POLYMER SCIENCE · 2025 · IF 2.8

Promoting Proton Conductivity and Methanol-Resistance of PVdF-Based PEM Membrane by Incorporating Dispersive CNT Dotted With α-Zr(HPO4)2∙H2O

Pengtao Lei,Xiangyang Xu,Chenyu Huang,Dongsheng Chen,Zhenkun Jiang

To optimize the proton transport performance of polyvinylidene fluoride (PVdF), a proton exchange membrane (PEM) material, carbon nanotube (CNT), and zirconium hydrogen phosphate (ZrP) have been blended into the PVdF matrix. Adopting a hydrothermal synthesis route, the acidic ZrP can be better conjugated with the positively charged CNT functionalized by cetyltrimethylammonium bromide (CTAB). As visualized using electroscopes, ZrP nanocrystallines are intimately dotted and homogeneously distributed on CNT. The ZrP–PVdF interaction can be attributed to hydrogen bonding between hydroxyl and F-terminal groups. By incorporating well CNT/ZrP into PVdF via solution casting, the pore architecture can be regulated; namely, the macro-voids in PVdF are greatly reduced. The composite membranes exhibit tensile stress of 48–52 MPa while sustaining the thermal stability of PVdF. The incorporated CNT/ZrP can suppress void porosity and enhance film hydrophilicity. With improved wettability, the methanol permeability can be reduced to less than 2 × 10 −9 cm 2 ∙s −1 , ca. one-sixth that of pure PVdF. The proton conductivity for PVdF-CNT 0.03 -ZrP 0.06 , with CNT and ZrP mass content respectively 3 and 6 wt% that of PVdF, attains 0.089 S·cm −1 at 100°C, showing upgraded conducting capability. The membrane selectivity can be remarkably enhanced, verifying that CNT/ZrP blending is a facile and profitable approach for PEM optimization.

CAS / MDL: 872-50-4 24937-79-9
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Journal of Environmental Chemical Engineering · 2025 · IF 7.2

Preparation of Zr-based MOF/PDMS Janus membrane for vacuum membrane distillation and its removal of phenolic pollutants from coal chemical wastewater

Qingqing Niu,Mingzhu Chen,Tengfei Shao,Weijun Zhen

The conventional blending method for preparing photocatalytic composite membranes often results in dense polymeric structures that encapsulate photocatalysts, thereby limiting their photocatalytic activity. To address this limitation, we developed an innovative Janus membrane through in-situ growth of polyaniline for hydrophilic modification of polydimethylsiloxane (PDMS), followed by controlled deposition of zirconium-based metal-organic framework (TFMOF) particles via a dip-coating process. The obtained TFMOF/PDMS Janus membrane exhibits significant asymmetric wettability (underwater oil contact angle >140°). In phenol degradation tests, the membrane achieved 93.78 % removal efficiency within 2 h under visible light irradiation. When applied to actual coal chemical wastewater treatment, the Janus membrane demonstrated removal rates of 68.71 % for volatile phenols and 77.22 % for COD in the feed solution, with corresponding values of 79.85 % and 86.18 % in the distillate, respectively. This work provides a robust solution for coal chemical wastewater treatment by synergistically combining asymmetric wettability structure with photocatalytic membrane distillation.

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Food Analytical Methods · 2025 · IF 3

An Ultra-Sensitive Electrochemical Sensing Platform Based on a Novel Ternary Heterostructured Ag-TiO2@Zr-TCBPE Nanocomposite for Ciprofloxacin Detection in Food

Li Congwei,Wang Beibei,Kang Kai,Wang Lanyue,Zhao Zhenzhen,Wang Yuping,Ji Xueping

To address ciprofloxacin (CIP) contamination in animal-derived foods, an ultrasensitive electrochemical sensing platform based on a novel ternary heterostructure (Ag-TiO 2 @Zr-TCBPE) was developed through interfacial engineering. The heterointerface was constructed by anchoring a metal–metal oxide electrocatalyst (Ag-TiO 2 ) onto a conductive metal–organic framework (Zr-TCBPE) with a 3D porous hexagonal prismatic structure and high conductivity. This work demonstrates for the first time that the large-scale conjugated architecture of Zr-TCBPE nanotubes enhances CIP enrichment, while the Ag-TiO 2 /Zr-TCBPE heterointerface optimizes electron transport pathways and synergistically promotes CIP oxidation via interfacial electric field-driven effects. Under acidic conditions (pH 5.0), the Ag-TiO 2 @Zr-TCBPE/GCE sensor exhibited optimal performance: a linear range spanning five orders of magnitude (2.5 nmol·L −1 to 150 μmol·L −1 ), a limit of detection (LOD) of 1.6 nmol·L −1 , surpassing most reported CIP sensors. The sensor also showed high anti-interference capability (97.1–107% signal retention), long-term stability (> 96.4% signal retention after 15 days), and satisfactory recovery rates (91.6–103%) in complex matrices (milk, eggs, and river water). This study provides fundamental insights into TCBPE-MOF heterointerface engineering and establishes a robust analytical platform for detecting trace antimicrobials in food and environmental samples.

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INORGANIC CHEMISTRY · 2025 · IF 4.7

Catalytic Effect of Pd0 NPs Encapsulated in UiO-66(Zr) under Microenvironment Modulation for the Degradation of Trimethoprim in Fenton-like Reaction

Ying Gao,Ruibin Yang,Qinqin Chen,Xinhao Shen,Dapeng Li,Juanhong Li,Feng Liu,Jianhua Wu,Sanjian Ma,Guoliang Dai,Dongmei Wang,Lei Xie,Zixia Lin,Xin Liu

The large-scale production of iron sludge and the safety issues of H2O2 usage are two limitations in the promotion and application of the Fenton reaction. To further solve the problems, an active hydrogen reduction strategy was proposed. Herein, the reducing property of active hydrogen was utilized to simultaneously generate H2O2 in situ and accelerate the regeneration of ferric in the reaction process. The composite metal–organic frameworks (MOFs) Pd@UiO-66(Zr) and Pd@UiO-66(Zr)-2OH, which were stable under acidic conditions, were synthesized for hydrogen activation. Under the condition of only trace amounts of ferrous and hydrogen added, both catalysts showed excellent performance in the degradation experiments of trimethoprim. The kobs of the Pd@UiO(Zr)-66-mediated system is 0.0487 min–1, which is 1.67 times that of Pd@UiO-66(Zr)-2OH. In the pollutant degradation reaction system constructed by these two materials, both of the hydroxyl radicals and singlet oxygen play a dominant role. The Bader charge analysis showed that the charge transfer from Pd to the MOF host was higher on Pd@UiO-66(Zr) than Pd@UiO-66(Zr)-2OH, which could be a key factor in distinguishing the catalytic activity of the catalysts. In addition, both catalysts showed excellent stability over six cycles. Nearly 100% degradation of trimethoprim could be achieved. This study provides some reference for the control of emerging pollutants by UiO-66(Zr) series materials.

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