Influence of molybdenum and tungsten doping/codoping for enhanced upconversion and photocatalysis activity of upconverting BiVO4:Ho3+-Yb3+

IF 9.6 1区化学 Q1 CHEMISTRY, APPLIED

Journal of Rare Earths Pub Date : 2026-10-01 Epub Date: 2025-12-29 DOI:10.1016/j.jre.2025.12.022

Manoj Hazarika, Lutukurthi D.N.V.V. Konda, Abinash Das, Vineet Kumar Rai

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引用次数: 0

Abstract

A series of upconverting BiVO₄:Ho³⁺-Yb³⁺ materials codoped with transition metal Mo⁶⁺ and W⁶⁺ ions were successfully synthesized via hydrothermal method and systematically characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FTIR), Raman and field emission scanning electron microscopy (FESEM) techniques. The optimal doping concentrations of Mo⁶⁺ and W⁶⁺ were identified based on upconversion luminescence (UCL) performance. Notably, Mo⁶⁺ or W⁶⁺ ions codoping significantly improves the UCL intensity, and the Mo⁶⁺-W⁶⁺ codoped sample with the highest enhancement of ∼21-fold compared to BiVO₄:Ho³⁺-Yb³⁺ has been reported. Photocatalytic dye degradation experiments reveal significantly improved activity for the optimized Mo⁶⁺-W⁶⁺ codoped sample, with the highest rate constant (∼0.0578 min⁻¹). This observed rate constant is ∼6 times and ∼10 times better as compared to the BiVO₄:Ho³⁺-Yb³⁺ and pure BiVO₄, respectively. This enhancement is attributed to the increased photogenerated charge carrier density, improved charge transfer ability, and reduced recombination rate. This has been further confirmed by the photoelectrochemical (PEC) studies combined with electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV). The Mo⁶⁺-W⁶⁺ codoped sample exhibits the lowest charge transfer resistance (R_ct = 448.71 Ω), highest photocurrent density (∼7.46 mA/cm²) and longer lifetime as observed from the time-resolved photoluminescence study (TRPL). Additionally, recyclability test confirms the catalyst's stability over multiple cycles, and scavenger studies reveal hydroxyl radicals (·OH) and holes (h⁺) as the dominant reactive species in the degradation process. Overall, the Mo⁶⁺-W⁶⁺ codoped BiVO₄:Ho³⁺-Yb³⁺ has its potential for applications in frequency upconversion and photocatalysis.

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钼钨掺杂/共掺杂对提高上转化BiVO4:Ho3+-Yb3+上转化和光催化活性的影响

采用水热法制备了一系列与过渡金属Mo6+和W6+离子共掺杂的上转换BiVO4:Ho3+-Yb3+材料，并利用x射线衍射（XRD）、x射线光电子能谱（XPS）、紫外-可见漫反射光谱（DRS）、傅里叶变换红外光谱（FTIR）、拉曼光谱和场发射扫描电镜（FESEM）技术对其进行了系统表征。基于上转换发光（UCL）性能，确定了Mo6+和W6+的最佳掺杂浓度。值得注意的是，Mo6+或W6+离子共掺杂显著提高了UCL强度，与BiVO4:Ho3+-Yb3+相比，Mo6+-W6+共掺杂样品的UCL强度最高提高了约21倍。光催化染料降解实验表明，优化后的Mo6+-W6+共掺杂样品的降解活性显著提高，速率常数最高（~ 0.0578 min−1）。与BiVO4:Ho3+-Yb3+和纯BiVO4相比，观察到的速率常数分别提高了~ 6倍和~ 10倍。这种增强是由于光生电荷载流子密度增加，电荷转移能力提高，复合率降低。光电化学（PEC）结合电化学阻抗谱（EIS）和线性扫描伏安法（LSV）的研究进一步证实了这一点。从时间分辨光致发光研究（TRPL）中观察到，Mo6+-W6+共掺杂样品表现出最低的电荷转移电阻（Rct = 448.71 Ω），最高的光电流密度（~ 7.46 mA/cm2）和更长的寿命。此外，可回收性测试证实了催化剂在多次循环中的稳定性，清除剂研究表明羟基自由基（·OH）和空穴（h+）是降解过程中的主要反应物质。综上所述，Mo6+-W6+共掺杂BiVO4:Ho3+-Yb3+在频率上转换和光催化方面具有潜在的应用前景。

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来源期刊

Journal of Rare Earths 化学-应用化学

CiteScore

8.70

自引率

14.30%

发文量

374

审稿时长

1.7 months

期刊介绍： The Journal of Rare Earths reports studies on the 17 rare earth elements. It is a unique English-language learned journal that publishes works on various aspects of basic theory and applied science in the field of rare earths (RE). The journal accepts original high-quality original research papers and review articles with inventive content, and complete experimental data. It represents high academic standards and new progress in the RE field. Due to the advantage of abundant RE resources of China, the research on RE develops very actively, and papers on the latest progress in this field emerge every year. It is not only an important resource in which technicians publish and obtain their latest research results on RE, but also an important way of reflecting the updated progress in RE research field. The Journal of Rare Earths covers all research and application of RE rare earths including spectroscopy, luminescence and phosphors, rare earth catalysis, magnetism and magnetic materials, advanced rare earth materials, RE chemistry & hydrometallurgy, RE metallography & pyrometallurgy, RE new materials, RE solid state physics & solid state chemistry, rare earth applications, RE analysis & test, RE geology & ore dressing, etc.