Advanced Science
·
2025
·
IF 14.1
Siqi Qiu,Hao Wan,Yuechao Yao,Xiao Xu,Zhangjian Li,Yongbiao Mu,Biaolin Peng,Hongliang Wu,Jizhao Zou,Lin Zeng
Iron-nitrogen-carbon (Fe-N-C) materials are promising non-precious metal catalysts for the oxygen reduction reaction (ORR), yet their long-term stability remains a critical challenge due to the dissolution of Fe-based active sites and corrosion of the carbon support. Here, a Fe-Zr dual-atom carbon-based catalyst (Fe,Zr-NC) via a one-step solid-state synthesis method is reported. The introduction of atomically dispersed Zr–N units adjacent to Fe–N 4 centers creates a dual-metal coordination structure that modulates the local electronic environment of Fe and weakens * OH adsorption, which is the rate-limiting step in the ORR process. Density functional theory (DFT) calculations reveal that the Fe–Zr synergy positions the catalyst near the apex of the ORR activity volcano. Extended experimental EXAFS confirms a Fe–Zr distance of ≈3.30 Å, closely matching the theoretical optimum (≈3.39 Å). As a result, Fe, Zr-NC achieves a high half-wave potential (0.891 V vs reversible hydrogen electrode (RHE)) with negligible activity loss over 5000 cyclic voltammetry cycles, outperforming commercial Pt/C. In zinc–air batteries, the catalyst delivers a peak power density of 185.7 mW cm −2 and operates stably for over 453 h. This work highlights the importance of dual-atom synergy in tuning intermediate binding energies and provides design principles for next-generation ORR electrocatalysts.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Siyuan Qiao,Pei Nian,Guisen Yang,Yingfei He,Xingrui Li,Yibin Wei
Vapor-phase deposition for the preparation of metal–organic framework (MOF) membranes is of great interest in its scalable and sustainable manufacturing. Nevertheless, there remains no report on vapor-assisted conversion (VAC) for preparation of zirconium-based MOF membranes to date. Here, we established a VAC protocol for preparing UiO-66 membranes on the porous α-Al 2 O 3 tube. It was found that the substrate surface modification, metal-to-ligand ratio and concentration of the modulator are crucial parameters to control the quality of the resulting membrane microstructure. The obtained UiO-66 membrane exhibited excellent dye rejection rates (>99.5 %) and reliable operation stability (no reduction in separation performance during 96 h). In addition, the VAC approach also can be adopted to synthesis of high-performance UiO-66-NH 2 and MOF-801 membranes. Therefore, the VAC protocol might open new horizons in sustainable production of water-stable MOF membranes for practical applications.
✓ 已验证
产品关联
DOI
高影响因子
Nanomaterials
·
2025
·Vol. 15
·期 11
·826
·
IF 4.3
Zan Cheng,Mei Yu,Yilong Wan,Huandong Xiang,Haoran Wei,Xu Zu,Xin Li,Ruiting Zhang,Fangshu Li,Shanshan Wang,Yongxin She
Metal–organic frameworks (MOFs) have great potential for drug delivery systems due to their tunnel pore size, structural versatility, and high surface area. Among them, UiO-67 have recently attracted substantial attention as functional nanocarriers for effective delivery of small molecule chemical drugs. However, the influence of the size on cellular uptake of UiO-67 remains ambiguous. Here, we use polyvinyl pyrrolidone (PVP) as the capping agent of UiO-67 to synthesize spherical Zr-based MOFs with various diameters, including 40 nm, 60 nm, and 120 nm. The highest cellular uptake is observed in the case of Zr-based MOFs with a diameter of 40 nm (PU 40 MOFs). Moreover, doxorubicin can be loaded into the inner pores of PU 40 MOF via π-π and electrostatic interactions (DPU 40 MOFs), with a loading capacity of 82 wt%, and gradually released under acidic conditions. In vitro, the resulting DPU 40 MOFs can be internalized by cancer cells more effectively, thereby enhancing the delivery of doxorubicin into cancer cells. Ultimately, this results in enhanced antitumor efficacy toward 4T1, Hs 578T, and MCF-7 cells. Our findings indicate that approximately 40 nm may be the optimum diameter for the special Zr-based MOFs to be internalized by cells more effectively, providing potent potential nanocarriers for drug delivery.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Yu Liu,Fengru Song,Xiaoshen Huang,Tingting Wu,Mingxing Tang,Hongyu Wang,Mengya Guo,Genkuo Nie
Taking into account that the selective ring-opening of the furan ring limits the efficiency of direct conversion of furfural to 1,5-pentanediol, a Zr-doped CuCo-based catalyst was developed to regulate the multistep reaction of furfural to 1,5-pentanediol in one pot and boost the overall step yield. Through the efficient synergistic action of multiple active sites, 56% yield of 1,5-pentanediol from furfural in one pot was obtained by Cu4.5Co3.5Zr1, surpassing other nonprecious metal catalysts. The improvement in the catalytic effect of this catalyst is attributed to doping CuCo-based species with Zr. The introduced Zr species not only provide medium-strength base sites but also promote the high dispersion of Cu atoms; both factors promote the conversion of furfural to furfuryl alcohol. Besides, Zr species promote the reduction of Cu/Co oxygen species, enriching oxygen vacancies, and combined with Co2+/Co3+ create an optimal Brønsted/Lewis acid ratio in Cu4.5Co3.5Zr1. Metals adjacent to oxygen vacancies adsorb oxygen species of compounds, and basic sites adsorb the H1-hydroxyl group of furfuryl alcohol. With the synergistic effect of Brønsted acid, the C2–O2 bonds of the furan ring are selectively polarized to enhance the selectivity toward 1,5-pentanediol. Additionally, dynamical reactions using furfural and furfuryl alcohol independently as feedstocks were conducted to investigate the reaction mechanism. The catalyst maintained stable performance over five runs with minimal deactivation. This work provides a method for improving the yield of 1,5-pentanediol from furfural over multiple nonprecious metal catalysts by enriching oxygen vacancies and combining suitable acid–base properties.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2022
·
IF 6.371
Xiyuan Tao,Li Yang,Jiali Liu,Zihao Zang,Peng Zeng,Changfei Zou,Lingguang Yi,Xiaoyi Chen,Xiaolin Liu,Xianyou Wang
Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) is a promising solid-state electrolyte (SSE) for next generation lithium batteries due to its high Li + conductivity and stability against lithium metal, especially the Li 7−3x Ga x La 3 Zr 2 O 12 (Ga-LLZO) is most valuable because of its high ionic conductivity (> 1 ×10 −3 S cm −1 ). However, it is difficult to prepare high-quality Ga-LLZO by the traditional air ambient sintering. Herein, we develop a simple and efficient rapid ultra-high-temperature sintering (RUHTS) method to prepare high-conductivity Ga-LLZO ceramic SSE. It has been found that the as-prepared Ga-LLZO ceramic SSE with the composition of Li 6.25 Ga 0.25 La 3 Zr 2 O 12 exhibits high relative density of 99%, good ionic conductivity of 1.48 × 10 −3 S cm −1 and large critical current density of 0.5 mA cm −2 after sintering at 1200 °C for 2 min. In addition, the Ga-LLZO SSE shows good electrochemical stability and interfacial compatibility against Li metal. The assembled Li-Li symmetric cell represents a small interfacial impedance of 37 Ω cm 2 . In the same time, the Li/Ga-LLZO/LE+LMNCO full battery has a total impedance of 205 Ω cm 2 , and can deliver a first discharge capacity of 235.1 mAh g −1 at 0.5 C, and the capacity retention rate is 88.3% after 100 cycles. This indicates that the as-prepared Ga-LLZO has good application prospect in the Li-metal solid-state batteries (LMSSBs). Moreover, this method does not require the use of mother powder during preparation process, which will effectively reduce the waste of raw materials, save manufacture costs and be beneficial to quantity production of Ga-LLZO ceramic electrolyte.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
TALANTA
·
2025
·
IF 6.1
Muhammad Hussnain Afzal,Wajeeha Pervaiz,You Xu,Nomair Elahi,Zhuo Huang,Guangfang Li,Hongfang Liu
The widespread use of acetaminophen (AP) has resulted in its frequent presence in pharmaceutical waste, posing ecological and health risks. To address this, a voltametric sensor based on a bimetallic UiO-66-NH 2 metal-organic framework incorporating Zirconium (Zr) and Cerium (Ce) was developed for sensitive AP detection. The incorporation of Ce 3+ not only introduced redox active sites but also reduced the particle size from 495-650 nm in (Zr)UiO-66-NH 2 to 230–365 nm in (Zr/Ce)UiO-66-NH 2 , increasing surface area and enhancing electrocatalytic activity. The combined synergistic effect of Zr and Ce significantly improved charge transfer and enhanced oxidation current response compared to the unmodified GCE. The sensor exhibited excellent electrocatalytic performance with a wide linear range (0.072–680 μM), high sensitivity (0.496 μAμM −1 cm −2 ), and a low limit of detection (0.024 μM). In addition, the sensor exhibited excellent selectivity against interfering species and maintained stable performance over 21 days. The sensor's practical applicability was validated by testing real environmental samples, achieving recovery rates of 97–103 %, and the results were consistent with those obtained using high-performance liquid chromatography (HPLC).
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Wentao Qu,Zhikun Wang,Jiaqi Feng,Xupeng Li,Liqiang Yang,Li Wang,Jie Guo,Huiling Su,Miantuo Li,Yu Fu,Songqing Hu
This work presents a dual-adsorbent strategy for enhanced phosphate removal via chitosan-based materials with molecular-level mechanistic elucidation. Two complementary adsorbents are designed: spherical bimetallic beads (CSQ@Zr/Fe) and a porous hydrogel (CSQ@Zr). The CSQ@Zr/Fe beads demonstrate outstanding cyclic stability, retaining 84.2 % adsorption capacity after 5 regeneration cycles, while achieving a maximum adsorption capacity of 122.51 mg/g under optimized conditions. The CSQ@Zr hydrogel exhibits superior single-cycle performance with a capacity of 126.50 mg/g and rapid uptake kinetics, reaching adsorption equilibrium within 240 min. Both materials maintain high removal efficiency over a broad pH range (3–9) and show remarkable selectivity in complex ionic environments, with phosphate removal exceeding 90 % even in the presence of competing anions (Cl − , NO 3 − , SO 4 2− ). Comprehensive characterization and simulation studies reveal a synergistic adsorption mechanism dominated by electrostatic interactions (85–92 % contribution to binding energy), complemented by outer-sphere coordination (P–O–Zr: 2.25 Å; P–O–Fe: 1.85 Å) and hydrogen bonding networks. The hydrogel exhibits stronger phosphate confinement (diffusion coefficient: 0.544 × 10 −12 m 2 /s) compared to the beads (0.685 × 10 −12 m 2 /s), which correlates with its enhanced adsorption performance. This work provides not only high-performance adsorbents but also fundamental insights into the design of chitosan-based materials for sustainable phosphate removal and recovery applications.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Materials Today Chemistry
·
2026
·
IF 7.4
Jin Chen,Naoyuki Hatada,Wenhao Li,Wenzhuo Chen,Donglin Han
Heavily acceptor-doped perovskite oxides have the potential to activate percolation conduction of protons at reduced temperatures, and the reported percolation proton conductors up to now are restricted to the systems containing high Sc content. However, larger trivalent rare earth elements (e.g., Y) are known to be better dopants for proton conducting zirconates, but their solubility is low. In this work, we propose a new strategy to design the percolation proton conducting perovskites, by introducing La and Y into the Sr and Zr-sites of SrZrO 3 , respectively, leading to the formation of (Sr 1.1- x La x -0.1 )(Zr 1- x Y x )O 2.95 (SLZY, x = 0.1 – 1.0), which takes Pnma and Pna 2 1 orthorhombic structures with x = 0.1 – 0.4 and 0.5 – 1.0, respectively. Interestingly, the conductivity decreases with the Y content increasing from 0.1 to around 0.7 and increases with the Y content further increasing to 1.0. Moreover, the activation energy of the bulk conduction shows the maximum value at x = 0.6. In addition to the expected monotonically increasing activation energy resulted from the enhanced structural asymmetry, these results imply that the trapping effect of protons plays an important role, which is enhanced with Y content increasing from 0.1 to around 0.6. Notably, higher Y content (e.g., x > 0.6) appears to activate the percolation conduction of protons, leading to the decreasing activation energy.
✓ 已验证
产品关联
DOI
高影响因子
TALANTA
·
2026
·
IF 6.1
Chu Zeng,Hong-Tao Jiang,Ming Xu,Zhi-Yuan Gu
Flexible metal–organic frameworks (MOFs) with dynamic adaptability offered exciting opportunities for advanced separation, yet their tendency to undergo void collapse severely limited their application as gas chromatography (GC) stationary phases. Here, we overcame this challenge by stabilizing the scu -topology Zr-MOF NU-903 through a linker installation strategy. By incorporating biphenyl-4,4′-dicarboxylic acid (BPDC) into the vacant coordination pockets along the c-axis, the resulting material, NU-903-BPDC, exhibited markedly enhanced stability and structural rigidity, retaining its porosity even at 250 °C. Comprehensive characterization confirmed that the original structure was preserved, while framework flexibility was effectively suppressed. Fluorescence spectroscopy further revealed restricted ligand dynamics, corroborating the rigidified framework environment. When employed as a GC stationary phase, NU-903-BPDC delivered significantly improved resolution for C 7 hydrocarbons and dichlorobenzene isomers, benefitting from stronger thermodynamic interactions and reduced band broadening. Crucially, NU-903-BPDC maintained stable separation performance after thermal treatment, in sharp contrast to the pronounced degradation observed for pristine NU-903. This work demonstrated linker installation as an effective strategy to modulate framework flexibility, opening a general pathway toward robust, high-performance MOF-based stationary phases for chromatographic separations.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2021
·
IF 5.455
Yang Hu,Hai-Liang Yang,San-Jian Ma,Juan-Hong Li,Xin Liu,Yong-Jing Tian,Long Jin,Zi-Xia Lin
The promotion of Fenton process in organic wastewater treatment has been hindered by the disposal of large amounts of iron sludge derived from the excess addition of ferrous salt. The operation of the Fenton reaction could be maintained using trace level Fe II through the effective acceleration reaction of active hydrogen. However, the H 2 which is the precursor of active hydrogen is insoluble in water. Herein, the composite catalyst Pd/MOF-808(Zr) was introduced into the H 2 -Fenton system to enhance the adsorption and activation of this reducing gas. In this novel improved Fenton system called MHACF-MOF-808(Zr), the hydroxyl radical would be unceasingly produced based on the unceasingly recycling of FeII/FeIII at normal temperature and pressure. 15 mg L −1 sulfamethazine could be thoroughly degraded during 2 h reaction process in the initial condition of 60 mL min −1 H 2 , 20 μmol L −1 Fe II , pH 3, 20 mmol L −1 H 2 O 2 and 2 g L −1 Pd/MOF-808(Zr). And so did 10 mg L −1 2,4-Dichlorophenol. The activity and stability of Pd/MOF-808(Zr) could be maintained after at least 6 consecutive reaction cycles. It provides new insight for improving the inherent shortcoming of the Fenton reaction which will generate large amounts of iron sludge.
研究领域:
环境科学
·
化学工程
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2016
·
IF 4.803
Zheng-Yao Li,Rui Gao,Limei Sun,Zhongbo Hu,Xiangfeng Liu
In this work, Zr 4+ doped P2-Na 0.75 Mn 0.55 Ni 0.25 Co 0.05 Fe 0.10 Zr 0.05 O 2 has been synthesized and investigated as high-rate sodium-ion battery cathode material for the first time. XRD results indicate that Zr-ion with a big size cannot completely dissolve into the crystal structure, but the residual ZrO 2 shows little impact on the electrochemical performance in comparison with the post-added ZrO 2 . With the substitution of Zr 4+ for Fe 3+ , the lattice parameter a decreases but c increases, resulting in the reduced lattice volume. In comparison with the Zr-free sample, Na 0.75 Mn 0.55 Ni 0.25 Co 0.05 Fe 0.10 Zr 0.05 O 2 (Zr05) can deliver a discharge capacity of about 95, 74, 61 and 53 mAh g −1 at 2C, 5C, 8C and 10C. At the current density of 2C, the capacity retention after 100 cycles has increased from 57% of Zr0 to 74% of Zr05. The results demonstrate that Zr-ion substitution can effectively improve the rate performance and cycling stability of P2-structure cathode materials. The role of Zr 4+ can be summarized as follows: (1) Zr-O ( △H f 298K (Zr-O) = 760 kJ mol −1 ) has a stronger bond energy than that of Fe O ( △H f 298K (Fe-O) = 409 kJ mol −1 ), which enhances the structure stability and cycling performance; (2) the aliovalent substitution of Zr 4+ for Fe 3+ enhances the electronic conductivity, which is favorable for the rate capability; (3) the substitution of Zr 4+ for Fe 3+ can be beneficial to Na + conduction because it increases disorder in the transition metal (TM) layers and can prevent Na+/vacancy ordering, which further enhances the rate capability.
研究领域:
材料科学
·
电化学
·
能源存储
·
无机化学
·
固态化学
✓ 已验证
DOI
高影响因子
RARE METALS
·
2017
·Vol. 36
·期 12
·934-941
·
IF 1.189
Yong Yao-Wei,Fu Wei,Deng Qi-Lin,Yang Jian-Guo
By adding mixture of ZrO 2 and carbon, a Zr-enhanced composite coating was produced onto an AISI 1045 substrate by laser cladding. The microstructure and phase formation, microhardness and wear resistance of the composite coating were studied. The experimental results indicate that the composite coating with metallurgical bonding to substrate consists of γ-Ni, massive ceramic particles of ZrC, NiZr 2 , Ni 7 Zr 2 , (Fe, Ni) 23 C 6 and Fe 3 C. The in situ-synthesized ZrC particles are uniformly dispersed in composite coating, which refines the microstructure of composite coating. With different ZrO 2 and carbon additions, the properties are improved differently. Finally, the fine in situ ZrC particles improve the microhardness of composite coating to HV 0.2 650, which is nearly 2.7 times that of Ni25 coating. Also, the composite coating has an advantage in wear resistance; it offers better wear resistance when more mixture of ZrO 2 and carbon was added in nickel alloys.
研究领域:
材料科学
·
金属学与热处理
·
表面工程
·
先进制造
·
复合材料
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）