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RSC Advances · 2017 ·Vol. 7 ·期 22 ·13325-13330 · IF 3.108

Growth of Zr/N-codoped TiO2 nanorod arrays for enhanced photovoltaic performance of perovskite solar cells

Zhenlong Zhang,Junfeng Li,Xiaoli Wang,Jianqing Qin,Wenjia Shi,Yuefeng Liu,Huiping Gao,Yanli Mao

In this paper, Zr and N co-doped TiO2 (Zr/N–TiO2) nanorod arrays were synthesized using a hydrothermal method and perovskite solar cells were fabricated using them as an electron transfer layer. The solar cells based on Zr/N–TiO2 presented an enhanced performance compared with those based on un-doped TiO2. The solar cell performance was optimized by changing the Zr doping content. The efficiency of solar cells based on Zr/N–TiO2 with a Zr doping content of 1% (Zr/Ti, atomic ratio) has been achieved at 12.6%, which was 31.6% higher than that of solar cells based on un-doped TiO2. To get an insight into the enhancement, some investigations were carried out. The results indicate that the larger open voltage (Voc) could be due to the larger conduction band offset resulting from the smaller energy band gap for Zr/N–TiO2, and the enlarged short current (Isc) could be attributed to the faster electron transfer and reduced recombination rate for Zr/N–TiO2 NRs. These induce the enhancement of solar cell efficiency.

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ACS Sustainable Chemistry & Engineering · 2024 · IF 7.1

Dual-Metal MOFs with High Proportion of Mo-Coordinated Zr–O Clusters for Promoting N2 Fixation

Xinyu Mao,Yu Chen,Shihao Li,Yang Yang,Chen Tao,Jiafu Shi,Zhongyi Jiang

Activation of the N≡N bond is of importance in photocatalytic nitrogen (N2) fixation, which strongly relies on the precise construction of catalytic active sites. Herein, we reported a dual-metal photocatalyst of Mo/UN(Zr) with a high proportion of Mo-coordinated Zr–O clusters (Zr–O–Mo dual-metal active sites) for photocatalytic N2 fixation, which was synthesized though post-modification to the defects of UN(Zr) by Mo. By contrast with the dual-metal photocatalyst of UN(Zr–Mo) synthesized via the co-mixing method, Mo/UN(Zr) possesses a higher proportion of Zr–O–Mo dual-metal active sites that is crucial for activating and polarizing N≡N bond as evidenced by in situ Fourier transform infrared (FTIR) spectroscopy combined with density functional theory (DFT) calculations. The synergistic effect of Zr–O–Mo dual-metal active sites resulted in a lower potential activation energy barrier for N2 activation which promoted the photocatalytic N2 fixation efficiency. The optimum photocatalytic N2 fixation rate of Mo/UN(Zr) was 255.7 μmol g–1 h–1 by adjusting the loading amount of Mo, which was enhanced about 2.5 times and 1.6 times compared with UN(Zr) and UN(Zr–Mo) photocatalyst, respectively. Our study will afford valuable guidance for designing efficient photocatalysts for photocatalytic N2 fixation.

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Progress in Natural Science-Materials International · 2024 · IF 4.8

High-efficiency solution blow spinning of flexible Zr-based ceramic fibers for advanced thermal insulation applications

Jiahao He,Chao Song,Longze Chen,Sicheng Xin,Pengfei Xiang,Wenbin Li,Chong He

Elastic zirconium-based ceramic fiber products have gain particular interest due to their exceptional high-temperature resistant performance. Nonetheless, commercial high-performance Zr-based fibers are still difficult to acquire which hinders its widely application in thermal insulation scenes. Herein, large-scale fabrication of various Zr-based (ZrO 2 , ZrSiO 4 ) ceramic fibers were achieved through solution blow spinning technology, which was endowed with merits such as cost-effectiveness, high production efficiency, reduced energy consumption, and exceptional product quality. Through high-temperature sintering to 1000 ​°C, blow spun organic fibers can be converted into Zr-based ceramic fibers with diameters ranging from 0.5 to 2 ​μm. Optimizing the crystalline structure of these fibers through high-temperature pyrolysis process enhanced their thermal resistance. Additionally, through introducing polysiloxane as the Si source, ZrSiO 4 fibers can be synthesized with markedly improved mechanical properties and high-temperature resistance. These blow-spun Zr-based fiber sponges exhibit advantageous internal pore structures, high-temperature elasticity and thermal insulation performance.

CAS / MDL: 64-17-5 23519-77-9
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Catalysts · 2025 ·Vol. 15 ·期 3 ·250 · IF 4

Investigation of Ternary CuZnM (M = Cr, Ce, Zr, Al) Catalysts in CO2 Hydrogenation for Methanol Synthesis

Jingjing Wang,Peixiang Shi,Jiahao Han,Yuhao Tian,Zhiqiang Yan,Pengcheng Luo,Hongyan Ban,Yanchun Li,Weijie Cai,Guanjing Lin,Zhiqiang Zhai,Congming Li

The hydrogenation of CO2to methanol over Cu-based catalysts is one of the attractive routes to reduce greenhouse gas emissions and generate high-value-added chemicals. Industrial CuZnAl catalysts possess some shortcomings, but various promoters can enhance the activity and durability of Cu-based catalysts for CO2hydrogenation. Herein, we systematically investigated the variations in the physicochemical properties of ternary CuZnM (M: Cr, Ce, Zr, Al) catalysts induced by different promoters, as well as their impact on CO2hydrogenation to methanol. The results demonstrate that the catalytic activity followed the order of CZCr > CZCe > CZZr > CZAl, with CZCr exhibiting the highest stability among them. Combined with XRD, SEM, TEM, H2-TPR, TPD, XPS, Raman findings and the experimental results, the smaller Cu particle size was conducive to increasing the CH3OH yield, and the lower Cu+/Cu0ratio exhibited better stability in CO2hydrogenation to methanol reaction. This approach offers theoretical insights and practical solutions for the industrial application of ternary Cu-based catalysts.

CAS / MDL: 10294-41-4 7789-02-8
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Anti-corrosion design of layered zirconium-based metal–organic frameworks (Zr-MOF) enhanced epoxy nanocomposite coatings

Bo Liu,Liangliang Xiong,Xiaoqiang Fan

In this work, two-dimensional UiO-67 nanosheets are successfully modified on graphene oxide (GO). The synthesized GO@2D-UiO-67 composite not only exhibits the electrical insulation characteristics of Zr-MOF, but also leverages the passive barrier effect of its 2D layered structure to prepare a highly anticorrosive epoxy coating. Electrochemical measurements reveal that the impedance modulus of the GO@UiO-67/EP composite coating remain two orders of magnitude higher than that of the pure EP coating even after 28 days of immersion in 3.5 wt% NaCl solution. This good long-term anti-corrosion performance could derive from the enhanced crosslinking density of composite coating due to the incorporation of GO@UiO-67 nanosheets. Furthermore, the shielding effect of layered structure and the corrosion inhibition behavior of organic ligands are proved to improve the corrosion resistance properties of composite coating. This research fills the application void of two-dimensional Zr-MOF composites in resin coatings, as well as serves as a forward-looking initiative to enhance the long-term corrosion protection of epoxy resin coatings.

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TALANTA · 2024 · IF 5.6

Phosphatase-mimicking Zr@PDA nanozyme with excellent dispersion stability for the detection of fructose 1,6-diphosphate

Yusha Huang,Chengli Xie,Longcheng Gong,Min Wang,Lianzhe Hu,Zhining Xia

Zr 4+ -doped polydopamine (Zr@PDA) nanozyme with phosphatase-like activity was synthesized by a one-pot hydrothermal method for the first time. Compared with previous representative phosphatase-mimicking nanozymes (i.e., CeO 2 NPs, ZrO 2 NPs and UiO-66), Zr@PDA not only exhibited higher dispersion stability in water, but also higher catalytical efficiency. K cat / K m of Zr@PDA is 35 and 12 times that of UiO-66 and ZrO 2 NPs, respectively, which would endow the Zr@PDA-based analytical methods with high sensitivity. As a demonstration, a novel colorimetric method based on Zr@PDA nanozyme was developed for sensitive detection of the drug fructose 1,6-diphosphate. The linear range is 1–15 μM with a detection limit as low as 0.38 μM.

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CATALYSIS LETTERS · 2025 ·Vol. 155 ·期 2 ·1-18 · IF 2.4

Synthesis of UiO–66–NH2(Ti/Zr) and its Catalytic Conversion of Cellulose to 5-HMF

Xu Lingling,Pan Xiaomei,Gao Lijing,Wei Ruiping,Li Jihang,Wen Xiu,Li Yuanzhuang,Xiao Guomin

UiO–66–NH 2 (Ti/Zr) modified by Ti metal oxide (TiO 2 ) was used to catalyze the hydrolysis of cellulose to prepare 5-HMF. Under the optimal reaction conditions of H 2 O(NaCl)/THF(1/4 mL), 190 °C, 2 h and 50 mg UNT-3(Ti/Zr) (TiO 2 and UiO–66–NH 2 with mass of 1.5 and 0.1 g, respectively), the yield of 5-hydroxymethylfurfural reached 59.88%. UiO–66–NH 2 (Ti/Zr) nanocomposites with different mass ratios were successfully prepared by simple solvent evaporation method. SEM and TEM have shown that the modified UiO–66–NH 2 (Ti/Zr) are wrapped into sphere by TiO 2 densely attached to the surface of UiO–66–NH 2 , which provides favorable conditions for the uniform dispersion of TiO 2 and coordination of the Lewis acidic site of UiO–66–NH 2 . NH 3 –TPD results confirmed the existence of super-strong, strong, middle and weak acid sites in UiO–66–NH 2 (Ti/Zr), and Py-FTIR confirmed the existence of Brønsted and Lewis acids. After four cycles, the yield of 5-HMF and FUR decreased slightly from 59.88 to 51.89% and 9.11 to 7.66%, respectively, and the yield of 5-HMF could still remain above 50%. The results showed that the modified composite treatment of TiO 2 with rich Lewis acid/base and UiO–66–NH 2 could provide a certain idea for the extensive application of biomass research in the future. Graphic

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JOURNAL OF THE AMERICAN CERAMIC SOCIETY · 2025 · IF 3.8

Precursor-modified strategy to in-situ fabricate lightweight SiC(Zr, rGO) nanocomposite PDCs for aerospace components

Tao Luo,Jinsheng Ye,Wenyan Huang,Ke Li,Yufan Wu,Yeqi Zhu,Siqi Lan,Shengjian Mao,Zhichao Xue,Rongqian Yao

Aimed at making SiC-based composites for thermal protection components to catch up with the increasing Mach number of hypersonic vehicles, a facile strategy is proposed to fabricate lightweight SiC(Zr, rGO) nanocomposite polymer-derived ceramics (PDCs). The key technique is repyrolyzing SiC(Zr, rGO) p /polyzirconocarbosilane–vinyltriethoxysilane–graphene oxide (PZCS–VTES–GO, PZVG) blends. Highly cross-linked PZVG can effectively optimize formability of precursors, and in-situ formed Zr-containing phases are beneficial in preventing further grain growth of β-SiC and improving bonding strength within ceramic network. More interestingly, ZrOSi transition zone tightly coupled with nanocrystals helps to increase structure disorder of amorphous ceramic matrix to tough nanocomposite structure. Particularly, SiC(Zr, rGO) 1300 nanocomposite PDCs own outstanding hardness (8.10 GPa), superior fracture toughness (3.84 MPa·m 1/2 ), high ceramic yield (92.60%), and low linear shrinkage (5.00%). Zr-modification enables them to retain favorable overall performances even after 60 min of oxidation under a 1300°C butane torch flame. Timely self-healing ZrO 2 (ZrSiO 4 )/SiO 2 protective layer can enhance high-temperature oxidation resistance. Meanwhile, ZrO 2 and ZrC have a unique combination of good high-temperature stability/resistance to corrosion, strongly improving structural integrality. As demonstrated, such in-situ construction of nanocomposite system and pyrolytic mechanism open new opportunities for obtaining PDCs with superior high-temperature ablation resistance, toward emerging uses in thermal protection system of hypersonic aerospace vehicles.

CAS / MDL: 17501-44-9 78-08-0
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BIORESOURCE TECHNOLOGY · 2025 · IF 9

Transform waste into profit: Extract licorice residue fiber to load Zr-MOF as a promising adsorbent

Jiao Long,Yan Gao,Kangjia Sheng,Junjie Yao,Xinglong Zheng,Tao Bao,Wanghui Jing,Sicen Wang

The research on the reuse of resources is crucial for achieving high-value utilization of traditional Chinese medicine (TCM). In this study, licorice residues were selected to extract fibers by alkaline hydrogen peroxide oxidation because of their high cellulose content and widespread use. The cellulose, hemicellulose and lignin content of obtained fibers were found to be 55 %, 8.2 % and 18.8 %, respectively. Immobilizing MOF-808 onto licorice residue fibers yields a composite material exhibiting enhanced adsorption capabilities. The synthesized material was employed to adsorb ketoprofen, naproxen and diclofenac sodium. The characterization results confirmed the successful modification. Adsorption performance experiments indicate that the adsorption behavior follows pseudo-second-order kinetic models and Langmuir isotherm. The adsorption is a process of rapid adsorption and slow equilibrium, showing satisfactory adsorption capacity. X-ray photoelectron spectroscopy and density functional theory calculation revealed that the sustained adsorption attributed to the synergy of π-π stacking, hydrogen bonding and coordination interaction. This study emphasizes the potential for reusing licorice residues and paves the way for the treatment of TCM residue after extracting active ingredients.

CAS / MDL: 13520-92-8 7778-77-0
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2025 · IF 3.9

Zr-Incorporated SiO2-Supported Cs for Effective Production of Methyl Methacrylate via One-Step Aldol Condensation

Jinguo Hao,Senlin Deng,Junyang Liu,Lei Wang,Shasha Cao,Junping Zhang,Gang Wang,Chunshan Li

Modification of supported Cs-based catalysts has stimulated researchers’ interests, considering their effective catalytic performance in methyl methacrylate (MMA) production via one-step aldol condensation. Herein, we developed a series of Zr-incorporated SiO2-supported Cs (Cs/Zr-SiO2) catalysts using sol–gel in combination with solvothermal and impregnation methods. The structure and physicochemical properties were analyzed systematically by employing multiple characterization techniques, which guided the optimization of synthesis parameters such as Si/Zr molar ratio, prehydrolysis time, and Cs loading. The effects of catalyst structure, acid–base properties and their balance, and the chemical state of Cs and Zr species on the catalytic performance were systematically correlated. Results indicate that Zr was incorporated into the SiO2 framework with a four-coordinated configuration to form Si–O–Zr structures to act as Lewis acid sites, while the Cs component provides base sites through the formation of Cs–O–Si configurations. As a result, the methyl propionate (MP) conversion could reach up to 34.9% with MMA selectivity of 88.4%, representing 10–12% enhancement over the traditional impregnation method. In situ IR spectroscopic insights elucidated that the activation of formaldehyde and MP proceeded severally on the Si–O–Zr and Cs–O–Si sites, which seemed to be more efficient than those on an impregnation-prepared sample. Kinetic studies determined the activation energy of 115 kJ/mol, with reaction orders of 1.04 and 1.14 for MP and FA, respectively. In addition, the catalyst exhibited excellent regeneration and recycling behavior during the long-term stability test, and the initial activity of sample deactivated due to carbon deposition could be easily recovered after thermal treatment.

CAS / MDL: 64-19-7
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ANALYTICA CHIMICA ACTA · 2025 · IF 6

LA-ICP-MS-quantitated boronate affinity magnetic Zr-MOFs prepared via post-modification for glycopeptides enrichment

Feng Zhang,Sen Zhang,Xing Liu,Wei Gao,Jun Luo,Yi-fan Pan,Wei-Juan Zheng,Xin Hu,Hong-zhen Lian

Background Glycoproteins are critical in various biological processes and attract lots of attention of researchers. It still remains a challenge to detect glycopeptides by mass spectrometry because of their low abundance with heterogeneity and lability, as well as signal suppression by non-glycopeptides. The boronate affinity-based enrichment is an effective solution for detecting cis -diols-containing compounds including glycopeptides in complex matrices. However, there has not been any report about absolute quantitation of boron in the absorbent materials for glycopeptides, which obstructed the tailored design of boronate affinity materials and deeper understanding of interaction mechanisms. Results This work presents the development of a boronic acid-functionalized magnetic zirconium metal-organic framework (mMOF–AAPBA) with actual boron content for specific capture of glycopeptides. The synthesized nanocomposite could enrich glycopeptides by magnetic solid-phase extraction (MSPE) via the synergistic effect of hydrophilic interaction and boronate affinity. After full characterization including quantitative analysis of boron by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), mMOF–AAPBA was applied as MSPE absorbent to capture glycopeptides. Under the optimized conditions, it could enrich 28 glycopeptides both from horseradish peroxidase and immunoglobulin digests, with a limit of detection of 1 fmol μL −1 coupled with matrix-assisted laser desorption/ionization time of flight mass spectrometry. The boronate affinity absorbent also possessed great ability of anti-interference and good reusability. Furthermore, it possessed high performance in enriching glycopeptides in real samples including human saliva and traditional Chinese medicine injections. Significance In the preparation of the boron-containing nanocomposites, there is a special interest that an accurate protocol was established to assay boron based on LA-ICP-MS assisted by home-made matrix reference substances for the first time. These findings highlight the quantitative boron-containing mMOF–AAPBA as a robust affinity material for glycopeptide enrichment in real biological samples, offering potential applications in glycoproteomics and other cis -diols compound related researches.

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JOURNAL OF FOOD COMPOSITION AND ANALYSIS · 2025 · IF 4.6

Organic ligand-dependent performance of Zr-MOF functionalized magnetic polydopamine nanocomposites for camel meat DNA purification

Jianmei Li,Qi Sun,Haiyu Li,Zongyao Zhao,Ting Gong,Mengqin Xiang,Feng Gao,Yong Tang

Traditional DNA purification methods face limitations in efficiency and complexity, particularly for food authenticity verification. To address this, we developed novel magnetic nanocomposites by integrating polydopamine-coated Fe 3 O 4 nanoparticles (Fe 3 O 4 @PDA) with zirconium-based metal-organic frameworks (Zr-MOFs) functionalized via varying organic ligands (terephthalic acid, 2-aminoterephthalic acid, and 1,2,4-benzenetricarboxylic acid). The resulting materials—MUIO-66, MUIO-66-NH₂, and MUIO-66-COOH—were characterized for structure, magnetism, and DNA adsorption performance. MUIO-66-COOH exhibited superior efficiency, achieving >80 % DNA recovery from camel meat under optimized conditions (25 °C, 10 min), outperforming commercial kits. Adsorption kinetics and isotherms revealed a multilayer process (Freundlich model) governed by pseudo-second-order kinetics, driven by "salt-bridge" interactions between DNA phosphate groups and surface carboxyl moieties. The method demonstrated high precision (RSD = 2.75 %), reproducibility, and reusability (>81 % efficiency after 5 cycles). This work establishes a rapid, ligand-tunable magnetic solid-phase extraction (MSPE) platform for high-quality DNA extraction, advancing biosensing applications in food authenticity.

CAS / MDL: 64-17-5 67-63-0 68-12-2
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