Journal of Rare Earths最新文献_第8页

Exploring influence of light rare-earth elements and zirconium co-substitution on physical and photocatalytic behavior of BiFeO3 探讨轻稀土元素与锆共取代对BiFeO3物理和光催化行为的影响

IF 7.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-04-28 DOI: 10.1016/j.jre.2025.04.019

Zahra Adineh, Ahmad Gholizadeh, Sakineh Hosseini

Rare earth metals and transition metals co-substitution have been shown to tailor the physical properties of BiFeO₃. In this work, a series of Bi_1–xRE_xFe_1–xZr_xO₃ (RE = La, Pr, Nd, Sm; x = 0.00, 0.03, 0.06) multiferroic ferrites was synthesized using the sol–gel method. To gain comprehensive insights into these materials, we employed a range of characterization techniques, including X-ray diffraction, Raman and Fourier transform infrared spectroscopies, field emission scanning electron microscopy, UV–Vis spectroscopy, and a vibrating sample magnetometer. Our analysis reveals a rhombohedral crystal structure (R3c space group) for the synthesized ferrites. Notably, we observe a substantial decrease in the optical band gap as the RE/Zr co-substitution increases. Further investigation into the magnetic properties shows a remarkable transition from antiferromagnetic to ferromagnetic behavior, which we attribute to the disruption of the long-range periodicity of the spin cycloid and 4f-3d orbital interactions. In addition, we tested the photocatalytic performance of the RE/Zr co-substituted BiFeO₃ nanoparticles for the degradation of methyl orange dye under sunlight. The results are quite impressive, with degradation efficiency reaching up to 100% at 40 min by the Bi_1–xRE_xFe_1–xZr_xO₃ (RE = La, Sm). Overall, our study demonstrates the vast potential of Bi_1–xRE_xFe_1–xZr_xO₃ ferrites in various fields, including optics, magnetism, water treatment, and environmental preservation.

稀土金属和过渡金属共取代可以改变BiFeO3的物理性质。本文采用溶胶-凝胶法制备了Bi1-xRExFe1-xZrxO3 （RE = La, Pr, Nd, Sm; x = 0.00, 0.03, 0.06）多铁氧体。为了全面了解这些材料，我们采用了一系列表征技术，包括x射线衍射、拉曼和傅立叶变换红外光谱、场发射扫描电子显微镜、紫外可见光谱和振动样品磁力仪。我们的分析表明，合成的铁氧体具有菱形晶体结构（R3c空间群）。值得注意的是，我们观察到随着RE/Zr共取代的增加，光学带隙显著减小。对磁性的进一步研究表明，从反铁磁性到铁磁性的显著转变，我们将其归因于自旋摆线和4f-3d轨道相互作用的远程周期性的破坏。此外，我们还测试了稀土/锆共取代BiFeO3纳米粒子在阳光下降解甲基橙染料的光催化性能。结果令人印象深刻，Bi1-xRExFe1-xZrxO3 （RE = La, Sm）在40分钟内降解效率达到100%。总的来说，我们的研究证明了Bi1-xRExFe1-xZrxO3铁氧体在光学、磁性、水处理和环境保护等各个领域的巨大潜力。

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引用次数: 0

Effect of rare earth doping on structural, optical, dielectric, and humidity properties of Cu–Mg–Zn ferrites 稀土掺杂对Cu-Mg-Zn铁氧体结构、光学、介电和湿度性能的影响

IF 7.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-04-16 DOI: 10.1016/j.jre.2025.04.006

Tuğba Şaşmaz Kuru , Mehmet Kuru

Rare earth (RE) doped ferrites with the chemical formula Cu_0.3Zn_0.3Mg_0.4T_xFe_2–xO₄ (x = 0, 0.1; T = La, Ce, Sr) were synthesized by chemical co-precipitation method. The structural, optical, electrical and humidity sensing properties of Cu–Mg–Zn ferrites with rare earth element doping were investigated. Single-phase cubic spinel structure was confirmed via X-ray diffraction (XRD), and the crystal size ranges from 22.12 to 63.17 nm according to the Scherrer formula and from 25.66 to 67.46 nm according to the Williamson–Hall method. Porous structure and elemental characterization of the samples were investigated by scanning electron microscopy (SEM). The optic band gap varies between 2.21 and 2.49 eV. Electrical measurements were conducted in the frequency range of 1 Hz–20 MHz and temperature range of 25–400 °C. It has been determined that the dielectric results are consistent with the Maxwell–Wagner method and exhibit a non-Debye relaxation model, as observed from the Nyquist plots. At a minimum frequency value of 1 Hz, the dielectric constants for pure, Ce, Sr, and La samples are 9 × 10⁴, 5 × 10⁴, 1 × 10⁸, and 2 × 10⁵ at 25 °C, and 1.85 × 10⁸, 1.34 × 10⁸, 1.15 × 10¹⁰, and 4.4 × 10⁸ at 400 °C. In the same order, for the maximum frequency value of 20 MHz, the dielectric constants at 25 °C are 169, 166, 3799, and 60, while at 400 °C they are 734, 624, 12108, and 774. The La doped sample's low dielectric loss makes it suitable for high-frequency applications. Humidity measurements were performed at room temperature and in the 5%–95% relative humidity range. The humidity properties of the samples were investigated through humidity mapping, sensitivity, hysteresis, and long-term stability tests. Compared to other samples, the results indicate that Ce exhibits better humidity performance with 99% sensitivity and the highest repeatability (91.2%). These results show that Ce-doped ferrite can be used as a low-cost, high-performance humidity sensor.

采用化学共沉淀法合成了化学式为Cu0.3Zn0.3Mg0.4TxFe2-xO4 （x = 0,0.1; T = La, Ce, Sr）的稀土掺杂铁氧体。研究了稀土元素掺杂Cu-Mg-Zn铁氧体的结构、光学、电学和湿度传感性能。通过x射线衍射（XRD）证实了该晶体的单相立方尖晶石结构，根据Scherrer公式，晶粒尺寸在22.12 ~ 63.17 nm之间，根据Williamson-Hall方法，晶粒尺寸在25.66 ~ 67.46 nm之间。利用扫描电镜（SEM）研究了样品的孔隙结构和元素表征。光学带隙在2.21 ~ 2.49 eV之间变化。电测量的频率范围为1 Hz-20 MHz，温度范围为25-400°C。从奈奎斯特图中可以看出，介电结果与麦克斯韦-瓦格纳方法一致，并表现出非德拜松弛模型。在最小频率为1 Hz时，纯样品、Ce、Sr和La样品在25℃时的介电常数分别为9 × 104、5 × 104、1 × 108和2 × 105，在400℃时的介电常数分别为1.85 × 108、1.34 × 108、1.15 × 1010和4.4 × 108。在最高频率为20 MHz时，25℃时介电常数依次为169、166、3799和60,400℃时介电常数依次为734、624、12108和774。La掺杂样品的低介电损耗使其适合于高频应用。湿度测量在室温和5%-95%的相对湿度范围内进行。通过湿度测绘、灵敏度、迟滞和长期稳定性试验研究了样品的湿度特性。结果表明，与其他样品相比，Ce具有较好的湿度性能，灵敏度为99%，重复性最高（91.2%）。这些结果表明，掺铈铁氧体可以作为一种低成本、高性能的湿度传感器。

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引用次数: 0

La-doped CeO2 nanoflowers catalysts for direct synthesis of dimethyl carbonate from CO2 and methanol la掺杂CeO2纳米花催化剂用于CO2和甲醇直接合成碳酸二甲酯

IF 7.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-03-26 DOI: 10.1016/j.jre.2025.03.026

Lihua Hu , Suning Zhang , Peishen Zhao , Jie Yang , Gongde Wu , Wei Xu

The catalytic direct synthesis of dimethyl carbonate (DMC) from CO₂ and methanol is a crucial approach to utilizing CO₂ and producing high-value chemicals. However, the high stability of the CO₂ molecule imposes thermodynamic limitations on this reaction pathway, along with challenges related to insufficient catalyst activity and stability. Currently, solutions primarily focus on developing efficient catalyst. Herein, La-doped CeO₂ nanoflower catalysts (La_xCeO₂) were synthesized via hydrothermal method. Characterization reveals that La doping optimizes the pore structure and enriched oxygen vacancies, thereby enhancing catalytic performance. Notably, La_0.1CeO₂ exhibits the largest pore size and highest oxygen vacancy content, achieving a remarkable DMC productivity of 9.42 mmol/g under 140 °C, 4 MPa of CO₂, and 3 h of reaction, surpassing pure CeO₂ nanoflowers. Based on experimental findings and in-situ diffuse infrared Fourier transform analysis, a plausible reaction pathway was proposed. This work underscores the potential of La_xCeO₂ nanoflowers as efficient catalysts for sustainable CO₂ conversion to DMC.

二氧化碳和甲醇催化直接合成碳酸二甲酯（DMC）是利用二氧化碳和生产高价值化学品的重要途径。然而，二氧化碳分子的高稳定性给这一反应途径带来了热力学限制，同时也带来了催化剂活性和稳定性不足的挑战。目前，解决方案主要集中在开发高效催化剂上。本文采用水热法合成了la掺杂的CeO2纳米花催化剂（LaxCeO2）。表征表明，La掺杂优化了孔隙结构，富集了氧空位，从而提高了催化性能。值得注意的是，La0.1CeO2具有最大的孔径和最高的氧空位含量，在140°C、4 MPa CO2和3 h的反应条件下，DMC产率达到了9.42 mmol/g，超过了纯CeO2纳米花。根据实验结果和现场漫反射红外傅里叶变换分析，提出了一种合理的反应途径。这项工作强调了LaxCeO2纳米花作为可持续的二氧化碳转化为DMC的有效催化剂的潜力。

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引用次数: 0

Biosorption selectivity of rare earth elements onto Euglena mutabilis suspensions and biofilms and the effect of divalent metal ions 稀土元素在突变藻悬浮液和生物膜上的生物吸附选择性及二价金属离子的影响

IF 7.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-03-19 DOI: 10.1016/j.jre.2025.03.018

Mitchell T.E. Zak, Vladimiros G. Papangelakis, D. Grant Allen

The increasing demand for electronics has led to a desire to recover rare earth elements (REEs) from non-conventional sources, including mining and liquid waste effluents. Biosorption could be a promising method for adsorbing REEs onto microalgae, but biomass immobilization and light delivery challenges remain. It was recently shown that REEs biosorb 160% more on algal biofilms than suspended biomass due to the extracellular polymeric substance (EPS) matrix that grows abundantly in biofilms. In this work, we present findings on biosorption selectivity for different REEs in sulfate solutions. The maximum adsorption capacities of Euglena mutabilis suspensions and biofilms were determined for a mixed REE sulfate solution at an equimolar initial concentration range of 0.1–1 mol/L of each REE ion. The highest adsorption capacities for the suspension are for Sm and Eu which are 57% and 46% higher, respectively, compared to the average REE adsorption capacity. The biofilms also preferentially adsorb Sm, Eu, Yb and Lu at 0.035, 0.033, 0.033, and 0.031 mmol/g, respectively. The impact of dissolved divalent ions of Ca, Mg, and Fe on REE adsorption was also assessed. When Ca and Mg are added in equimolar amounts to 0.1–1 mmol/L solutions of equimolar La, Eu, and Yb sulfate, the amount of REEs adsorbed onto suspensions increases by 30% while when Fe is added, it decreases by 10%. No change is observed in biofilms except when Fe is added resulting in a reduction of the adsorption capacity by 40%. A possible explanation for the role of Fe is attributed to the formation of stronger bonds at the binding sites compared to Ca and Mg.

对电子产品日益增长的需求导致人们希望从非常规来源（包括采矿和液体废水）中回收稀土元素（ree）。生物吸附是一种很有前途的将稀土吸附到微藻上的方法，但生物质固定化和光传递仍然存在挑战。最近的研究表明，由于细胞外聚合物（EPS）基质在生物膜中大量生长，藻类生物膜对稀土的生物吸收率比悬浮物高160%。在这项工作中，我们介绍了硫酸盐溶液中不同稀土元素的生物吸附选择性的研究结果。测定了异绿藻悬浮液和生物膜在初始等摩尔浓度范围为0.1 ~ 1 mol/L的稀土混合硫酸盐溶液中的最大吸附量。该悬浮液对钐和铕的吸附量最高，分别比REE平均吸附量高57%和46%。在0.035、0.033、0.033和0.031 mmol/g浓度下，生物膜对Sm、Eu、Yb和Lu具有较强的吸附能力。还评估了溶解的Ca、Mg和Fe二价离子对REE吸附的影响。当Ca和Mg以等摩尔量加入到0.1-1 mmol/L等摩尔的La、Eu和Yb硫酸盐溶液中时，稀土吸附量增加30%，而加入Fe时，稀土吸附量减少10%。在生物膜中没有观察到任何变化，除非添加铁导致吸附能力降低40%。对铁的作用的一种可能的解释是，与Ca和Mg相比，铁在结合位点形成了更强的键。

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引用次数: 0

Recent advances in lanthanide metal–organic framework-based catalysts for thermocatalysis of volatile organic compounds 挥发性有机化合物热催化镧系金属-有机骨架催化剂的研究进展

IF 7.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-03-16 DOI: 10.1016/j.jre.2025.03.011

Hao Lin , Xiaoying Lin , Jingquan Liu , Lifang Xu , Ronghui Shi , Hui Zhao , Zhen Zhou

Volatile organic compounds (VOCs) are significant indoor and outdoor air pollutants. Thermocatalysis is one of the most common methods for their removal, capable of completely mineralizing VOCs. Nanomaterials derived by pyrolytic means, based on the high specific surface area and high tunability of metal–organic frameworks (MOFs), have received increasing attention in the field of efficient catalysis of VOCs. Lanthanide metal–organic frameworks (Ln-MOFs) have significant research value in thermocatalytic applications for VOCs by virtue of their flexible and rich coordination behaviors, Lewis acidity, excellent oxygen storage and discharge capabilities, unique electronic structure properties of lanthanide coordination metals. Herein, a comprehensive review of the recent advances in Ln-MOF-based catalysts for thermally catalyzed VOCs elaborates on the effects based on the structure, including pyrolysis strategy, metal substitution, surface modification, and composite doping. The review addresses the mechanistic issues of Ln-MOF-based catalysts in the thermocatalysis of VOCs and highlights their characteristic advantages as efficient catalysts for VOCs. Finally, this review also summarizes the key issues and challenges, provides perspectives and outlooks on the development and design of Ln-MOF-based catalysts. It serves as a reference for enhancing the performance and selecting appropriate Ln-MOF-based catalysts for treating VOCs.

挥发性有机化合物（VOCs）是重要的室内外空气污染物。热催化是去除挥发性有机化合物最常用的方法之一，能够完全矿化挥发性有机化合物。基于金属-有机骨架（MOFs）的高比表面积和高可调性，通过热解手段制备的纳米材料在高效催化VOCs领域受到越来越多的关注。镧系金属-有机骨架（mn - mofs）由于其灵活丰富的配位行为、刘易斯酸性、优异的储氧放电能力、镧系配位金属独特的电子结构性质，在VOCs热催化方面具有重要的研究价值。本文综述了近年来基于mn - mof的热催化VOCs催化剂的研究进展，从热解策略、金属取代、表面改性、复合掺杂等方面阐述了基于结构的影响。综述了基于mn - mof的催化剂在VOCs热催化中的机理问题，并强调了其作为高效VOCs催化剂的特点优势。最后，总结了目前研究中存在的关键问题和面临的挑战，并对基于mn - mof的催化剂的开发和设计进行了展望。为提高催化剂的性能和选择合适的mn - mof基催化剂处理VOCs提供参考。

{"title":"Recent advances in lanthanide metal–organic framework-based catalysts for thermocatalysis of volatile organic compounds","authors":"Hao Lin , Xiaoying Lin , Jingquan Liu , Lifang Xu , Ronghui Shi , Hui Zhao , Zhen Zhou","doi":"10.1016/j.jre.2025.03.011","DOIUrl":"10.1016/j.jre.2025.03.011","url":null,"abstract":"<div><div>Volatile organic compounds (VOCs) are significant indoor and outdoor air pollutants. Thermocatalysis is one of the most common methods for their removal, capable of completely mineralizing VOCs. Nanomaterials derived by pyrolytic means, based on the high specific surface area and high tunability of metal–organic frameworks (MOFs), have received increasing attention in the field of efficient catalysis of VOCs. Lanthanide metal–organic frameworks (Ln-MOFs) have significant research value in thermocatalytic applications for VOCs by virtue of their flexible and rich coordination behaviors, Lewis acidity, excellent oxygen storage and discharge capabilities, unique electronic structure properties of lanthanide coordination metals. Herein, a comprehensive review of the recent advances in Ln-MOF-based catalysts for thermally catalyzed VOCs elaborates on the effects based on the structure, including pyrolysis strategy, metal substitution, surface modification, and composite doping. The review addresses the mechanistic issues of Ln-MOF-based catalysts in the thermocatalysis of VOCs and highlights their characteristic advantages as efficient catalysts for VOCs. Finally, this review also summarizes the key issues and challenges, provides perspectives and outlooks on the development and design of Ln-MOF-based catalysts. It serves as a reference for enhancing the performance and selecting appropriate Ln-MOF-based catalysts for treating VOCs.</div></div>","PeriodicalId":16940,"journal":{"name":"Journal of Rare Earths","volume":"43 12","pages":"Pages 2579-2592"},"PeriodicalIF":7.2,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A review of biomass-based adsorption for rare earth elements recovery 生物质吸附法回收稀土元素研究进展

IF 7.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-03-07 DOI: 10.1016/j.jre.2025.03.006

Victor Famobuwa , Deniz Talan , Oishi Sanyal , Shawn Grushecky , Hassan Amini

This review provides a comprehensive summary of biomass-based adsorption, with a particular focus on biochar as an innovative, sustainable, and eco-friendly technique for recovering rare earth elements (REEs) from various sources. This study details primary adsorption mechanisms, including physical adsorption, ion exchange, electrostatic attraction, surface complexation, and precipitation, providing a nuanced understanding of how these processes contribute to metal recovery. Additionally, it discusses various biochar modification methods aimed at enhancing surface functionalities, thereby improving adsorption capacity and selectivity. It further addresses the critical challenge of biochar regeneration, outlining methods such as thermal, solvent, microwave irradiation, and supercritical fluid regeneration to sustain biochar's efficacy over multiple cycles. Overall, this comprehensive analysis highlights biochar's versatility and potential in environmental remediation and resource recovery, emphasizing the importance of optimized regeneration techniques to maintain its adsorption efficiency and future research directions for large-scale applications.

本文综述了基于生物质的吸附技术，重点介绍了生物炭作为一种创新的、可持续的、环保的从各种来源回收稀土元素的技术。这项研究详细介绍了主要的吸附机制，包括物理吸附、离子交换、静电吸引、表面络合和沉淀，为这些过程如何有助于金属回收提供了细致入微的理解。此外，还讨论了各种旨在增强表面功能的生物炭改性方法，从而提高吸附能力和选择性。它进一步解决了生物炭再生的关键挑战，概述了热、溶剂、微波辐照和超临界流体再生等方法，以维持生物炭在多个循环中的功效。综上所述，本综合分析强调了生物炭在环境修复和资源恢复方面的多功能性和潜力，强调了优化再生技术以保持其吸附效率的重要性和未来大规模应用的研究方向。

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引用次数: 0

High capacitive rare-earth co-doped transition metal/graphene oxide composites as effective electrode material for supercapacitors 高电容性稀土共掺杂过渡金属/氧化石墨烯复合材料作为超级电容器的有效电极材料

IF 7.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-03-07 DOI: 10.1016/j.jre.2025.02.018

Tayyaba Raza , Muhammad Arshad , Zahida Batool , Mashkoor Ahmad , Imran Murtaza , Akber Ali , Muhammad Arsalan Raza , Husna Zaheer , Rehana Kousar

In recent times, there has been a surge of attention towards advanced high-performance materials for storing energy, specifically in supercapacitors. One encouraging method involves utilizing nanocomposites based on transition metal oxides/graphene which have demonstrated significant potential for improving capacitance. The electrochemical properties of titanium oxide doped graphene in current research have been improved through the incorporation of rare earth metals. The hydrothermal technique was chosen for the fabrication of nanocomposites as electrode materials. X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM) approaches were employed for the characterization of nanocomposites. Ternary and quaternary nanocomposites with 2 wt% rare earth elements doped with titanium oxide and graphene were synthesized with various ratios of lanthanum and cerium as dopants. In 2 wt% La:Ce-TiO₂/rGO, lanthanum, and cerium were doped in 1:1, 1:3, and 1:5 ratios. 2 wt% La:Ce(1:5)-TiO₂/rGO among co-doped composites exhibits better capacitive performance as determined through cyclic voltammetry and galvanostatic charge–discharge. Among all the nanocomposites 422 F/g was the maximum depicted by 2 wt% La:Ce(1:5)-TiO₂/rGO at a scan rate of 10 mV/s (potential window from −0.4 to +0.6 V) and 1895 F/g at 1 mV/s (potential window −0.6 to +0.6 V). specific capacitance was also determined via GCD, and a maximum capacitance of 486 F/g is depicted by 2 wt% La:Ce(1:5)-TiO₂/rGO. The same composites have also served as promising electrode materials in terms of columbic efficiency, power, and energy density.

近年来，人们对用于存储能量的先进高性能材料，特别是超级电容器的关注激增。一种令人鼓舞的方法是利用基于过渡金属氧化物/石墨烯的纳米复合材料，这已经证明了提高电容的巨大潜力。目前研究的氧化钛掺杂石墨烯的电化学性能通过稀土金属的掺入得到了改善。采用水热技术制备纳米复合材料作为电极材料。采用x射线衍射（XRD）、拉曼光谱（Raman spectroscopy）、傅里叶变换红外光谱（FT-IR）和扫描电镜（SEM）等方法对纳米复合材料进行表征。以不同比例的镧和铈为掺杂剂，在氧化钛和石墨烯中掺杂2 wt%稀土元素，合成了三元和四元纳米复合材料。在2 wt%的La:Ce-TiO2/rGO中，镧和铈以1:1、1:3和1:5的比例掺杂。通过循环伏安法和恒流充放电测试，发现2 wt% La:Ce(1:5)-TiO2/rGO共掺杂复合材料具有更好的电容性能。在所有纳米复合材料中，2 wt% La:Ce(1:5)-TiO2/rGO在扫描速率为10 mV/s（电位窗口从- 0.4到+0.6 V）时最大可描绘422 F/g， 1 mV/s（电位窗口从- 0.6到+0.6 V）时最大可描绘1895 F/g。通过GCD测定了比电容，2 wt% La:Ce(1:5)-TiO2/rGO描绘了最大电容486 F/g。同样的复合材料在哥伦比亚效率、功率和能量密度方面也被用作有前途的电极材料。

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引用次数: 0

Sea urchin-like NiPt/TiCeO2 catalyst for rapid and efficient hydrogen production from hydrous hydrazine 海胆样NiPt/TiCeO2催化剂用于水合肼快速高效制氢

IF 5.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-03-07 DOI: 10.1016/j.jre.2025.03.007

Wenting Ren , Shuyu Liu , Yan Wang , Jing Xie , Chao Wan , Lixin Xu , Shenglai Li , Jiapei Wang , Pavel S. Postnikov

Controllable hydrogen production via the catalytic decomposition of hydrous hydrazine (N₂H₄·H₂O) holds significant promise for mobile and portable applications. However, current catalysts suffer from unsatisfactory reaction activity and hydrogen (H₂) selectivity. Based on the unique redox properties of CeO₂, this article aims to enhance the thermal catalytic performance for the decomposition of N₂H₄·H₂O by improving metal-support interactions between the TiCeO₂ and NiPt active components. Meanwhile, the sea urchin-like TiCeO₂ support, which is more conducive to the dispersion of the NiPt nanoparticles and provides more reactive sites for the reaction, was used to immobilize Ni-Pt into the Ni_xPt_1‒x/TiCeO₂ sample using the impregnation-reduction method. By modulating Ce doping and the Ni-Pt molar ratio, samples with different Ni-Pt compositions were synthesized. The optimal Ni_0.5Pt_0.5/TiCeO₂ (n_Ni: n_Pt = 1) shows the highest catalytic performance compared with the other samples, with a TOF (turnover frequency) of 212.58 min⁻¹ and 100% hydrogen selectivity at 323 K. Furthermore, the hydrogen selectivity remains 100% after six cycles. This remarkable activity and stability provide valuable insights and encouragement for accelerating the practical application of N₂H₄·H₂O as a viable hydrogen carrier.

通过催化分解水合肼（N2H4·H2O）的可控制氢技术在移动和便携式应用中具有重要的前景。然而，目前的催化剂的反应活性和氢（H2）选择性不理想。基于CeO2独特的氧化还原性能，本文旨在通过改善TiCeO2与NiPt活性组分之间的金属-载体相互作用来增强对N2H4·H2O分解的热催化性能。同时，采用浸渍还原法将Ni-Pt固定在NixPt1-x /TiCeO2样品中，采用海胆样TiCeO2载体更有利于NiPt纳米颗粒的分散，为反应提供更多的反应位点。通过调节Ce掺杂和Ni-Pt摩尔比，合成了具有不同Ni-Pt成分的样品。与其他样品相比，最佳的Ni0.5Pt0.5/TiCeO2 （nNi: nPt = 1）表现出最高的催化性能，在323 K时，TOF（周转频率）为212.58 min−1，氢选择性为100%。6次循环后，氢的选择性仍为100%。这种显著的活性和稳定性为加速N2H4·H2O作为可行的氢载体的实际应用提供了有价值的见解和鼓励。

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引用次数: 0

Constructing a core–shell rare earth-manganese-zirconium composite compound to improve catalytic activity of NO oxidation 构建核壳型稀土-锰-锆复合化合物提高NO氧化催化活性

IF 7.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-02-27 DOI: 10.1016/j.jre.2025.02.008

Weixin Zhao , Yongqi Zhang , Zheng Zhao , Yuqing Ling , Yongke Hou , Rui Chen , Dongming Chen , Meisheng Cui , Juanyu Yang , Xiaowei Huang

NO catalytic oxidation is the key performance of the diesel oxidation catalyst (DOC). We present a facile deposition method for the core–shell rare-earth manganese-zirconium composite oxide that shows the Mn mullite phase uniform loading on the surface of zirconium-based composite (YMO/CYZO), which demonstrates a superior NO oxidation catalytic performance in simulated diesel combustion conditions and better thermal stability than mullite phase YMn₂O₅ oxide. The NO oxidation at 250 °C over YMO/CYZO-a approaches 25.2% in contrast to 13.52% over YMn₂O₅-a. Then the catalytic performance of YMO/CYZO, YMO and commercial 1 wt% Pt/Al₂O₃ in a NO + O₂ atmosphere was compared. The maximum conversion rate of YMO/CYZO to NO oxidation is 89.6% at 274 °C with a GHSV of 50000 h^–1, and the performance is superior to that of YMO (82.8% at 293 °C) and 1 wt% Pt/Al₂O₃ (68.6%, 335 °C). The NO-temperature programmed desorption (NO-TPD) and diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that YMO/CYZO has multiple NO adsorption sites and high storage capacity. Furthermore, density functional theory (DFT) calculation indicates that YMO/CYZO has lower oxygen vacancy formation energies (E_v = 0.93 eV) and favorable NO adsorption energies (E_ads = −2.1 eV). Moreover, in situ X-ray photoelectron spectroscopy (XPS) characterization shows that the core–shell structure of YMO/CYZO has the potential to transmit active oxygen species to help realize Mn³⁺ to Mn⁴⁺ during the reaction process to enhance the conversion of NO∗ molecules, while NO oxidation reactions follow the MvK mechanism.

NO催化氧化是柴油氧化催化剂（DOC）的关键性能。本文提出了一种快速沉积的方法，将Mn莫来石相均匀负载在锆基复合材料（YMO/CYZO）表面，该方法在模拟柴油燃烧条件下具有优越的NO氧化催化性能，并且比莫来石相的YMn2O5氧化物具有更好的热稳定性。250℃时，YMO/CYZO-a的NO氧化率接近25.2%，而YMn2O5-a的NO氧化率为13.52%。然后比较了YMO/CYZO、YMO和1 wt% Pt/Al2O3在NO + O2气氛中的催化性能。当温度为274℃，GHSV为50000 h-1时，YMO/CYZO氧化成NO的最大转化率为89.6%，性能优于YMO（293℃时的82.8%）和1wt % Pt/Al2O3（335℃时的68.6%）。无温度程序脱附（NO- tpd）和漫反射红外傅里叶变换光谱（DRIFTS）结果表明，YMO/CYZO具有多个NO吸附位点和高存储容量。密度泛函理论（DFT）计算表明，YMO/CYZO具有较低的氧空位形成能（Ev = 0.93 Ev）和较好的NO吸附能（Eads = - 2.1 Ev）。此外，原位x射线光电子能谱（XPS）表征表明，YMO/CYZO的核壳结构具有传递活性氧的潜力，有助于在反应过程中实现Mn3+到Mn4+，从而增强NO *分子的转化，而NO氧化反应遵循MvK机制。

{"title":"Constructing a core–shell rare earth-manganese-zirconium composite compound to improve catalytic activity of NO oxidation","authors":"Weixin Zhao , Yongqi Zhang , Zheng Zhao , Yuqing Ling , Yongke Hou , Rui Chen , Dongming Chen , Meisheng Cui , Juanyu Yang , Xiaowei Huang","doi":"10.1016/j.jre.2025.02.008","DOIUrl":"10.1016/j.jre.2025.02.008","url":null,"abstract":"<div><div>NO catalytic oxidation is the key performance of the diesel oxidation catalyst (DOC). We present a facile deposition method for the core–shell rare-earth manganese-zirconium composite oxide that shows the Mn mullite phase uniform loading on the surface of zirconium-based composite (YMO/CYZO), which demonstrates a superior NO oxidation catalytic performance in simulated diesel combustion conditions and better thermal stability than mullite phase YMn2O5 oxide. The NO oxidation at 250 °C over YMO/CYZO-a approaches 25.2% in contrast to 13.52% over YMn2O5-a. Then the catalytic performance of YMO/CYZO, YMO and commercial 1 wt% Pt/Al2O3 in a NO + O2 atmosphere was compared. The maximum conversion rate of YMO/CYZO to NO oxidation is 89.6% at 274 °C with a GHSV of 50000 h–1, and the performance is superior to that of YMO (82.8% at 293 °C) and 1 wt% Pt/Al2O3 (68.6%, 335 °C). The NO-temperature programmed desorption (NO-TPD) and diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that YMO/CYZO has multiple NO adsorption sites and high storage capacity. Furthermore, density functional theory (DFT) calculation indicates that YMO/CYZO has lower oxygen vacancy formation energies (Ev = 0.93 eV) and favorable NO adsorption energies (Eads = −2.1 eV). Moreover, in situ X-ray photoelectron spectroscopy (XPS) characterization shows that the core–shell structure of YMO/CYZO has the potential to transmit active oxygen species to help realize Mn3+ to Mn4+ during the reaction process to enhance the conversion of NO∗ molecules, while NO oxidation reactions follow the MvK mechanism.</div></div>","PeriodicalId":16940,"journal":{"name":"Journal of Rare Earths","volume":"43 10","pages":"Pages 2186-2194"},"PeriodicalIF":7.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145157530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Confined rare earth cerium dioxide nanoparticles film for gas sensing: Experimental and theoretical studies 气敏用受限稀土二氧化铈纳米颗粒薄膜：实验与理论研究

IF 5.2 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths

Pub Date : 2025-02-26 DOI: 10.1016/j.jre.2025.02.013

Yan Liang , Hua Tang , Chunbo Ru , Xiaojian Zhao , Lu Tang , Yong Yang

Nanostructured materials with small particle sizes have been widely used in resistive gas sensors due to their high specific surface area and surface activity. However, phenomena including agglomeration, growth and structural damage of nanostructures are almost inevitable during the processes of device fabrication or sensing tests, which makes it difficult to exert their expected activity. To address this issue, rare earth metal oxide CeO₂ was chosen as the model material to explore confined nanostructures in resistive gas sensors. The experiment successfully achieves the preparation of confined CeO₂ nanoparticles film using a pulsed laser deposition combined with rapid annealing technology. It is found that the confined CeO₂ nanoparticles film enables the efficient detection of volatile organic compound triethylamine, demonstrating a significant response of 20 (R_a/R_g) towards 100 ppm triethylamine, a fast response of 2 s, excellent stability and selectivity. By in-situ confinement in porous carbon matrix, dispersion and fixation of CeO₂ nanoparticles can be achieved, thereby fully utilizing their high surface activity. In addition, the porous carbon matrix can serve as a transport pathway for the target gas molecules and electrons, enabling efficient gas–solid reactions and effective collection of gas sensing signals. More importantly, the confined CeO₂ nanoparticles film was grown in-situ on commercial alumina flats gas sensing substrate, which can be directly used as sensing layer for gas sensors. Based on first-principles calculations, the triethylamine sensing mechanism of the confined CeO₂ nanoparticles film was systematically analyzed at the atomic and electronic scale. This study offers new insights into enhancing the gas sensing performance of resistive gas sensors through confined nanostructures design.

小粒径的纳米结构材料由于其高比表面积和表面活性而被广泛应用于电阻式气体传感器中。然而，在器件制造或传感测试过程中，纳米结构的团聚、生长和结构损伤等现象几乎是不可避免的，这使得纳米结构难以发挥其预期的活性。为了解决这一问题，我们选择稀土金属氧化物CeO2作为模型材料来探索电阻式气体传感器的受限纳米结构。实验成功地采用脉冲激光沉积结合快速退火技术制备了受限氧化铈纳米颗粒薄膜。实验结果表明，封闭的CeO2纳米颗粒薄膜能够有效地检测挥发性有机化合物三乙胺，对100 ppm三乙胺的响应率为20 (Ra/Rg)，响应时间为2s，具有良好的稳定性和选择性。通过原位约束在多孔碳基体中，可以实现CeO2纳米颗粒的分散和固定，从而充分利用其高表面活性。此外，多孔碳基质可以作为目标气体分子和电子的传输途径，实现高效的气固反应和有效的气敏信号收集。更重要的是，在商用氧化铝平板气敏衬底上原位生长了受限的CeO2纳米颗粒薄膜，该薄膜可直接用作气敏传感器的传感层。基于第一性原理计算，在原子和电子尺度上系统分析了受限氧化铈纳米颗粒薄膜的三乙胺传感机理。该研究为通过限制纳米结构设计来提高电阻式气体传感器的气敏性能提供了新的见解。

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引用次数: 0