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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Deep eutectic system based C3N4-Zr composite material for highly efficient removal of fluoride in hydrochloric acid

Qin Wang,Xue Bai,Shiyu Sun,Yan Li,Mingzhe Tan,Yanfeng Wang,Na Wang,Ting Wang,Lina Zhou,Zijian Zhou,Xin Huang,Hongxun Hao

The fluorine chemical industry's rapid growth demands efficient strategies for treating and utilizing the costly and inefficient byproduct, fluoride-containing hydrochloric acid, posing a significant challenge. In this study, a cost-effective method was developed for preparing an acid-resistant and efficient defluorination material. Carbon nitride (C 3 N 4 ) was chosen for its exceptional acid resistance and was modified via template-free doping with different zirconium source. Characterization results through XRD, FTIR, BET, XPS, SEM, and TEM confirm the successful synthesis of CN-Zr using zirconium chloride (ZrCl 4 ) with a specific surface area of 87.77 m 2 /g. Furthermore, the adsorption results indicate outstanding fluoride adsorption performance of CN-Zr in hydrochloric acid, with a maximum adsorption capacity of 145.34 mg/g and minimal zirconium leaching. Moreover, the adsorption mechanism was systematically studied using Zeta potential, FTIR and XPS characterization. The findings indicate that Zr was integrated with C 3 N 4 uniformly by forming a deep eutectic system (DES), utilizing exposed terminal amino groups for effective hydrogen bonding with HF which predominates as the primary fluorine existence in hydrochloric acid. Meanwhile, the enhanced ion exchange, complexation of Zr-F and strong electrostatic attraction all contribute to improving adsorption. Finally, the assessment of recyclability performance and operation cost demonstrate that the material can maintain 80% of its initial adsorption capacity after five cycles. The cost analysis results indicate that the adsorption cost is only 0.3157 CNY/g, making it considerable competitive in the industry.

CAS / MDL: 57-13-6 10026-11-6
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JOURNAL OF ENVIRONMENTAL MANAGEMENT · 2024 · IF 8

Heterogeneous activation of self-generated H2O2 by Pd@UiO-66(Zr) for trimethoprim degradation: Efficiency and mechanism

Yijun Chen,Meina Cheng,Long Jin,Hailiang Yang,Sanjian Ma,Zixia Lin,Guoliang Dai,Xin Liu

The Fenton reaction is recognized as an effective technique for degrading persistent organic pollutants , such as the emerging pollutant trimethoprim (TMP). Recently, due to the excellent reducibility of active hydrogen ([H]), Pd–H 2 has been preferred for Fenton-like reactions and the specific H 2 activation of Pd-based catalysts. Herein, a heterogeneous Fenton catalyst named the hydrogen-accelerated oxygen reduction Fenton (MHORF@UiO-66(Zr)) system was prepared through the strategy of building ships in the bottle. The [H] has been used for the acceleration of the reduction of Fe(III) and self-generate H 2 O 2 . The systematic characterization demonstrated that the nano Pd 0 particle was highly dispersed into the UiO-66(Zr). The results found that 20 mg L −1 of TMP was thoroughly degraded within 90 min in the MHORF@UiO-66(Zr) system under conditions of initial pH 3, 30 mL min −1 H 2 , 2 g L −1 Pd@UiO-66(Zr) and 25 μM Fe 2+ . The hydroxyl radical as well as the singlet oxygen were evidenced to be the main reactive oxygen species by scavenging experiments and electron spin resonance . In addition, both reducing Fe(III) and self-generating H 2 O 2 could be achieved due to the strong metal-support interaction (SMSI) between the nano Pd 0 particles and UiO-66(Zr) confirmed by the correlation results of XPS and calculation of density functional theory. Finally, the working mechanism of the MHORF@UiO-66(Zr) system and the possible degradation pathway of the TMP have been proposed. The novel system exhibited excellent reusability and stability after six cyclic reaction processes.

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NEW JOURNAL OF CHEMISTRY · 2024 ·Vol. 48 ·期 42 ·18166-18176 · IF 2.7

Functionalization of Zr@FMA with phosphonic acid groups for efficient separation of Th(IV) from aqueous solutions

Jing Xiao,Linshan Peng,Ailan Ouyang,Xin Mo,Yiping Yao,Chunyan Wang,Chunpei Yan

A phosphonate-functionalized Zr@FMA material was prepared in this work as an adsorbent for the efficient recovery and enrichment of Th(IV) from aqueous solutions. The adsorbent, prepared by functionalizing Zr@FMA with alendronate sodium (ALS), a well-known active bisphosphonate, demonstrates good water stability and a large surface area, making it suitable for the separation and enrichment of Th(IV) in aqueous solutions. A comparison of the adsorption behavior of Th(IV) on Zr@FMA-ALS with the unfunctionalized Zr@FMA reveals that the introduction of phosphonate groups significantly enhances the maximum adsorption capacity and rate of Zr@FMA-ALS. The adsorption data aligns well with the Langmuir isotherm model, suggesting a uniform distribution of Th(IV) on the adsorbent surface in a monolayer coverage. Thermodynamic analysis indicates an endothermic and spontaneous adsorption process. Zr@FMA-ALS also shows excellent selectivity for Th(IV) over other metal ions in mixed solutions. Insights into the adsorption mechanism are provided through SEM, XPS, and FT-IR analyses, indicating that ALS molecules play a crucial role in capturing Th(IV) on the surface of Zr@FMA-ALS.

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Journal of Water Process Engineering · 2024 · IF 6.3

Hydrogen-promoted oxygen reduction Fenton reaction system constructed by Pd/UiO-66(Zr) to efficiently degradate trimethoprim

Yijun Chen,Hailiang Yang,Sanjian Ma,Meina Cheng,Zixia Lin,Long Jin,Xin Liu

As a representative antibiotic, trimethoprim (TMP), the emerging pollutant has been frequently detected in water bodies, and its potential harm has aroused the attention of society. Although the emerging pollutant could be efficiently degraded by the advanced oxidation process (AOP) represented by the Fenton reaction , both the problem of iron sludge disposal and the safe use of H 2 O 2 have plagued the further promotion of this technology. The H 2 (precursor of the active hydrogen [H]) and catalyst Pd/UiO-66(Zr) were introduced into the Fenton reaction in this paper. It was found that the process of reducing Fe(III) and self-generating H 2 O 2 could be facilitated due to the reduction of [H]. Under certain reaction conditions (initial pH 3, trace total iron 25 μM, H 2 30 mL·min −1 , catalyst 2 g·L −1 ) and without H 2 O 2 , a Fenton-like system was constructed, named MHORF-UiO-66(Zr). While achieving zero iron sludge discharge, 100 % of 20 mg·L −1 TMP was rapidly degraded within 1 h. It was found that the degradation of TMP could be attributed to the attack of singlet oxygen and hydroxyl radical . Furthermore, the performance changes of catalyst before and after six rounds of reactions were studied and it was found that Pd/UiO-66(Zr) had excellent and stable catalytic performance.

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JOURNAL OF HAZARDOUS MATERIALS · 2024 · IF 12.2

Nitrogen-rich and core-sheath polyamide/polyethyleneimine@Zr-MOF for iodine adsorption and nerve agent simulant degradation

Yu-Xuan Zheng,Xuwen Wu,Wei-Guang Yang,Bai-Xue Li,Kejing Gao,Jingsheng Zhou,Yunfang Liu,Dongzhi Yang

Radioactive nuclides and highly toxic organophosphates are typical deadly threats. Materials with the function of radioactive substances adsorption and organophosphates degradation provide double protection. Herein, dual-functional polyamide (PA)/polyethyleneimine (PEI)@Zr-MOF fiber composite membranes, fabricated by in-situ solvothermal growth of Zr-MOF on PA/PEI electrospun fiber membranes, are designed for protection against two typical model compounds of iodine and dimethyl 4-nitrophenyl phosphate (DMNP). Benefiting from the unique core-sheath structure composed of inner nitrogen-rich fibers and outer porous Zr-MOF, the composite membranes rapidly enrich iodine through abundant active sites of the outer sheath and form complexes with the amine of inner PEI, exhibiting a highly competitive adsorption capacity of 609 mg g −1 . Moreover, it can adsorb and degrade DMNP with the synergy of PEI component and Zr-MOF, achieving an 80 % removal of DMNP within 7 min without any additional co-catalyst. This work provides a feasible strategy to fabricate dual-functional materials that protect against radioactive and organophosphorus contaminants.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2024 · IF 5.8

NiO/ZrO2 hollow microspheres derived from bimetallic Ni/Zr-MOFs for fast and sensitive detection of triethylamine

Wangchang Geng,Pengfei Song,Xinrou Cao,Libing Duan

Metal oxides derived from metal-organic frameworks (MOFs) can maintain the porosity and unique structure of MOFs, giving them significant development potential in the field of gas sensing. In this study, bimetallic Ni/Zr-MOFs solid microspheres were synthesized via the solvothermal method, and NiO/ZrO 2 composites with p-p heterostructure were further prepared through an annealing process. The morphology, structure, specific surface area, and pore size of NiO/ZrO 2 composites were analyzed using a series of characterization techniques. The gas sensing performance study showed that the NiO/ZrO 2 -2 sensor exhibited higher response (32.3–100 ppm), lower detection limit (7.2 ppb), shorter response/recovery time (55 s/83 s), and excellent repeatability to triethylamine gas at the operating temperature of 240 ℃. Additionally, within a specific range (1–200 ppm), a strong linear relationship was observed between the response value and the gas concentration for the NiO/ZrO 2 -2 sensor (R 2 =0.9588). This study is expected to provide a valuable reference for designing high-performance triethylamine sensors.

CAS / MDL: 554-95-0
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OPTICAL MATERIALS · 2018 · IF 2.32

Simultaneous multi-wavelength ultraviolet excited single-phase white light emitting phosphor Ba1-x(Zr,Ti)Si3O9:xEu

Zhenzhen Zhou,Guanghui Liu,Jia Ni,Wanlu Liu,Qian Liu

A kind of novel compound Ba 1-x (Zr,Ti)Si 3 O 9 :xEu simultaneously activated by different-valence Eu 2+ and Eu 3+ ions has been successfully synthesized. The existence of Ti 4+ -O 2- charge transfer (CT) transitions in Ba 1-x ZrSi 3 O 9 :xEu is proved by the photoluminescence spectra and first principle calculations, and the Ti 4+ ions come from the impurities in commercial ZrO 2 raw materials. Under the excitation of multi-wavelength ultraviolet radiation (λ EX  = 392, 260, 180 nm), Ba 1-x ZrSi 3 O 9 :xEu (x = 0.15) can directly emit nearly white light. The coexistence of multiple luminescent centers and the energy transfer among Zr 4+ -O 2- CT state, Ti 4+ -O 2- CT state, Eu 2+ and Eu 3+ ions play important roles in the white light emission. Ba 1-x ZrSi 3 O 9 :xEu (x = 0.15) has good thermal stability, in particular, the intensity of emission spectrum (λ EX  = 392 nm) at 150 °C is ∼96% of that at room temperature. In general, the multi-wavelength ultraviolet-excited single-phase white light emitting phosphor Ba 1-x (Zr,Ti)Si 3 O 9 :xEu possesses a promise for applications in white light emitting diodes (WLEDs), agriculture, medicine and other photonic fields.

CAS / MDL: 1314-23-4
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COLLOID AND POLYMER SCIENCE · 2025 · IF 2.3

Biocompatible Zr-based nanoscale MOFs coated with hyaluronic acid as promising drug delivery system for sports injuries

Zhang Fei,Xie Mingzhu,Zhao Jing

With the rapid development of nanotechnology, nanocarriers play an important role in achieving precise drug delivery and controlled release. Among them, nanoscale metal organic frameworks (NMOFs) have shown great potential due to ultra-high specific surface area, controllable size, tunable structure and open metal sites. The aim of this study is to enhance the multifunctionality of UiO-66-NH 2 NMOFs, such as physiological stability, biocompatibility, pH responsiveness, and targeting, by post-synthetic modification with hyaluronic acid-dopamine (HA-DA) functional material. The structure, size, and morphology were characterized by IR, XRD, DLS, and SEM, and the stability, drug-loading capacity, controlled release, and biocompatibility under different conditions were evaluated. The results showed that the particle size distribution and surface properties were improved after modification. This modification not only enhanced the stability in physiological environment, but also accelerated drug release in the acidic environment and improved drug bioavailability, which was of great significance for targeting acidic microenvironments. Cytotoxicity experiments further showed that the introduction of HA-DA effectively reduced the cytotoxicity and provided more suitable environment for cell growth. This study can achieve responsive release, alleviate inflammatory response, and promote tissue repair, especially for sports injuries, which provides a new approach for developing efficient and safe drug delivery systems. Graphical abstract Based on the structural properties of NMOF, a UiO-66-NH 2 NMOF drug delivery system was constructed by the post-synthetic modification of hyaluronic acid-dopamine (HA-DA). This kind of drug delivery system exhibits excellent stability and biocompatibility, and achieves responsive release, which may alleviate inflammatory response and promote tissue repair. This study provides a new approach for developing efficient and safe drug delivery systems.

CAS / MDL: 25952-53-8 6066-82-6
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JOURNAL OF ALLOYS AND COMPOUNDS · 2024 · IF 5.8

Al/Zr synergetic modification tailored low-cobalt single crystal LiNi0.72Co0.05Mn0.23O2 cathode for high-performance lithium-ion battery

Hua Yan,Yu-hong Luo,Ying Lei,Qing-lin Pan,Jun-chao Zheng

N ickle (Ni)-rich layered oxides as promising candidate of high-capacity cathode materials have aroused extensive concern primarily regarding their higher specific capacity. However, the major hurdle of Ni-rich cathodes (Ni content ≥0.7) is their poor cycling stability, which often suffers from the release of oxygen, structural degradation and increased impedance during cycling, especially at high voltage or high temperature. Herein, we demonstrated a feasible solid phase method for easy industrialization based on the Al 3+ /Zr 4+ co-doping in LiNi 0.72 Co 0.05 Mn 0.23 O 2 (A X Z Y -NCM) single-crystal cathode. The optimized A 0.5 Z 0.5 -NCM single-crystal material exhibited greatly enhanced structural and thermal stability. XRD refinement results indicated that both Al 3+ and Zr 4+ were mainly located in transition metal (TM) sites, strengthening the layered structure through strong M-O bonds and inhibiting cation mixing. In-situ XRD revealed that the synergistic rivet effect of Al/Zr co-doping alleviates anisotropic lattice stress-strain during charge/discharge process. Accordingly, the A 0.5 Z 0.5 -NCM cathode can output a high initial capacity of 177.3 mAh g −1 at 1 C, and captured a more desirable capacity retention of 85.10 % than that of U-NCM (74.33 %) at 1 C over 200 cycles. Even at a high voltage of 4.5 V, its capacity retention can still reach 82.37 %, significantly surpassing the unmodified U-NCM (31.0 %). The above results demonstrated that well-designed dual doping is highly effective for strengthen structure stability and cycling performance of Ni-rich cathodes.

CAS / MDL: 1310-66-3 1314-23-4
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GREEN CHEMISTRY · 2017 ·Vol. 19 ·期 20 ·4829-4837 · IF 9.125

Direct use of humic acid mixtures to construct efficient Zr-containing catalysts for Meerwein–Ponndorf–Verley reactions

Yufei Sha,Zhenhuan Xiao,Huacong Zhou,Keli Yang,Yinmin Song,Na Li,Runxia He,Keduan Zhi,Quansheng Liu

With the increasing demands for energy and carbon resources, exploration of novel utilization approaches of fossil resources and promotion of the conversion of sustainable resources become critical issues facing human society. In this study, we used humic acids (HAs), which are important derivatives from the low-rank coal, and the transition metal zirconium (Zr) to construct novel Zr-containing catalysts (Zr-HAs) for Meerwein–Ponndorf–Verley (MPV) reactions of biomass-derived platforms. Both commercial HAs and HAs extracted directly from lignite without any purification were used as raw materials to prepare the catalysts. The results showed that Zr-HAs catalysts were highly efficient for the conversion of furfural, with a high furfuryl alcohol yield of up to 97%, and also effective for the conversion of other carbonyl compounds with different structures under mild conditions. This novel strategy to construct catalysts using HAs as raw materials may be beneficial for both value-added utilization of low-rank coal and the conversion of biomass resources.

CAS / MDL: 1415-93-6
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Journal of the Australian Ceramic Society · 2024 · IF 1.8

Preparation and property characterization of Zr-modified Si-O-C-based precursor ceramics through three-dimensional printing

Lin Jia,Wang Shuai,Yang Yihang,Huang Guimei,Wang Jinhuo

In this study, Zr-modified Si-O-C precursor ceramics were prepared using three-dimensional (3D) printing. Ceramic sintering was completed by printing four precursors containing different zirconium acetylacetone contents. Comparative analysis was conducted on the ceramic yield, size shrinkage, mechanical properties, and microstructure. The results showed that the ceramic yield and size shrinkage of the four samples were increased with the increasing zirconium acetylacetone contents. The sample containing 30 wt% zirconium acetylacetone exhibited good compressive performance, with a compressive strength of 50.2 ± 0.6 MPa. Cracks were observed on the surface of samples containing 40 wt% zirconium acetylacetone, while those containing 10, 20, and 30 wt% zirconium acetylacetone were relatively intact. Therefore, a stable Si-Zr-O-C precursor ceramic with good mechanical properties, which can be used for 3D printing, was obtained.

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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Self-healing and antistatic waterborne polyurethane hybrid coating resulting from hard but reversible Zr-O-Si networks

Kai Han,Chen Zhou,Jianlong Wang,Nana Zhao,Jinfeng Yuan,Zhicheng Pan,Mingwang Pan

Robust, self-healing waterborne coatings have become the preferred choice in the field of flexible electronic devices owing to their outstanding compliance, restorability, and environmental friendliness. Nevertheless, most of the existing self-healing waterborne polymers exhibit viscoelasticity, irreversible fatigue damage, and the challenge of reconciling self-healing functions with mechanical properties, all stemming from inherent molecular structure contradictions between flexibility and rigidity. Here, we propose a novel strategy that utilizes a nanofiller with dynamic reversible bonds to overcome the self-healing limitations that theoretically demand flexible chain, for achieving both mechanical robustness and self-healing ability in the waterborne polyurethane (WPU) hybrid coating system. We modified tetrapropyl zirconate (TPOZ) with 3-aminopropyltriethoxysilane (APTES) to enhance compatibility between the matrix and inorganic particles, while the formation of dynamic reversible bonds through both condensation hydrolysis endows the self-healing abilities. The WPU hybrid coating was designed by covalently incorporating amino-modified TPOZ (A-ZrO 2 ) into a glycinamide-functionalized WPU network, conferring excellent fracture energy (50.3 kJ/m 2 ), elastic recovery, along with antistatic capability to the coating. Furthermore, the hybrid coating maintains a robust mechanical performance alongside 92.58 % of healing efficiency, exhibiting a potential for flexible electronics application. The hybridization strategy via incorporation of the nanofillers with hard but reversible covalent bond resolves the inherent robustness-healing trade-off, providing exciting thoughts to expand WPU applications.

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