Ji Li , Hongsheng Huang , Jia Zheng , Hongyan Zhang , Jincheng Zhong
{"title":"Morphology-dependent thermal decomposition kinetics of (NH4)[Fe2(PO4)2(OH)(H2O)]·H2O","authors":"Ji Li , Hongsheng Huang , Jia Zheng , Hongyan Zhang , Jincheng Zhong","doi":"10.1016/j.jssc.2025.125697","DOIUrl":"10.1016/j.jssc.2025.125697","url":null,"abstract":"<div><div>Polyhedral (sample 1), ellipsoidal (sample 2), and quasi spherical (sample 3) (NH<sub>4</sub>)[Fe<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>(OH)(H<sub>2</sub>O)]·H<sub>2</sub>O were prepared by hydrothermal method. Their thermal decomposition process, which proceeds in three distinct stages, was investigated using model-free methods (KAS, OFW, Starink) in conjunction with the masterplot procedure to determine the activation energy (Eα) and reaction mechanism for each stage. The results indicate that both the decomposition mechanism and Eα are influenced by the sample morphology and particle size. The activation energy increases in the order of stage I < stage II < stage III across all morphologies. For any given stage, the Eα values follow the trend: sample 1 > sample 2 > sample 3. Mechanistic analysis revealed that the first and second stages for all samples are governed by the phase boundary reaction model (g(α) = 1-(1-α)<sup>1/2</sup>), and the nucleation and growth model, respectively. In the third stage, samples 1 and 2 follow a stochastic nucleation and subsequent growth mechanism (g(α) = [-ln(1-α)]<sup>n</sup>) model with varying n values, while sample 3 follows a chemical reaction model (g(α)=(1-α)<sup>−1</sup>-1). Finally, the morphological evolution and its mechanism during thermal decomposition were studied and analyzed.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125697"},"PeriodicalIF":3.5,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263322","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"NiCoCu-carbonate hydroxide as high performed OER electrocatalyst under neutral conditions","authors":"Li Yu, Qin Liang","doi":"10.1016/j.jssc.2025.125693","DOIUrl":"10.1016/j.jssc.2025.125693","url":null,"abstract":"<div><div>In this study, a novel (NiCoCu) (OH)<sub>2</sub>(CO<sub>3</sub>)-10 h-100 °C (M<sub>3</sub>-10 h-100 °C, M = metal) catalyst with a loose spherical morphology and enhanced oxygen evolution activity under neutral electrolyte conditions was developed by incorporating transition metals Ni and Cu into Co<sub>2</sub>(OH)<sub>2</sub>CO<sub>3</sub>. The introduction of Ni and Cu not only effectively increased the active surface area of the material but also significantly enhanced its electron transfer efficiency. Experimental results indicate that the synthesized M<sub>3</sub>-10 h-100 °C exhibits excellent electrocatalytic performance in the OER. Specifically, at a current density of 10 mA cm<sup>−2</sup>, it achieves an overpotential of 490 mV and demonstrates good stability, maintaining its initial catalytic activity even after continuous operation for more than 24 h. The catalytic performance of this material is markedly superior to that of pure Co<sub>2</sub>(OH)<sub>2</sub>CO<sub>3</sub>, indicating that the incorporation of Ni and Cu elements through doping significantly enhances catalytic activity and broadens its potential applications in related fields. The introduction of Ni and Cu alters the electronic structure and surface properties of the material, thereby considerably improving the reaction efficiency and stability during the catalytic process. This doping strategy provides a novel and effective method for the design and development of high-performance catalysts, underscoring its important scientific significance and practical application potential.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125693"},"PeriodicalIF":3.5,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoli Wang , Lina An , Xinyu Wang , Chaoqing Quan , Yan Feng
{"title":"Design of Cr3+-activated broadband near-infrared garnet phosphors with abnormal thermal quenching behavior for advanced NIR pc-LEDs in night vision","authors":"Xiaoli Wang , Lina An , Xinyu Wang , Chaoqing Quan , Yan Feng","doi":"10.1016/j.jssc.2025.125694","DOIUrl":"10.1016/j.jssc.2025.125694","url":null,"abstract":"<div><div>In recent years, near-infrared(NIR) phosphor-converted light-emitting diodes have wide and important application prospects of agricultural production, night vision monitoring and biological imaging. However, it is still a huge challenge to prepare a new type of near-infrared luminescent material with excellent thermal quenching behavior to improve applications such as night vision monitoring. In this study, a series of SrLu<sub>2</sub>ScAl<sub>3</sub>SiO<sub>12</sub>:<em>x</em>%Cr<sup>3+</sup>(<em>x</em> = 0.016, 0.020, 0.024, 0.028, 0.032) phosphors with excellent thermal stability and high quantum efficiency were synthesized by high-temperature solid-state method. At 441 nm wavelength excitation, the emission spectrum shows the broadband emission range from 600 nm to 850 nm corresponds to the <sup>4</sup>T<sub>2</sub>→<sup>4</sup>A<sub>2</sub> transition and the sharp peak emission at 687 nm and 704 nm corresponds to the <sup>2</sup>E→<sup>4</sup>A<sub>2</sub> transition. The SrLu<sub>2</sub>ScAl<sub>3</sub>SiO<sub>12</sub>:<em>x</em>%Cr<sup>3+</sup> samples exhibit good thermal stability (473K, 57 %@687 nm, 72 %@704 nm, 113 %@750 nm). Furthermore, the internal quantum efficiency(IQE) and the external quantum efficiency(EQE) of SrLu<sub>2</sub>ScAl<sub>3</sub>SiO<sub>12</sub>:Cr<sup>3+</sup> are 71.46 % and 42.31 %, respectively. The NIR pc-LED device using the SrLu<sub>2</sub>ScAl<sub>3</sub>SiO<sub>12</sub>:<em>x</em>%Cr<sup>3+</sup> phosphor presents a NIR output power (30.86 mW) and a photoelectric conversion efficiency(3.25 %) under a driving current of 300 mA. Through experimental testing, materials with excellent performance are used to encapsulate NIR pc-LEDs, which demonstrates the good potential of this material in the application of night vision.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125694"},"PeriodicalIF":3.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Customized hierarchical heterostructure in quasi metal-organic-framework for durable and sensitive NO2 chemiresistive detection","authors":"Haotian Cai , Qi Zhang , Yue Yao, Yanchen Qian, Yuanjing Cui, Guodong Qian","doi":"10.1016/j.jssc.2025.125696","DOIUrl":"10.1016/j.jssc.2025.125696","url":null,"abstract":"<div><div>Semiconducting metal oxides (SMO) are widely utilized as NO<sub>2</sub> gas sensors due to their stability and tunable properties. However, pure SMOs typically exhibit low response and poor selectivity at room temperature, which limits their practical application. Herein, we address these limitations by designing a hierarchical heterostructure, namely a quasi-metal-organic-framework (quasi-MOF) embedded with highly dispersed CeO<sub>2</sub> nanoparticles (∼3 nm) and enveloped by hydroxyl-rich SiO<sub>2</sub> (denoted QMOF-HHS), synthesized via low-temperature calcination of a Ce-MOF precursor. This architecture thus enables abundant reactive sites through uniformly dispersed CeO<sub>2</sub> nanocrystals, enhanced NO<sub>2</sub> adsorption via –OH-rich SiO<sub>2</sub>, and promoted charge transfer via interfacial heterojunctions, delivering highly sensitive and selective NO<sub>2</sub> detection at room temperature. Notably, the QMOF-HHS sensor demonstrates a superior NO<sub>2</sub> response of 244 % at 30 ppm, surpassing that of pure CeO<sub>2</sub>, while also achieving excellent repeatability and selectivity. This work introduces a novel strategy for constructing hierarchical quasi-MOF heterostructures for efficient, room-temperature NO<sub>2</sub> sensing.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125696"},"PeriodicalIF":3.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Junjie Peng , Cheng Du , Yu Yang , Jiqin Zhong , Xin Chen , Zewei Liu , Feng Xu , Daofei Lv , Xun Wang , Jian Yan
{"title":"Reinforced CH4/N2 separation on a scalable azolate metal-organic framework with uncoordinated nitrogen sites and amine groups","authors":"Junjie Peng , Cheng Du , Yu Yang , Jiqin Zhong , Xin Chen , Zewei Liu , Feng Xu , Daofei Lv , Xun Wang , Jian Yan","doi":"10.1016/j.jssc.2025.125689","DOIUrl":"10.1016/j.jssc.2025.125689","url":null,"abstract":"<div><div>Recovering low-concentration methane (CH<sub>4</sub>) from coal mine methane (CMM) is of great significance for environmental and industrial requirement. Pressure swing adsorption (PSA) can serve as a promising technique if the adsorbents can achieve excellent capacity and selectivity toward CH<sub>4</sub> while exhibiting moderate regeneration conditions. Herein, we demonstrate an ultramicroporous triazolate metal-organic framework (MAF-66), featuring multiple amine groups and uncoordinated nitrogen sites, demonstrates high-performance CH<sub>4</sub>/N<sub>2</sub> separation in PSA process. Inspiringly, MAF-66 shows a high CH<sub>4</sub> capacity of 30.0 cm<sup>3</sup> g<sup>−1</sup> at 298 K and 100 kPa, together with a reasonable selectivity of 4.9 according to ideal adsorbed solution theory (IAST). In addition, MAF-66 enables complete CH<sub>4</sub> regeneration under vacuum without the need of heating, indicative of its potential for PSA applications. Molecular simulations reveal amine groups and uncoordinated nitrogen sites are the major active sites for the selective CH<sub>4</sub> from N<sub>2</sub>. Dynamic breakthrough experiments confirm efficient separation of CH<sub>4</sub>/N<sub>2</sub> mixture on MAF-66. Moreover, a scaled-up synthesis was conducted to produce 19.7-g MAF-66, which showed almost identical characteristics and CH<sub>4</sub>/N<sub>2</sub> separation performance, further verifying the feasibility of MAF-66 as a practical adsorbent for the recovery of CH<sub>4</sub> from CMM.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125689"},"PeriodicalIF":3.5,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263261","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Large strain in Bi0.5(Na0.84K0.16)0.5TiO3 lead-free relaxor ferroelectrics modified by Bi(Zn2/3Nb1/3)O3","authors":"Chang Liu, Min Li, Chongguang Lyu","doi":"10.1016/j.jssc.2025.125690","DOIUrl":"10.1016/j.jssc.2025.125690","url":null,"abstract":"<div><div>Actuators have gained significant attention from researchers owing to their fantastic merits, including quick response time, large displacement value, relatively low energy consumption, and small size. Bi<sub>0.5</sub>Na<sub>0.5</sub>TiO<sub>3</sub> (BNT) ceramics, with relatively high Curie temperatures and good piezoelectric performance, are promising candidates for actuator applications. Nevertheless, pure BNT ceramics possess relatively low strain values, and it is urgent to find appropriate strategies to address this issue. Here, we introduced Bi(Zn<sub>2/3</sub>Nb<sub>1/3</sub>)O<sub>3</sub> (BZN) into the Bi<sub>0.5</sub>(Na<sub>0.84</sub>K<sub>0.16</sub>)<sub>0.5</sub>TiO<sub>3</sub> (BNKT) matrix with the intention of manipulating electric properties. The phase structural measurement demonstrates rhombohedral (R) and tetragonal (T) phases coexist in the resultant samples. All samples display uniform surface morphology and decreased grain sizes with increased BZN doping. Ferroelectric measurements indicate that the resultant samples exhibit slender hysteresis loops with increasing BZN dopant. Notably, the BNKT-2BZN sample exhibits a large electric field-induced strain of 0.57 % and a high normalized strain (<em>d</em><sub>33</sub>∗) of 950 pm/V, which are both almost three times greater than the values in undoped BNKT ceramics. The dielectric measurements indicate that BZN-doped ceramics display superior relaxor behavior in comparison to that of the pure BNKT sample. These works provide feasible research pathways for optimizing strain properties in the application of large displacement actuators.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125690"},"PeriodicalIF":3.5,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Unravelling 3D-3D topotactic transformation behavior in mesoporous zeolite via ultrasonic-assisted strategy","authors":"Yemei Liu, Haixin Shan, Huizhi Zhang, Yuhan Li, Liwei Xu, Na Hu, Xiangshu Chen","doi":"10.1016/j.jssc.2025.125684","DOIUrl":"10.1016/j.jssc.2025.125684","url":null,"abstract":"<div><div>Synthesizing mesoporous zeolites using organotemplate-free methods remains a significant challenge. Here, hierarchical chabazite (CHA) zeolites with uniform mesoporosity were rapidly synthesized via a green, ultrasound-assisted route that operates without organic structure-directing agents, fluorides or seeds. Systematic screening revealed that only 1 h of ultrasoonic aging is sufficient to transform the crystallization pathway from phillipsite (PHI) to pure CHA within 20–24 h at 363 K. Comprehensive characterization techniques identified hydroxyl (•OH) and Si-based (≡Si•) radicals generated by acoustic cavitation; which facilitated the depolymerization–repolymerization of aluminosilicate species and enabled the topotactic reconstruction of PHI 4<sup>5</sup>8<sup>3</sup> composite building units (CBUs) into CHA-type double 6-membered rings (D6Rs) and <em>cha</em> cages. Optimal synthesis conditions (<em>n</em>(SiO<sub>2</sub>)/<em>n</em>(Al<sub>2</sub>O<sub>3</sub>) = 20, <em>n</em>(H<sub>2</sub>O)/<em>n</em>(SiO<sub>2</sub>) = 12, <em>n</em>(Na<sub>2</sub>O + K<sub>2</sub>O) <em>n</em>(SiO<sub>2</sub>) = 0.38, and <em>n</em>(Na<sup>+</sup>)/<em>n</em>(K<sup>+</sup>) ≥ 3) yielded spherical CHA aggregates (1.5 μm) with a Brunauer-Emmett-Teller (BET) surface area of 42.1 m<sup>2</sup> g<sup>−1</sup>, a narrow mesopore distribution centered at 3.8 nm, and 95 % mesoporosity (V<sub>Meso</sub>/V<sub>Total</sub>). Compared to PHI crystals, the CHA product exhibited a 4.3-fold increase in surface area and a 34 % enhancement in CO<sub>2</sub> uptake (3.47 mmol g<sup>−1</sup> at 298 K and 101 kPa), while maintaining high CO<sub>2</sub>/N<sub>2</sub> and CO<sub>2</sub>/CH<sub>4</sub> selectivities. This study offers critical insights into ultrasound-induced radical-assisted crystallization, advancing the design of mesostructured zeolites through sustainable synthesis pathways.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125684"},"PeriodicalIF":3.5,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217002","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jingyang Li , Dongge Xu , Chuanxue You , Yunchao Ma , Wei Jiang , Chunbo Liu , Guangbo Che
{"title":"Donor-acceptor covalent organic framework containing thiadiazole for photocatalytic production of hydrogen peroxide","authors":"Jingyang Li , Dongge Xu , Chuanxue You , Yunchao Ma , Wei Jiang , Chunbo Liu , Guangbo Che","doi":"10.1016/j.jssc.2025.125687","DOIUrl":"10.1016/j.jssc.2025.125687","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) have been commonly used in photosynthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) due to tunable morphology, controllable pore size and exposed active sites. However, the recombination between photogenerated electrons and holes still hinder the application of COFs. Donor-acceptor (D-A) heterojunctions which are constructed by electron-riched and electron-deficient units, could effectively modify the band gap and optoelectronic properties. Meanwhile, D-A structure accelerates the rate of charge transfer during the process. Herein, thiadiazole-linked D-A COF has been devised and prepared using 1,3,5-triformylphloroglucino (Tp) and 1,3,4-thiadiazole-3,5-diamine (TD) through solvothermal reaction. The resultant COF-TD1 present the production rate of 527.50 μmol g<sup>−1</sup> h<sup>−1</sup>, showing good performance in photocatalytic preparation of hydrogen peroxide. Eventually, the most possible mechanism is demonstrated to be two-step one-electron ORR reaction, suggesting robust organic photocatalysts by the introduction of D-A structure with heterocycle for future photosynthesis of H<sub>2</sub>O<sub>2</sub>.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125687"},"PeriodicalIF":3.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Effect of Li2O–ZnO–B2O3 as an additive on the sinterability and microwave dielectric properties of forsterite ceramics","authors":"Aravind Radha, Sea-Fue Wang","doi":"10.1016/j.jssc.2025.125686","DOIUrl":"10.1016/j.jssc.2025.125686","url":null,"abstract":"<div><div>Microwave dielectric ceramics are increasingly used in a variety of advanced communication devices and serve as key components in the fabrication of microwave dielectric filters and resonators. The range of applications for these ceramics has expanded alongside the rapid development of related technologies. Among these materials, magnesium orthosilicate (Mg<sub>2</sub>SiO<sub>4</sub>) is highly promising for 5G communication systems due to its low dielectric constant and excellent performance. However, Mg<sub>2</sub>SiO<sub>4</sub> typically requires a high sintering temperature, which poses limitations for practical applications. To address this, the present study investigates the effect of adding small amounts (1, 3, 5, and 7 wt%) of low-temperature Li<sub>2</sub>O–ZnO–B<sub>2</sub>O<sub>3</sub> (LZB) glass into Mg<sub>2</sub>SiO<sub>4</sub> to reduce the sintering temperature and enhance its microwave dielectric properties. Phase formation and microstructural characteristics were confirmed and analyzed by X-ray diffraction, scanning electron microscopy (SEM), high-resolution transmission electron microscopy, Raman spectroscopy, and Fourier-transform infrared spectroscopy. Notably, the addition of 3 wt% LZB significantly reduced the sintering temperature from 1300 °C to 1150 °C, attributed to the liquid-phase sintering effect, while maintaining substantial densification. Additionally, the LZB-doped Mg<sub>2</sub>SiO<sub>4</sub> ceramics demonstrated outstanding microwave dielectric characteristics, such as a low dielectric loss (tan <em>δ</em>) of 0.0006, a dielectric constant (ε<sub>r</sub>) of 6.4, and a quality factor (Q × <em>f</em>) of 15,501.90 GHz. These findings show that adding LZB glass lowers the sintering temperature while maintaining the desired dielectric characteristics, which makes LZB-doped Mg<sub>2</sub>SiO<sub>4</sub> ceramics feasible for low-temperature co-fired ceramic (LTCC) technology.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125686"},"PeriodicalIF":3.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A.V. Nimmy , J. Indujalekshmi , S. Chithra , V.M. Anandakumar , V. Biju
{"title":"Elucidation of augmented visible-light photocatalysis in surface-modified coloured rutile TiO2","authors":"A.V. Nimmy , J. Indujalekshmi , S. Chithra , V.M. Anandakumar , V. Biju","doi":"10.1016/j.jssc.2025.125685","DOIUrl":"10.1016/j.jssc.2025.125685","url":null,"abstract":"<div><div>The prevalent TiO<sub>2</sub> photocatalysts have some glaring limitations, viz., (i) their inactivity under visible light irradiation and (ii) the irreversible temperature-dependent transformation of photocatalytically active anatase phase into inactive rutile. In this study, we employed a facile method to develop visible-light sensitive coloured rutile photocatalysts to tackle these issues. Here, we executed a surface modification technique on sol-gel derived, crystalline rutile TiO<sub>2</sub> using sodium borohydride (NaBH<sub>4</sub>). This was done in favourable atmospheric conditions, rendering it cost-effective and scalable. A series of rutile TiO<sub>2</sub> samples, with colour varied from white to black, were prepared by changing the amount of NaBH<sub>4</sub>. Surface-modified samples exhibited crystalline core and disordered shell heterostructure. The pristine rutile sample was rich in Ti<sup>3+</sup> and doubly charged oxygen vacancy V<sub>o</sub><sup>++</sup>, respectively corresponding to shallow and deep defect states. In contrast, the surface-modified samples are rich in photocatalytically active shallow-trapped surface Ti<sup>3+</sup> and singly charged oxygen vacancy (V<sub>o</sub><sup>+</sup>) defects, which act as colour centers. Hence, the photocatalytic activities of the surface-modified rutile TiO<sub>2</sub> enhanced significantly upon white LED irradiation. Amongst a series of surface-modified samples, rR3 (treated with 0.1 g of NaBH<sub>4</sub>) showed the highest visible-light photocatalytic degradation rate constant (10.35 × 10<sup>−3</sup> min<sup>−1</sup>) for methylene blue (MB) dye. In addition to MB, sample rR3 showed better degradation of rhodamine B (RhB) and phenol than the pure rutile and commercial photocatalyst Degussa P25 under visible-light irradiation. Since rutile is the thermodynamically stable form of TiO<sub>2</sub>, surface-modified samples could be effective in high-temperature applications, especially without the assistance of regularly utilized UV radiation.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"353 ","pages":"Article 125685"},"PeriodicalIF":3.5,"publicationDate":"2025-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}