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Nano Energy · 2025 · IF 17.1

Modulating Cu-O-Zr interfaces on high-roughness MgO surface for reinforced hydrogen production from sorption-enhanced steam reforming of methanol

Zhao Sun,Huicai Wang,Xingxu Wang,Riguang Zhang,Zhiqiang Sun

Sorption-enhanced steam reforming of methanol (SE-SRM) offers a promising route for high-quality hydrogen production with in situ CO 2 capture; however, achieving an optimal balance between catalytic activity and CO 2 uptake capability, while ensuring catalyst stability, remains a significant challenge. In this study, a series of Zr-doped (0 wt%, 5 wt%, 15 wt%, 25 wt%) Cu-MgO catalytic sorbents are synthesized for SE-SRM. At 180℃, the hydrogen concentration and yield reach nearly 100 % and 10.35 μmol·g −1 ·s −1 . Moreover, the catalytic sorbent basically retains its catalytic activity and CO 2 uptake capacity after 30 cycles with merely slight deactivation. Results demonstrate that the doped Zr, presents as tetragonal ZrO 2 , enhances metal-support interactions with the formation of a Cu-O-Zr interfacial structure, promoting Cu nanocluster dispersion and altering the Cu + /Cu 0 distributions. Zr doping also enables the modulation of the medium-strong basic sites. Moreover, the AFM and TEM confirmed the formation of high-roughness MgO surface on the substrate, thereby facilitating CO 2 diffusion and adsorption. DFT calculation results further confirm the advantages of Zr-doped Cu-MgO catalytic sorbents due to its stronger capability on CH 3 OH activation and CO 2 adsorption.

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LANGMUIR · 2022 · IF 4.331

Environmentally Friendly Zr-Based MOF for Pesticide Delivery: Ultrahigh Loading Capacity, pH-Responsive Release, Improved Leaf Affinity, and Enhanced Antipest Activity

Saijie Song,Minghui Wan,Wenli Feng,Yu Tian,Xuefeng Jiang,Yi Luo,Jian Shen

The stimuli responsive pesticide delivery system (PDS) has drawn increasing attention in recent years, a system which can effectively improve the utilization of pesticides. In the current research, we report a pH responsive PDS by using carboxymethyl cellulose (CMC) modified Zr-based metal organic frameworks (UiO-66-NH2) as the nanocarrier for acetamiprid (ATP). UiO-66-NH2-CMC possesses a large surface area and abundant pores, which can effectively load ATP, and the loading rate is as high as 90.79%. Compared with free ATP, the ATP@UiO-66-NH2-CMC nanopesticide exhibits pH responsive controlled release behavior, and the pesticide can sustained release to the medium. In addition, it also shows improved leaf affinity, which makes it easier to wet the leaf surface and improve the utilization of pesticide. Therefore, ATP@UiO-66-NH2-CMC displays better antipest activity against aphids than free ATP does. Meanwhile, ATP@UiO-66-NH2-CMC shows no negative effects on the germination and growth of maize, showing good biosafety. Moreover, the ATP@UiO-66-NH2-CMC nanopesticide does not contain any toxic organic solvents or additives. Therefore, we hope that it can be a suitable candidate for plant protection and sustainable agriculture.

✓ 已验证 DOI PubMed 高影响因子
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2021 · IF 3.171

Enhancing the activity of MoS2/SiO2-Al2O3 bifunctional catalysts for suspended-bed hydrocracking of heavy oils by doping with Zr atoms

Yongde Ma,Rengan Liang,Wenquan Wu,Jiayin Zhang,Yanning Cao,Kuan Huang,Lilong Jiang

Developing catalysts with not only hydrogenation activity but also cracking activity is very important for the advancement of suspended-bed hydrocracking technology. Within this respect, MoS 2 /SiO 2 -Al 2 O 3 bifunctional catalyst is a kind of typical catalysts with both hydrogenation and cracking activity. Herein, a series of Zr-doped SiO 2 -Al 2 O 3 mixed oxides were synthesized by a sol-gel coupled with hydrothermal method. The synthesized mixed oxides were characterized for chemical structures and acidic properties. It is found that doping SiO 2 -Al 2 O 3 with Zr atoms significantly increases the numbers of acidic sites. The Zr-doped SiO 2 -Al 2 O 3 mixed oxides were then combined with dispersed MoS 2 , which was in-situ produced from oil-soluble Mo precursors, to fabricate a novel kind of bifunctional catalysts for suspended-bed hydrocracking of heavy oils. Owing to the significantly increased numbers of acidic sites in Zr-doped SiO 2 -Al 2 O 3 mixed oxides, corresponding bifunctional catalysts demonstrate much enhanced activity for suspended-bed hydrocracking of heavy oils in relative to MoS 2 /SiO 2 -Al 2 O 3 bifunctional catalysts.

✓ 已验证 DOI 高影响因子
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Materials Today Communications · 2023 · IF 3.8

Effects of oxygen vacancies on electric properties of high valence ions Mo/Zr/Ti doped Bi0.85Nd0.15FeO3 ceramics with morphotropic phase boundary

Jingxin Tian,Hongjun Zhang,Liwei Zhang,Dongliang Wang,Yong Huang,Elena Balashova,Boris Krichevtsov,Hua Ke

The effects of oxygen vacancies on electric properties of high valence ions (Mo/Zr/Ti) doped Bi 0.85 Nd 0.15 FeO 3 (marked as BNFM, BNFZ, BNFT) ceramics with morphotropic phase boundary (MPB) are investigated. MPB structures consisting of rhombohedral, intermediate and orthorhombic phases exist in all samples, which is confirmed by the XRD Rietveld refinements and TEM analyses. The BNFT has the maximum remnant polarization of 34.5 μC/cm 2 at 180 kV/cm, owing to its lowest paraelectric orthorhombic phase content. XPS and impedance results reveal that the BNFT ceramic has the relatively low oxygen vacancy contents and the largest impedance value, which is beneficial for the ferroelectric test. The best comprehensive properties of BNFT open wide prospects for improving BiFeO 3 -based ceramics.

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Green Processing and Synthesis · 2022 ·Vol. 11 ·期 1 ·184-194 · IF 3.97

Fabrication of silicotungstic acid immobilized on Ce-based MOF and embedded in Zr-based MOF matrix for green fatty acid esterification

Qiuyun Zhang,Binbin Yang,Yuanyuan Tian,Xianju Yang,Rongfei Yu,Jialu Wang,Taoli Deng,Yutao Zhang

In the present study, a facile solvothermal method was used for the synthesis of silicotungstic acid (HSiW) immobilized on Ce-based metal organic framework (Ce-BDC) and embedded in Zr-based metal-organic framework (UiO-66(Zr)) composite catalyst, namely, Ce-BDC@HSiW@UiO-66 for the production of biodiesel through green fatty acid esterification. The obtained hybrids were characterized by various characterization technologies, including Fourier transform infrared, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N 2 physisorption, X-ray photoelectron spectroscopy, and temperature-programmed desorption of NH 3 (NH 3 -TPD) analysis. The characterization analyses showed that the hybrids have been successfully synthesized. Also, the volume and pore size of UiO-66(Zr) were changed by introducing HSiW@Ce-BDC, and the resulting Ce-BDC@HSiW@UiO-66 possessed the mesoporous structure and relatively high surface area. Simultaneously, the NH 3 -TPD analysis of Ce-BDC@HSiW@UiO-66 reveals that the acid strength was increased in comparison with HSiW@Ce-BDC. In addition, the composite Ce-BDC@HSiW@UiO-66 demonstrated high catalytic activity, and the oleic acid esterification gave 81.5% conversion at optimum conditions of 0.2 g catalysts, 1:30 oleic acid to methanol molar ratio at 130°C for 4 h. More interestingly, after six recycling cycles, the reduction in the conversion rate was only 4.6%, indicating that Ce-BDC@HSiW@UiO-66 has excellent reusability. Our study provides an effective approach to synthesize multifunctional hybrids for green biofuel production.

✓ 已验证 DOI 高影响因子
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KOREAN JOURNAL OF CHEMICAL ENGINEERING · 2017 ·Vol. 34 ·期 12 ·3132-3141 · IF 2.007

Deep desulfurization of model oil by photocatalytic air oxidation and adsorption using Ti(1−x)M x O2 (M=Zr, Ce)

Zhang Wei,Li Xin,Wang Hong,Song Yongji,Zhang Shenghong,Li Cuiqing

Deep desulfurization of model oil by photocatalytic air oxidation and adsorption using Ti (1− x ) M x O 2 (M=Zr, Ce) was investigated. Ti (1− x ) M x O 2 (M=Zr, Ce) was prepared by urea gelation/co-precipitation method, and characterized by N 2 adsorption, XRD and UV-vis spectra. UV irradiation greatly enhanced the adsorptive capacity and selectivity of TiO 2 -ZrO 2 for organosulfur in model oil because organosulfur compounds were first photocatalytically oxidized to sulfoxides and sulfones over TiO 2 -ZrO 2 , which were then selectively adsorbed on the bifunctional material due to much higher polarities of generated sulfoxides and sulfones. The Ti/Zr molar ratio and calcination temperature were optimized to 5 : 5 and 500 °C with the sulfur removal of 99.6% after reaction for 2 h under UV irradiation. After adding 25 wt% toluene into model oil, the sulfur removal could still reach 97.2% after reaction for 7 h. TiO 2 -ZrO 2 could be well regenrated by washing with acetonitrile followed by thermal treatment in air.

✓ 已验证 DOI 高影响因子
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FUEL PROCESSING TECHNOLOGY · 2019 · IF 4.507

Comparative study on dry reforming of methane over Co-M (M = Ce, Fe, Zr) catalysts supported on N-doped activated carbon

Yinghui Sun,Guojie Zhang,Ying Xu,Yongfa Zhang,Yongkang Lv,Riguang Zhang

A series of Co-M (M = Ce, Fe, Zr) binary oxides supported on N-doped catalysts were prepared by impregnation methods and tested for DRM reaction. Moreover, the influence of Co and Ce atomic contents in the catalysts on DRM performance was investigated. Significant enhancement of activity performance over Ce promoted 3Co-1Ce/AC-N catalyst was observed. Compared with Fe and Zr, the catalyst with 1/4 mol% of Ce showed the highest activity and was higher than the supported Co catalyst . The calcined and spent catalysts were characterized by XPS , H 2 -TPR, TEM and EDX mapping studies. The characterization results demonstrated that the increase of 3Co-1Ce/AC-N reforming reactivity was attributed to the presence of Ce in Co-based catalyst, which modified the chemical states of Co-Ce composite oxide and redox properties, and increased the presence of Co 2+ species, the content of chemisorbed oxygen and the oxygen mobility. Among the different Co/Ce ratio catalysts, the one with a Co/Ce molar ratio at 1 exhibited better catalytic performance. As the Ce content increases, the content of chemisorbed oxygen was further decreased. In addition, the introduction of N on the support could also affect the catalyst reduction property and interaction of Co-Ce bimetal, which would improve catalytic performance.

✓ 已验证 DOI 高影响因子
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ANALYTICAL CHEMISTRY · 2020 · IF 6.785

Specific Coordination between Zr-MOF and Phosphate-Terminated DNA Coupled with Strand Displacement for the Construction of Reusable and Ultrasensitive Aptasensor

Weiwei Qiu,Feng Gao,Natsumi Yano,Yusuke Kataoka,Makoto Handa,Weiqiang Yang,Hidekazu Tanaka,Qingxiang Wang

Electrochemical aptasensors involved in chemical labeling are often single-use and sensitivity-limited because the probes are commonly single-point labeled and irreversible. In this work, the specific coordination between Zr4+ and phosphate group (−PO43–) was employed to construct a new aptasensor that is highly sensitive and reusable, using Ochratoxin A (OTA) as the test model. The OTA binding aptamer (OBA) was hybridized with the thiolated supporting sequence (TSS) immobilized on the surface of a gold electrode. The UiO-66 with a formula of [Zr6O4(OH)4(BDC)6], one of the class of Zr metal–organic frameworks (MOFs), was then particularly grafted on the terminal of OBA through the specific coordination between Zr4+ and 5′-PO43–, i.e., the Zr–O–P coordination bond. Similarly, as much as the 5′-PO43– and 3′-methylene blue dual-labeled sequences (DLS) were further assembled on UiO-66 due to the large surface area of MOF and rich active sites of Zr4+. Owing to the specific coordination for signal amplification, the developed aptasensor shows greatly enhanced sensitivity. A wide detection range from 0.1 fM to 2.0 μM and an ultralow detection limit of 0.079 fM (S/N = 3) for OTA were obtained. Additionally, the TSS can rehybridize with a new OBA to regenerate the aptasensor but without complicated pretreatments, enabling a aptasensor that is readily reusable for OTA detection. The aptasensor was successfully applied for OTA detection in the red wine samples, demonstrating a promising prospect for food safety monitoring.

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Materials · 2021 ·Vol. 14 ·期 21 ·6666 · IF 3.623

Improved Non-Piezoelectric Electric Properties Based on La Modulated Ferroelectric-Ergodic Relaxor Transition in (Bi0.5Na0.5)TiO3-Ba(Ti, Zr)O3 Ceramics

Xingru Zhang,Yinan Xiao,Beining Du,Yueming Li,Yuandong Wu,Liyuan Sheng,Wenchang Tan

The characteristic transition from ferroelectric (FE) to ergodic relaxor (ER) state in (Bi0.5Na0.5)TiO3(BNT) based lead-free ceramics provides an efficient approach to bring a highly ordered phase back to a disordered one. It would be rational to utilize this transition to improve relevant non-piezoelectric properties based on domain decomposition. In this work, different La contents were introduced to 0.93(Bi0.5Na0.5)TiO3-0.07Ba(Ti0.945Zr0.055)O3ceramics (BNT-BZT-xLa) to induce evolution of ergodic degree. The results reveal that with increasing La content, both the FE-ER transition temperatureTF-Rand depolarization temperatureTdshift towards room temperature, implying a deepened ergodic degree. By modulation of ergodic degree, thermally stimulated depolarization current experiment shows a higher current density peak, and corresponding pyroelectric coefficient increases from 2.46 to 2.81 μC/(cm2∙°C) atTd. For refrigeration, the indirect measurement demonstrates the ΔTmaximum increases from 1.1 K to 1.4 K, indicating an enhanced electrocaloric effect. Moreover, the optimized energy storage effect is observed after La doping. With appearance of “slimmer”P-Eloops, both calculated recoverable energy storage densityWrecand storage efficiencyηincrease to 0.23 J/cm3and 22.8%, respectively. These results denote La doping conduces to the improvement of non-piezoelectric properties of BNT-based ceramics in a certain range. Therefore, La doping should be an adopted modification strategy for lead-free ceramics used in areas like refrigerator and pulse capacitors.Keywords:BNT-based lead-free ceramics;electric properties;ferroelectric to ergodic relaxor state transition;La doping

✓ 已验证 DOI PubMed 高影响因子
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2021 ·Vol. 32 ·期 3 ·2685-2695 · IF 2.478

Microstructure, magnetic, and dielectric properties of Co–Zr co-doped hexagonal barium ferrites based on the sintering temperature and doping concentration

Zhang Hongbo,Fan Lining,Cao Hechun,Yu Yishi,Zhang Tianchi,Feng Qianqian,Zheng Hui,Wu Qiong,Zhang Yang

In this work, M-type hexagonal barium ferrites co-doped with Co and Zr atoms were prepared by a solid-phase method based on the sintering temperature and doping concentration. First, the influences of the sintering temperature on the crystal structure, microstructure, and magnetic properties of ferrites were studied. The crystallinity of the materials increases with the sintering temperature and obtaining high density and uniform grain size at 1300 °C, which promotes grain-boundary diffusion and suppresses grain-boundary migration. Second, the dependence of the crystal structure, microstructure, magnetic, and dielectric properties of Ba(Co x Zr x )Fe 12−2 x O 19 on the doping concentration ( x  = 0, 0.2, 0.4, 0.6) was investigated at sintering temperature of 1300 °C. The increase of the crystal parameter c with x value reveals that the ions of Co 2+ and Zr 4+ successfully replace the Fe 3+ ions. Additionally, the co-doping ions of Co 2+ –Zr 4+ promote the grain-boundary migration and result in some large size grain (> 20 mm) that appeared and increased with the doping concentration. The magnetic hysteresis loops reveal the saturation magnetization increases from 60.45 to 68.6 emu/g, and the coercivity decreases from 1800 to 190 Oe with the x increased to 0.6. The dielectric properties measurement displays the Co–Zr co-doping can improve the dielectric and reduce the dielectric loss. The highest value of the real part of permittivity ( ε ′) and the lowest value of the imaginary part of permittivity ( ε ″) can be obtained at a doping concentration of x  = 0.4.

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JOURNAL OF THE EUROPEAN CERAMIC SOCIETY · 2015 · IF 2.947

A novel facile way to synthesize proton-conducting Ba(Ce,Zr,Y)O3 solid solution with improved sinterability and electrical performance

Xiaowei Chi,Zhaoyin Wen,Jingchao Zhang,Yu Liu

A novel hybrid route, combining simple co-precipitation and conventional solid state reaction, is proposed for the first time to synthesize BaCe 0.4 Zr 0.4 Y 0.2 O 3− δ powders at a temperature as low as 1150   °C. This temperature is much lower than that used for conventional solid state reaction method and even comparable to that used in sol–gel route. The reasons for the low calcination temperature are analyzed in detail from the macroscopic to microscopic viewpoints. Moreover, with the powders made by the novel method, dense ceramic could be easily obtained. Further, impedance data illustrated that its electrical conductivity in wet H 2 at 750   °C is up to 1.39   ×   10 −2   S/cm, which is the highest among all the samples prepared by the three different methods and much higher than the reported results related to BCZY proton conductors . Also, the new method is particularly suitable for other multi-component oxides .

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Catalysis Science & Technology · 2025 · IF 4.2

Aldol condensation of acetaldehyde over Zr-β zeolites with tailored Lewis acidity and passivated Brønsted sites: toward environmentally benign crotonaldehyde synthesis

Haoxi Jiang,Qian Ran,Yingying Zhao,Guochao Yang,Lingtao Wang

In response to the challenges of equipment corrosion and environmental pollution associated with the homogeneous catalytic production of crotonaldehyde via acetaldehyde aldol condensation, this work focused on the synthesis of Zr-β zeolites with Lewis acidity. The crotonaldehyde selectivity was significantly improved by tailoring the acidic properties of the zeolites. A comparative study of three distinct Lewis acid sites identified isolated framework tetra-coordinated Zr sites as the most efficient catalytic centers, which were successfully constructed using hydrothermal synthesis and liquid-phase incorporation methods. Zr-β zeolites synthesized via liquid-phase incorporation demonstrated higher conversion and selectivity owing to larger pore size, greater total Lewis acidity and a higher proportion of weak and medium Lewis acid sites. These properties were further optimized by adjusting the precursor and solvent during the synthesis process. In situ DRIFTS analysis revealed that the Lewis acid sites activated the α-H of acetaldehyde, forming carbanion intermediates essential for the enolization and subsequent aldol condensation. The main by-product, methyl cyclopentenone, was found to originate from the Prins reaction of sorbaldehyde formed through excessive aldol condensation, which was mediated by Brønsted acid sites. To suppress this side reaction, the zeolites were modified with alkali cations (Na+, K+) to selectively passivate the Brønsted acid sites while enhancing the Lewis acidity significantly. This strategy effectively reduced by-product formation and ultimately achieved a crotonaldehyde selectivity of 94.7%.

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