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CHINESE JOURNAL OF CATALYSIS · 2018 · IF 3.525

Oxidative coupling of methane: MOx-modified (M = Ti, Mg, Ga, Zr) Mn2O3-Na2WO4/SiO2 catalysts and effect of MOx modification

Pengwei Wang,Xin Zhang,Guofeng Zhao,Ye Liu,Yong Lu

Mn 2 O 3 -Na 2 WO 4 /SiO 2 is considered as the most promising catalyst for the oxidative coupling of methane (OCM) process; however, it only has a better catalytic performance over 800 °C. To improve its low-temperature performance, an attempt has been made to modify the Mn 2 O 3 -Na 2 WO 4 /SiO 2 catalyst using TiO 2 , MgO, Ga 2 O 3 , and ZrO 2 . Among the synthesized catalysts, the TiO 2 -modified Mn 2 O 3 -Na 2 WO 4 /SiO 2 catalyst shows markedly improved low-temperature OCM performance, achieving a high CH 4 conversion of ~23% and a good C 2 -C 3 selectivity of ~73% at 700 °C (the catalyst bed temperature), along with promising stability for at least 300 h without signs of deactivation. In comparison with the unmodified Mn 2 O 3 -Na 2 WO 4 /SiO 2 catalyst, the TiO 2 modification results in significant improvement in the low-temperature activity/selectivity, whereas the MgO modification has almost no impact and the Ga 2 O 3 and ZrO 2 modifications have a negative effect. The X-ray diffraction (XRD) and Raman results reveal that the formation of a MnTiO 3 phase and a MnTiO 3 -dominated catalyst surface is crucial for the improvement of the low-temperature activity/selectivity in the OCM process.

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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Regulating the Interface Polarity Distribution of Zr-Based MOFs by Amino Acid-Like Ligand Functionalization Enables Efficient Recovery of Gold

Guangyuan Hu,Zhiwei Wang,Changqing Xia,Xinliang Wang,Hongxing He,Zhifeng Nie,Shixing Wang,Weili Li

The recovery of gold from industrial effluents is crucial for environmental conservation, sustainable resource management, and promoting the green development of gold resources. We designed a Zr-based MOF (UKM-78) by incorporating functional organic ligands that resemble amino groups, using MOFs’ inherent sieving effect for ion separation. This novel material exhibited enhanced gold recovery under acidic conditions, with an adsorption capacity three times and an adsorption rate four times higher than those of nonfunctionalized UKM-77. Notably, UKM-78 efficiently captured gold solutions at concentrations as low as 1 ppm and achieved an adsorption rate exceeding 90%, owing to the electrostatic interactions and coordination between its functionalized groups and the synergistic effect of its porous structure. Despite multiple regeneration cycles, UKM-78 retains 99.4% of its adsorption capacity. X-ray photoelectron spectroscopy (XPS), kinetic studies, and thermodynamics collectively demonstrated that Au(III) binding on UKM-78 involved cooperative electrostatic interactions and chemical adsorption through coordination. This study highlights the potential of MOFs for efficient and sustainable recovery of gold from complex waste streams.

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ENVIRONMENTAL RESEARCH · 2024 · IF 7.7

Preparation of Zn/Zr-MOFs by microwave-assisted ball milling and adsorption of lomefloxacin hydrochloride and levofloxacin hydrochloride in wastewater

Fuhua Wei,Jie Gong,Qinhui Ren,Xiang Yu,Yan Wang,Hongliang Chen,Zhao Liang

The Zn/Zr-MOFs were synthesized via microwave-assisted ball milling and subsequently characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The thermal stability of the Zn/Zr-MOFs was evaluated through thermogravimetry (TGA). The results demonstrated the exceptional adsorption properties of the Zn/Zr-MOFs towards Lomefloxacin hydrochloride and Levofloxacin hydrochloride. At a concentration of 30 ppm for Lomefloxacin hydrochloride, the addition of 30 mg of Zn/Zr-MOFs material resulted in an adsorption capacity of 179.2 mg•g−1. Similarly, at a concentration of 40 ppm for Levofloxacin hydrochloride, the addition of 30 mg Zn/Zr-MOFs material led to an adsorption capacity of 187.1 mg•g−1. Kinetic analysis revealed that the experimental data aligned well with a pseudo-second order kinetic model. Overall, these findings highlight the significant potential application of Zn/Zr-MOF materials in wastewater treatment.

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Russian Journal of Physical Chemistry A · 2026 ·Vol. 100 ·期 10 ·2407-2418 · IF 0.7

Synergistic Plasmon-Piezoelectric Enhancement in Ag-Modified Gd and Zr Co-doped BiFeO3 Nanoparticles for Piezo-photocatalysis Degradation of Ofloxacin

Xuan Liu,Huang Jinliang,Guo Feifei,Chang Liangliang,Zhou Chunsheng,Xi Zengzhe

This study presents a novel strategy to significantly enhance the piezocatalytic performance of BiFeO 3 for antibiotic degradation by integrating cation co-doping and noble metal decoration. To address the inherent limitations of rapid charge recombination and insufficient active sites in pristine BiFeO 3 , Gd, and Zr co-doped BiFeO 3 (BGFZ9) NPs were first synthesized via a sol-gel method. Subsequently, Ag NPs were uniformly deposited on the BGFZ9 surface through a facile photochemical reduction process to construct Ag/BGFZ9 nanocomposites. Comprehensive characterizations including XRD, XPS, TEM, and VSM confirmed the successful formation of the perovskite structure, uniform dispersion of Ag NPs, and tailored magnetic properties. The optimized Ag2/BGFZ9 catalyst demonstrated remarkable piezocatalytic and piezo-photocatalytic activity towards ofloxacin, achieving degradation efficiencies of 82.54 and 86.98% within 120 min under ultrasonic and combined ultrasonic/visible-light irradiation, respectively. The corresponding first-order rate constants were 0.0147 and 0.0164 min –1 , representing a significant enhancement over the undoped and unmodified counterparts. The superior performance is attributed to the synergistic interplay of multiple factors: (1) the Gd/Zr co-doping induced lattice distortion and optimized band structure, enhancing the intrinsic piezoelectric response; (2) the formation of a Schottky junction at the Ag/BGFZ9 interface, which acted as an efficient electron sink to suppress charge carrier recombination; and (3) the LSPR effect of Ag NPs under visible light, which broadened light absorption and generated hot electrons. Radical trapping experiments and EPR spectroscopy identified \( \bullet {\kern 1pt} {\text{O}}_{2}^{ - }\) and \( \bullet {\kern 1pt} {\text{OH}}\) as the primary reactive oxygen species. The catalyst maintained 82.13% of its initial activity after five consecutive cycles, demonstrating excellent stability and magnetic recoverability. This work elucidates a synergistic piezoelectric-plasmonic coupling mechanism and provides a viable design principle for developing efficient, stable, and magnetically separable multiferroic catalysts for advanced oxidation processes in wastewater remediation.

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MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING · 2025 · IF 4.6

Construction of MWCNT-Bridged ternary S-scheme BiVO4/NH2-UiO-66 (Zr) heterojunction for enhanced visible-light photocatalytic degradation of tetracycline

Mingming Dong,Shuyong Yang,Peng Zhou,Yue Gao,Anshun Wang,Shenghui Tu

The accumulation of antibiotics in aquatic ecosystems poses a serious threat to the environment and to human health. Tetracyclines (TC) account for a significant proportion of antibiotic residues worldwide. In order to overcome the limitations of conventional degradation methods, we created a three-component S-scheme heterojunction consisting of BiVO 4 /MWCNTs@NH 2 -UiO-66 (Zr) using a two-step solvothermal process. This synergistic integration utilises: (i) MWCNTs as electron transport bridges; (ii) NH 2 -UiO-66 (Zr) for high TC adsorption (surface area of 931.86 m 2  g −1 ); and (iii) BiVO 4 for visible light harvesting. This architecture broadens light absorption, reduces charge recombination and enables dual-pathway Reactive Oxygen Species (ROS) generation. Under visible light, the optimised catalyst achieves 95.2 % TC degradation within 90 min–7.73 times faster than pristine BiVO 4 (k = 0.02721 vs. 0.00352 L mg −1 ·min −1 ). Radical trapping and EPR analyses confirm ·O 2 − and h + as the dominant species, while LC-MS reveals three degradation pathways. With 85.3 % activity retention after five cycles, this work provides a blueprint for the design of efficient, antibiotic-mineralising photocatalysts.

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FUEL · 2025 · IF 7.5

Experimental and DFT investigations of multiple active sites in Zr/Co-MOFs catalysts for tandem catalysis of styrene to styrene carbonate

Yuanyuan Cui,Gang Fu,Jiaxing Wen,Li Yang,Jiaxu Zhang,Jianmin Sun

The direct synthesis of cyclic carbonates from olefins involves a tandem process of olefin epoxidation and CO 2 cycloaddition, but designing a single catalyst with multiple active sites remains a challenge. In this work, a series of dual ligands quaternized Zr-based MOFs (Zr-Bpydc(Py + Br − )/CoTCPP-x, x = 1–5) were successfully synthesized by co-assembling 2,2′-bipyridine-5,5′-dicarboxylic acid (Bpydc) and cobalt(II) 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (CoTCPP) with Zr 6 clusters, followed by post-synthetic quaternization to incorporate nucleophilic Br − sites. Among them, Zr-Bpydc(Py + Br − )/CoTCPP-4 exhibited the best catalytic performance under mild reaction conditions (80 °C, 1.0 MPa, 12 h), achieving styrene conversion of 94.2 % and styrene carbonate (SC) selectivity of 66.5 %, significantly outperforming most previously reported heterogeneous catalytic systems under cocatalyst-free conditions. The excellent catalytic activity was attributed to the synergistic effect among redox-active Co 2+ sites, Lewis acidic Zr 4+ and Co 2+ sites, Br − sites, and basic pyridyl sites. Importantly, the catalyst also demonstrated broad substrate applicability and good recyclability, with negligible activity loss over five consecutive cycles. Furthermore, density functional theory (DFT) calculations elucidated the energy profile and reaction pathway of the styrene oxidative carboxylation reaction, revealing the cooperative roles of multiple active sites in both epoxidation and CO 2 cycloaddition reactions. Therefore, this work proposes a strategy based on the synergy of multiple active sites for developing efficient and recyclable heterogeneous MOF catalysts for CO 2 conversion.

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CHEMICAL ENGINEERING JOURNAL · 2026 · IF 12.5

Selective purification of polymer-grade succinic acid from fermentation broths using a designed type III porous liquids [diOTMG]Cl@Zr-bptc

Jiahui Li,Fulin Li,Yunzheng Li,Yuqing Wan,Xingran Xu,Xiang Zou

[diOTMG]Cl@Zr-bptc porous liquid (PL) was successfully prepared. • PL enhanced succinic acid yield 8.71-fold compared to organic amine. • 99.98% pure succinic acid was obtained by PL extraction and crystallization. • Carboxylic acids are separated via affinity and molecular size differences. Global environmental deterioration and plastic pollution drive the demand for biodegradable polymers, which rely on ultrapure monomer, such as succinic acid (SA). However, current bio-SA purification suffers from low purity (94–98%) and complex multistep processes due to similar affinity of homologues. Here, we introduce a type III porous liquid (PL) composed of ionic liquid [diOTMG]Cl and metal-organic framework Zr-bptc for SA purification, achieving 99.98 ± 0.01 wt% SA purity with 84.15% yield after crystallization. This represents an 8.71-fold yield increase in yield and 6.55-fold improvement in selectivity over tri-n-octylamine. Laboratory-scale assessment confirms the PL solution as a sustainable process. Mechanistically, carboxylic acids are extracted synergistically through hydrogen bonding/anion exchange, while Grand Canonical Monte Carlo (GCMC) simulations showed selective adsorption of acetic acid in Zr-bptc pores. Weak interactions and kinetic size sieving ensure high SA purity. This PL provides an efficient solution for producing polymer-grade monomers, addressing the long-standing challenge in fermented homologue separation. Download: Download high-res image (122KB) Download: Download full-size image

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APPLIED SURFACE SCIENCE · 2026 · IF 6.6

Experimental study and reaction mechanism of anti-poisoning of high KCl content in NH3-SCR over Zr(HPO4)2-based catalyst

Jiahao Wei,Gonggang Sun,Zheng Hong,Qi Wang,Xinbao Li

Catalysts for NH 3 selective catalytic reduction (NH 3 -SCR) suffer from severe alkali metal poisoning, particularly by potassium (K). In this study, a series of K-resistant zirconium phosphate supported CeO 2 -SnO 2 catalysts (CeSn/ZrPs) were prepared by a hydrothermal-impregnation method and the simulated poisoning process with K loading amounts ranging from 1 wt% to 10 wt% was achieved by impregnating the catalysts with a KCl solution. The catalyst that contained 20 wt% Ce and 1 wt% Sn exhibited excellent SCR activity and K-poisoning resistance. The NO conversion over the CeSn/ZrP catalyst achieved 91.6% at 350 °C after 5 wt% K poisoning, and even retained 80.2% when the K content was increased to 8 wt%. The resistance mechanism of CeSn/ZrP against K-poisoning was studied by a series of characterizations. The results demonstrate that CeSn/ZrP exhibits a high surface area, strong acidity and enhanced redox properties due to Sn doping. The abundant Brønsted acid sites provided by the zirconium phosphate support played a crucial role in resisting K poisoning. In-situ DRIFTS revealed that KCl poisoning primarily suppresses the SCR reaction by occupying acid sites and reducing NH3 adsorption. The abundant acid sites of CeSn/ZrP can ensure that the catalyst retains a certain NH 3 adsorption capacity under high KCl loading.

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ADVANCED FUNCTIONAL MATERIALS · 2026 · IF 19.9

Interfacial O-Cl Exchange via Transition Metal Oxide Fillers Boosts Performance and Cost-Efficiency in Zr-Based Chloride Li-Ion Conductors

Yuxin Gong,Mengyu Fu,Yingmin Jin,Yumeng Li,Ruifan Lin,Yong Zhang,Lei Lei,Ying Zhang,Changsong Dai,Yueping Xiong

Halide solid-state electrolytes (HSSEs), exemplified by low-cost Li 2 ZrCl 6 , exhibit high ionic conductivity and a wide electrochemical stability window, making them promising for all-solid-state batteries (ASSBs). Yet, optimizing HSSEs by elemental doping is either inefficient or costly, necessitating alternative approaches. Inspired by the filler-modified LiI-Al 2 O 3 system with fast-conductive interfacial percolation layer (IPL) and with regard to the underlying insufficient interfacial filler/electrolyte contact with Li 2 ZrCl 6 matrix, which hinders the IPL formation, the use of transition metal oxide Fe 2 O 3 is pioneered as a filler to generate oxygen vacancies and foster benign filler/electrolyte interfaces. At the Fe 2 O 3 /electrolyte interface, synchrotron X-ray adsorption spectra and electron energy loss spectra mapping reveal a distinctive O-Cl exchange reaction and improved interfacial contact. Density function theory, bond-valence site energy calculations, and finite-element simulations validate improved Li + migration via mitigated electrostatic confinement, reduced migration energy barriers, and spatially confined electric-field-accelerated IPLs. Benefiting from these merits, the ionic conductivity of the composite electrolyte surges from 0.4 to 2.15 mS cm −1 , with Li + migration activation energy reduced to 0.28 eV. Paired with the NCM811 cathode, the ASSB delivers 90% capacity retention over 1000 cycles at 0.5 C. This work offers a novel, cost-effective strategy for high-performance halide-oxide composite electrolytes from the counterintuitive perspective of nanofiller integration.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2026 · IF 9.1

Electrospinning-hydrothermal synergistic synthesis of Zr/Al-MOF@PAN/PEI nanofiber membrane: toward efficient emulsion separation and simultaneous heavy metal removal

Yujia Zhang,Wanwan Peng,Tianmi Zhang,Daqing Wu,Yufei Suo,Chengyi Wang,Chunfang Huang,Yi He

Treating oily wastewater containing heavy metal ions is a major challenge for traditional membranes, mainly due to limited fouling resistance and versatility. Based on this, this paper develops a hydrophilic zirconium/aluminum bimetallic organic framework functionalized superhydrophilic nanocomposite fiber membrane (Zr/Al-MOF@PAN/PEI) for simultaneous separation of oil-water emulsion and heavy metal removal. This membrane has excellent hydrophilicity and underwater oleophobicity, with a WCA of 3.5° and UOCA of 150°. Surprisingly, this composite membrane also demonstrated excellent separation performance for various oil-in-water emulsions, with a penetration flux of up to 4990 L·m −2 ·h −1 , separation efficiency exceeding 99.99%, and stable separation performance maintained even after 20 separation cycle tests. Moreover, this composite membrane achieves outstanding heavy metal adsorption capacity, especially for Pb (II) adsorption at 210.86 mg g −1 , with a removal efficiency exceeding 99. 8%. Moreover, this composite membrane exhibits stable structural characteristics and excellent anti-fouling performance in a wide pH (3−11) range and high salinity environment, while also featuring high osmotic flux, excellent heavy metal adsorption capacity, and good recycling and regeneration performance, effectively solving the challenges of managing complex oily composite polluted wastewater. This work provides a simple method for manufacturing multifunctional membranes, offering a novel technical approach for efficient remediation of complex heavy metal-rich oily wastewater.

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CHEMICAL ENGINEERING JOURNAL · 2026 · IF 12.5

Trade-off between microwave absorption and mechanical properties of Core-Shell Zr-Si-C/O fibrous aerogels via phase transformation effect

Jinfeng Jiang,Wei Xia,Yu Feng,Weihua Gu,Weiwei Wang,Cao Wu,Wenbo Du,Yong Yang,Hailiang Deng,Yusuke Yamauchi

Ceramic fibrous aerogels are promising lightweight thermal insulators, yet concurrently enhancing mechanical robustness, acoustic attenuation and electromagnetic (EM) wave absorption remains challenging because these functions demand conflicting architectures. Here we introduce a phase-transition-driven multiphase evolution strategy in Si Zr crystals combined with a one-step thermally induced core–shell conversion. This approach enables coordinated regulation of the chemical states, dislocation density and oxygen-vacancy concentration in Zr Si ceramic fibers, and forms a heterogeneous “oxide shell (ZrO 2 /SiO 2 )-carbide core (SiC/ZrC)” within each fiber. The resulting interfacial enrichment and improved impedance matching synergistically strengthen the aerogel and boost EM dissipation. The obtained ZSCO fibrous aerogels deliver a compressive stress up to 255.73 kPa, a minimum reflection loss of −21.87 dB and an average sound absorption coefficient of 0.61. Mechanistic analysis reveals a thermally driven, multimodal regulation pathway for tailoring multifunctional ceramic fibers, offering a scalable route to aerogels for extreme environments.

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Journal of Materials Chemistry A · 2026 · IF 9.5

Multi Capture Site Design in a Bifunctional Zr-MOF for Broad Spectrum and Efficient Removal of Short and Long Chain PFAS

Qiang Bi,Shiping Zhao,Yumiao Zhang,Cai Zhang,Kechun Wang,Jingfeng Tian,Yi Zhao,Juanqin Xue

The escalating threat of per and polyfluoroalkyl (PFAS) substances to human health and the ecological environment has intensified the need for advanced porous adsorbents. Herein, we report a series of mono and bifunctionalized MOF 808 materials grafted with fluoroalkyl and amino groups, systematically evaluating the contribution of the trifluoromethylalanine (TFMA) moiety toward broad spectrum PFAS uptake. Batch adsorption experiments reveal exceptional capacities of MOF 808 TFMA for perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA), reaching 1558.3 and 605.4 mg g-1, respectively, with equilibration achieved within 30 minutes. Over 85% removal efficiency was maintained even at trace concentrations, alongside strong anti interference capability. The material retained 81% of its initial efficiency after five regeneration cycles using methanol–ammonia. Combined experimental characterization and density functional theory (DFT) calculations elucidate a multi synergistic site mechanism: amino enabled hydrogen bonding and electrostatic interactions dominate short chain PFAS capture, while fluorophilic and hydrophobic interactions enhance long chain PFAS adsorption. Notably, we identify for the first time an “adsorption trough” for perfluorohexanoic acid (PFHxA), attributed to a pore size–molecular dimension critical matching effect (ΔS° < 0), providing a theoretical early warning for avoiding synergistic failure in adsorbent design. The bifunctional MOF 808 TFMA demonstrates outstanding PFAS removal performance in real wastewater, offering a foundational strategy for the rational design of next generation PFAS adsorbents.

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