Pub Date : 2026-01-22DOI: 10.1016/j.jpcs.2026.113554
Meryem Sabri, Houda Siah, Aya Chelh, Hamid Ez-Zahraouy
The present study describes the detailed first-principles investigation of the mechanical, electronic, optical, photocatalytic, and thermodynamic behaviors of the CsBBr (B = Si, Ti, Sn) double perovskite family. The calculated formation energies confirm their thermodynamic favorability, while elastic parameters indicate robust mechanical stability with distinct variations in stiffness, ductility, and anisotropy across the series. In addition, the indirect band gaps from electronic band-structure and density-of-states results show magnitudes that are strongly dependent on the B-site cation, underlining the role of chemical substitution in modulating electronic behavior. Strong absorption features, notable dielectric responses, and high optical conductivity in the optical analyses suggest their feasibility in optoelectronic applications. Evaluation of the band edges also revealed that all the compounds have energetically appropriate positions for both water-splitting reactions and CO reduction pathways, with CsSnBr being the most favorable compound for photocatalytic activity. Thermodynamic properties derived using the quasi-harmonic Debye model revealed predictable heat-capacity evolution, decreasing Gibbs free energy with temperature, and pressure-induced lattice stiffening. Overall, the CsBBr perovskites emerge as promising candidates for various renewable-energy technologies like hydrogen production, photocatalysis, and CO conversion.
{"title":"First-principles exploration of lead-free halide double perovskites Cs2BBr6 (B = Si, Ti, Sn) as candidates for hydrogen production and CO2 reduction","authors":"Meryem Sabri, Houda Siah, Aya Chelh, Hamid Ez-Zahraouy","doi":"10.1016/j.jpcs.2026.113554","DOIUrl":"10.1016/j.jpcs.2026.113554","url":null,"abstract":"<div><div>The present study describes the detailed first-principles investigation of the mechanical, electronic, optical, photocatalytic, and thermodynamic behaviors of the Cs<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>BBr<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span> (B = Si, Ti, Sn) double perovskite family. The calculated formation energies confirm their thermodynamic favorability, while elastic parameters indicate robust mechanical stability with distinct variations in stiffness, ductility, and anisotropy across the series. In addition, the indirect band gaps from electronic band-structure and density-of-states results show magnitudes that are strongly dependent on the B-site cation, underlining the role of chemical substitution in modulating electronic behavior. Strong absorption features, notable dielectric responses, and high optical conductivity in the optical analyses suggest their feasibility in optoelectronic applications. Evaluation of the band edges also revealed that all the compounds have energetically appropriate positions for both water-splitting reactions and CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> reduction pathways, with Cs<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>SnBr<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span> being the most favorable compound for photocatalytic activity. Thermodynamic properties derived using the quasi-harmonic Debye model revealed predictable heat-capacity evolution, decreasing Gibbs free energy with temperature, and pressure-induced lattice stiffening. Overall, the Cs<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>BBr<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span> perovskites emerge as promising candidates for various renewable-energy technologies like hydrogen production, photocatalysis, and CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> conversion.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113554"},"PeriodicalIF":4.9,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.jpcs.2026.113553
Yohandys A. Zulueta , Cam-Nhung Le , My-Phuong Pham-Ho , Minh Tho Nguyen
The development of solid-state electrolytes with tunable defect chemistry and robust mechanical properties is vital for advancing metal-ion battery technologies. This study presents a multiscale computational investigation of NaAlCl4 and NaGaCl4, evaluating their structural, mechanical, and defect-driven transport characteristics in pristine and aliovalently doped forms. Optimized geometries yield lattice parameters in excellent agreement with experiment, especially for NaGaCl4, validating the applied force fields. Mechanical analysis confirms elastic stability and ductility, with NaAlCl4 showing superior machinability and NaGaCl4 exhibiting enhanced isotropy and metallic bonding traits favorable for interfacial contact. Defect calculations reveal that Na + migration is dominated by intrinsic NaCl-type Schottky defects. Divalent doping at Na+ sites emerges as the most effective strategy for generating Na+ vacancies, supported by low solution energies and strong dopant-vacancy binding. Substitution at the A3+ site introduces Na + interstitials with improved energetics, especially in the flexible Ga-based framework. Bond valence site energy analysis reveals that Sr2+ doping in NaGaCl4 lowers migration barriers and enables quasi-3D conduction. Doped NaGaCl4 systems achieve activation energies near 0.42 eV and conductivities ∼10−7 Scm−1, highlighting their promise as scalable, defect-tolerant candidates for next-generation sodium-ion solid-state batteries.
{"title":"Defect-driven ion transport of NaAlCl4 and NaGaCl4 for advanced solid-state battery electrolytes: A multiscale computational study","authors":"Yohandys A. Zulueta , Cam-Nhung Le , My-Phuong Pham-Ho , Minh Tho Nguyen","doi":"10.1016/j.jpcs.2026.113553","DOIUrl":"10.1016/j.jpcs.2026.113553","url":null,"abstract":"<div><div>The development of solid-state electrolytes with tunable defect chemistry and robust mechanical properties is vital for advancing metal-ion battery technologies. This study presents a multiscale computational investigation of NaAlCl<sub>4</sub> and NaGaCl<sub>4</sub>, evaluating their structural, mechanical, and defect-driven transport characteristics in pristine and aliovalently doped forms. Optimized geometries yield lattice parameters in excellent agreement with experiment, especially for NaGaCl<sub>4</sub>, validating the applied force fields. Mechanical analysis confirms elastic stability and ductility, with NaAlCl<sub>4</sub> showing superior machinability and NaGaCl<sub>4</sub> exhibiting enhanced isotropy and metallic bonding traits favorable for interfacial contact. Defect calculations reveal that Na <sup>+</sup> migration is dominated by intrinsic NaCl-type Schottky defects. Divalent doping at Na<sup>+</sup> sites emerges as the most effective strategy for generating Na<sup>+</sup> vacancies, supported by low solution energies and strong dopant-vacancy binding. Substitution at the A<sup>3+</sup> site introduces Na <sup>+</sup> interstitials with improved energetics, especially in the flexible Ga-based framework. Bond valence site energy analysis reveals that Sr<sup>2+</sup> doping in NaGaCl<sub>4</sub> lowers migration barriers and enables quasi-3D conduction. Doped NaGaCl<sub>4</sub> systems achieve activation energies near 0.42 eV and conductivities ∼10<sup>−7</sup> Scm<sup>−1</sup>, highlighting their promise as scalable, defect-tolerant candidates for next-generation sodium-ion solid-state batteries.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113553"},"PeriodicalIF":4.9,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146078195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.jpcs.2026.113552
Manmeet Kaur, Amit Dhir, Shilpi Verma
Rapid industrialization and insufficient wastewater management have led to the extensive occurrence of chlorophenols (CPs) in aquatic environments, where their persistence, toxicity, and bioaccumulation pose a significant threat to ecology and human health. This review entails tungsten oxide (WO3) and it's composites as visible light responsive photocatalysts for the degradation of mono-, di-, and trichlorophenols in water. Initially, the structural diversity, morphology control of WO3, and phase behaviour have been discussed while emphasizing how the crystal structure, bandgap, and nano-structuring affect light absorption, charge separation, and surface reactivity. Different synthesis routes, including sol-gel, hydrothermal, co-precipitation, green synthesis, and template-assisted techniques, are assessed in terms of the resulting textural, optical, and electronic properties that affect the photocatalytic efficiency of WO3 and its composites. This review further highlights various modification strategies, including doping, co-catalyst hybridization, and Z-scheme heterojunction formation, highlighting their roles in enhancing radical generation, suppressing electron-hole recombination, and extending the visible light response. Further emphasis is directed towards operational parameters and the role of key reactive oxygen species in degradation pathways, as well as the efficiency of the composites in the mineralization of the cholorophenols. Finally, detailed mechanistic insights including the identification of intermediates formed, and ring opening routes are discussed, guiding the rational design of next-generation WO3-based photocatalysts for efficient remediation of chlorophenol - contaminated water.
{"title":"A comprehensive review of the WO3 and its composites for the removal of priority pollutant: Chlorophenols in wastewater treatment","authors":"Manmeet Kaur, Amit Dhir, Shilpi Verma","doi":"10.1016/j.jpcs.2026.113552","DOIUrl":"10.1016/j.jpcs.2026.113552","url":null,"abstract":"<div><div>Rapid industrialization and insufficient wastewater management have led to the extensive occurrence of chlorophenols (CPs) in aquatic environments, where their persistence, toxicity, and bioaccumulation pose a significant threat to ecology and human health. This review entails tungsten oxide (WO<sub>3</sub>) and it's composites as visible light responsive photocatalysts for the degradation of mono-, di-, and trichlorophenols in water. Initially, the structural diversity, morphology control of WO<sub>3</sub>, and phase behaviour have been discussed while emphasizing how the crystal structure, bandgap, and nano-structuring affect light absorption, charge separation, and surface reactivity. Different synthesis routes, including sol-gel, hydrothermal, co-precipitation, green synthesis, and template-assisted techniques, are assessed in terms of the resulting textural, optical, and electronic properties that affect the photocatalytic efficiency of WO<sub>3</sub> and its composites. This review further highlights various modification strategies, including doping, co-catalyst hybridization, and Z-scheme heterojunction formation, highlighting their roles in enhancing radical generation, suppressing electron-hole recombination, and extending the visible light response. Further emphasis is directed towards operational parameters and the role of key reactive oxygen species in degradation pathways, as well as the efficiency of the composites in the mineralization of the cholorophenols. Finally, detailed mechanistic insights including the identification of intermediates formed, and ring opening routes are discussed, guiding the rational design of next-generation WO<sub>3</sub>-based photocatalysts for efficient remediation of chlorophenol - contaminated water.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113552"},"PeriodicalIF":4.9,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146078196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.jpcs.2026.113550
Aimée Giovanna Jerônimo , Kallyandra Amorim , Willams Albuquerque , Pollyana Trigueiro , Y. Romaguera-Barcelay , Rodrigo Prado Feitosa , Maria del Mar Orta , Josy A. Osajima , Ramón Raudel Peña-Garcia
In this work, cadmium sulfide–rice husk ash (CdS/RHA) composites were synthesized by co-precipitation of cadmium nitrate and ammonium sulfide, followed by dispersion and assembly of the resulting cadmium sulfide nanoparticles with rice husk ash at mass ratios of 1:1, 1:2, and 1:3. Structural analysis using X-ray diffraction (XRD) confirmed the presence of hexagonal and cubic cadmium sulfide, as well as α-quartz (SiO2). Additionally, Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy coupled with energy-dispersive analysis (EDS) demonstrated strong interfacial contact and a uniform dispersion of nanoparticles. Nitrogen adsorption–desorption measurements revealed mesoporous surfaces, with specific surface areas of 15.9, 9.3, and 6.1 m2 g−1 for the 1:1, 1:2, and 1:3 composites, respectively. Diffuse reflectance spectroscopy (DRS) showed negligible changes in the optical band gap (2.413–2.434 eV) but a 20–35 % decrease in visible reflectance upon incorporation of ash. Photoluminescence measurements showed a quenching of near-band-edge emission for the CdS/RHA composites, indicating enhanced separation of photogenerated charges. Lettuce seed bioassays revealed that the control exhibited a germination rate of 76.5 % under the test conditions, whereas pure cadmium sulfide and the CdS/RHA(1:1) composite completely inhibited germination, while the 1:2 and 1:3 composites restored germination rates to 31.5(2)% and 50.0(1)% at 1000 μg mL−1, respectively. Under UV irradiation, the CdS/RHA(1:1) composite achieved 83.5(2)% degradation of metronidazole (MNZ) in 150 min (apparent rate constant, k = 0.01239 min−1), outperforming the 1:2 (74.0(1) %, k = 0.01000 min−1) and 1:3 (74.8(1) %, k = 0.009713 min−1) materials. Complementary dark experiments revealed that adsorption alone was responsible for only 11.1 %, 18.0 %, and 15.2 % removal in the 1:1, 1:2, and 1:3 composites, respectively, confirming that metronidazole removal was primarily photocatalytic. Scavenger tests identified photogenerated holes and electrons as the primary reactive species, with superoxide radicals playing a secondary role. The CdS/RHA(1:1) composite retained 40.3(1)% of its initial activity after three consecutive reuse cycles, with degradation efficiencies decreasing from 83.5 % in the first cycle to 58.4 % and 40.3 % in the second and third cycles, respectively. These results demonstrate that integrating CdS with rice husk ash yields a recyclable, high-performance photocatalyst with reduced phytotoxicity at higher RHA loadings, suitable for sustainable pharmaceutical removal from water.
{"title":"Rice husk ash–supported CdS composites for efficient photocatalytic degradation of metronidazole with minimized phytotoxicity","authors":"Aimée Giovanna Jerônimo , Kallyandra Amorim , Willams Albuquerque , Pollyana Trigueiro , Y. Romaguera-Barcelay , Rodrigo Prado Feitosa , Maria del Mar Orta , Josy A. Osajima , Ramón Raudel Peña-Garcia","doi":"10.1016/j.jpcs.2026.113550","DOIUrl":"10.1016/j.jpcs.2026.113550","url":null,"abstract":"<div><div>In this work, cadmium sulfide–rice husk ash (CdS/RHA) composites were synthesized by co-precipitation of cadmium nitrate and ammonium sulfide, followed by dispersion and assembly of the resulting cadmium sulfide nanoparticles with rice husk ash at mass ratios of 1:1, 1:2, and 1:3. Structural analysis using X-ray diffraction (XRD) confirmed the presence of hexagonal and cubic cadmium sulfide, as well as α-quartz (SiO<sub>2</sub>). Additionally, Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy coupled with energy-dispersive analysis (EDS) demonstrated strong interfacial contact and a uniform dispersion of nanoparticles. Nitrogen adsorption–desorption measurements revealed mesoporous surfaces, with specific surface areas of 15.9, 9.3, and 6.1 m<sup>2</sup> g<sup>−1</sup> for the 1:1, 1:2, and 1:3 composites, respectively. Diffuse reflectance spectroscopy (DRS) showed negligible changes in the optical band gap (2.413–2.434 eV) but a 20–35 % decrease in visible reflectance upon incorporation of ash. Photoluminescence measurements showed a quenching of near-band-edge emission for the CdS/RHA composites, indicating enhanced separation of photogenerated charges. Lettuce seed bioassays revealed that the control exhibited a germination rate of 76.5 % under the test conditions, whereas pure cadmium sulfide and the CdS/RHA(1:1) composite completely inhibited germination, while the 1:2 and 1:3 composites restored germination rates to 31.5(2)% and 50.0(1)% at 1000 μg mL<sup>−1</sup>, respectively. Under UV irradiation, the CdS/RHA(1:1) composite achieved 83.5(2)% degradation of metronidazole (MNZ) in 150 min (apparent rate constant, k = 0.01239 min<sup>−1</sup>), outperforming the 1:2 (74.0(1) %, k = 0.01000 min<sup>−1</sup>) and 1:3 (74.8(1) %, k = 0.009713 min<sup>−1</sup>) materials. Complementary dark experiments revealed that adsorption alone was responsible for only 11.1 %, 18.0 %, and 15.2 % removal in the 1:1, 1:2, and 1:3 composites, respectively, confirming that metronidazole removal was primarily photocatalytic. Scavenger tests identified photogenerated holes and electrons as the primary reactive species, with superoxide radicals playing a secondary role. The CdS/RHA(1:1) composite retained 40.3(1)% of its initial activity after three consecutive reuse cycles, with degradation efficiencies decreasing from 83.5 % in the first cycle to 58.4 % and 40.3 % in the second and third cycles, respectively. These results demonstrate that integrating CdS with rice husk ash yields a recyclable, high-performance photocatalyst with reduced phytotoxicity at higher RHA loadings, suitable for sustainable pharmaceutical removal from water.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"213 ","pages":"Article 113550"},"PeriodicalIF":4.9,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191868","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.jpcs.2026.113536
O.M. Sousa , D. Nafday , F.O. Carvalho , L.V.C. Assali , M.V. Lalic , A. Delin , C.M. Araujo , O. Eriksson , H.M. Petrilli , A.B. Klautau
In this study, we employ ab initio density functional theory (DFT) calculations to elucidate the microscopic origin of the Jahn–Teller distortion suppression and magnetic moment quenching in LiNiO2 (LNO) during delithiation. Our results reveal that these effects arise not from changes in the Ni oxidation state but from an electronic charge redistribution between the and orbitals derived from Ni–3d states. This internal electronic rearrangement, driven by strong hybridization between Ni–3d and O–2p orbitals, accounts for the inactivation of the Jahn–Teller distortion and the quenching of the magnetic moment at the NiO6 octahedra. The same mechanism also explains the shifts observed in the Ni and O K-edge X-ray absorption near-edge structure (XANES) spectra during delithiation. Our findings provide a new microscopic interpretation of the LNO redox process, highlighting the role of electron redistribution within the Ni–3d manifold as the true origin of its structural and magnetic transformations.
{"title":"Unveiling the mechanism of Jahn-Teller distortion and magnetic suppression in LiNiO2 during delithiation: Insights from electron redistribution","authors":"O.M. Sousa , D. Nafday , F.O. Carvalho , L.V.C. Assali , M.V. Lalic , A. Delin , C.M. Araujo , O. Eriksson , H.M. Petrilli , A.B. Klautau","doi":"10.1016/j.jpcs.2026.113536","DOIUrl":"10.1016/j.jpcs.2026.113536","url":null,"abstract":"<div><div>In this study, we employ <em>ab initio</em> density functional theory (DFT) calculations to elucidate the microscopic origin of the Jahn–Teller distortion suppression and magnetic moment quenching in LiNiO<sub>2</sub> (LNO) during delithiation. Our results reveal that these effects arise not from changes in the Ni oxidation state but from an electronic charge redistribution between the <span><math><mrow><msub><mi>e</mi><mi>g</mi></msub></mrow></math></span> and <span><math><mrow><msub><mi>t</mi><mrow><mn>2</mn><mi>g</mi></mrow></msub></mrow></math></span> orbitals derived from Ni–3d states. This internal electronic rearrangement, driven by strong hybridization between Ni–3d and O–2p orbitals, accounts for the inactivation of the Jahn–Teller distortion and the quenching of the magnetic moment at the NiO<sub>6</sub> octahedra. The same mechanism also explains the shifts observed in the Ni and O K-edge X-ray absorption near-edge structure (XANES) spectra during delithiation. Our findings provide a new microscopic interpretation of the LNO redox process, highlighting the role of electron redistribution within the Ni–3d manifold as the true origin of its structural and magnetic transformations.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113536"},"PeriodicalIF":4.9,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146078256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.jpcs.2026.113548
Defeng Wu , Bing Zhou , Yun Li , Siyu Lu , Zongbiao Liu , Jianlong Zhang , Mingliang Ma , Na Wang , Xin Shang , Kaiying Wang
Enhancing the visible light response of wide-bandgap semiconductors is crucial for the advancement of oxide-based solar devices. Here, we report a TiO2 nanorod array (TNRAs)/BiVO4 heterojunction photoanode fabricated via a cyclic spin-coating strategy, where the number of coating cycles (10, 15 or 20) is used to regulate the deposition of BiVO4. The formation of a type-II band alignment facilitated efficient charge separation, while the incorporation of BiVO4 extended the light absorption from ∼400 nm to ∼500 nm, as confirmed by UV–Vis spectroscopy. Electrochemical impedance spectroscopy revealed reduced charge transfer resistance, and density functional theory (DFT) calculations showed that the bandgap narrowed and visible-light absorption increased with increasing BiVO4 thickness. The optimized heterojunction (15 deposition cycles) delivers a photocurrent density of 1.41 mA cm-2 in the quasi-solid-state solar cell ∼19 times that of the pristine TNRAs (0.075 mA cm-2) with a power conversion efficiency of 0.277%. The device also exhibits remarkable photocurrent stability in the quasi solid electrolyte (QSE). This study elucidates the interplay between heterointerface structure and optoelectronic performance and offers a scalable route to engineering stable, high-efficiency, oxide-based solar energy systems.
提高宽禁带半导体的可见光响应对氧化物基太阳能器件的发展至关重要。在这里，我们报道了一个TiO2纳米棒阵列(TNRAs)/BiVO4异质结光阳极通过循环自旋镀膜策略制备，其中涂层循环次数（10,15或20）用于调节BiVO4的沉积。ii型带对准的形成促进了有效的电荷分离，而BiVO4的加入将光吸收从~ 400 nm扩展到~ 500 nm，这是由UV-Vis光谱证实的。电化学阻抗谱显示电荷转移电阻减小，密度泛函理论（DFT）计算表明，随着BiVO4厚度的增加，带隙缩小，可见光吸收增加。优化后的异质结（15个沉积周期）在准固态太阳能电池中提供的光电流密度为1.41 mA cm-2，是原始TNRAs （0.075 mA cm-2）的19倍，功率转换效率为0.277%。该器件在准固体电解质（QSE）中也表现出显著的光电流稳定性。该研究阐明了异质界面结构与光电性能之间的相互作用，并为工程稳定、高效、基于氧化物的太阳能系统提供了可扩展的途径。
{"title":"Unraveling the mechanism underlying the enhanced photoresponse in BiVO4-modified TiO2 nanorod arrays for quasi-solid-state solar cells","authors":"Defeng Wu , Bing Zhou , Yun Li , Siyu Lu , Zongbiao Liu , Jianlong Zhang , Mingliang Ma , Na Wang , Xin Shang , Kaiying Wang","doi":"10.1016/j.jpcs.2026.113548","DOIUrl":"10.1016/j.jpcs.2026.113548","url":null,"abstract":"<div><div>Enhancing the visible light response of wide-bandgap semiconductors is crucial for the advancement of oxide-based solar devices. Here, we report a TiO<sub>2</sub> nanorod array (TNRAs)/BiVO<sub>4</sub> heterojunction photoanode fabricated via a cyclic spin-coating strategy, where the number of coating cycles (10, 15 or 20) is used to regulate the deposition of BiVO<sub>4</sub>. The formation of a type-II band alignment facilitated efficient charge separation, while the incorporation of BiVO<sub>4</sub> extended the light absorption from ∼400 nm to ∼500 nm, as confirmed by UV–Vis spectroscopy. Electrochemical impedance spectroscopy revealed reduced charge transfer resistance, and density functional theory (DFT) calculations showed that the bandgap narrowed and visible-light absorption increased with increasing BiVO<sub>4</sub> thickness. The optimized heterojunction (15 deposition cycles) delivers a photocurrent density of 1.41 mA cm<sup>-</sup><sup>2</sup> in the quasi-solid-state solar cell ∼19 times that of the pristine TNRAs (0.075 mA cm<sup>-</sup><sup>2</sup>) with a power conversion efficiency of 0.277%. The device also exhibits remarkable photocurrent stability in the quasi solid electrolyte (QSE). This study elucidates the interplay between heterointerface structure and optoelectronic performance and offers a scalable route to engineering stable, high-efficiency, oxide-based solar energy systems.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113548"},"PeriodicalIF":4.9,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-19DOI: 10.1016/j.jpcs.2026.113543
Lin Gao , Chunjian Ai , Liang Liang , Xiuying Li , Xue Lin , Junyou Shi
Photocatalytic technology represents an effective and cost-efficient approach to the degradation of organic pollutants. This paper presents an investigation into the degradation ability of ms-BVO/TCN/Ag composite for organic pollutants at different ratios. The 7.5 % ms-BVO/TCN/Ag sample was observed to exhibit the most effective degradation performance under visible light irradiation, with degradation rates of 83.12 % and 84.45 % for TC and DEP in 120 min. This is attribute to the distinctive tubular configuration of TCN, which enhances the number of reactive sites. The addition of Ag nanoparticles to TCN expands the light absorption spectrum of TCN through the surface plasmon resonance (SPR) effect. Furthermore, the construction of Z-scheme heterojunctions between TCN/Ag and ms-BVO preserves the robust redox capabilities of these components while mitigating the rapid complexation of photogenerated electron pairs. This paper presents a novel strategy and approach for the further construction of heterojunctions, based on the morphological control of carbon nitride.
{"title":"BiVO4 nanoparticles and Ag nanoparticles co-decorated with tubular carbon nitride: A ternary heterostructure photocatalyst for degradation of organic pollutants in water","authors":"Lin Gao , Chunjian Ai , Liang Liang , Xiuying Li , Xue Lin , Junyou Shi","doi":"10.1016/j.jpcs.2026.113543","DOIUrl":"10.1016/j.jpcs.2026.113543","url":null,"abstract":"<div><div>Photocatalytic technology represents an effective and cost-efficient approach to the degradation of organic pollutants. This paper presents an investigation into the degradation ability of <em>ms</em>-BVO/TCN/Ag composite for organic pollutants at different ratios. The 7.5 % <em>ms</em>-BVO/TCN/Ag sample was observed to exhibit the most effective degradation performance under visible light irradiation, with degradation rates of 83.12 % and 84.45 % for TC and DEP in 120 min. This is attribute to the distinctive tubular configuration of TCN, which enhances the number of reactive sites. The addition of Ag nanoparticles to TCN expands the light absorption spectrum of TCN through the surface plasmon resonance (SPR) effect. Furthermore, the construction of Z-scheme heterojunctions between TCN/Ag and <em>ms</em>-BVO preserves the robust redox capabilities of these components while mitigating the rapid complexation of photogenerated electron pairs. This paper presents a novel strategy and approach for the further construction of heterojunctions, based on the morphological control of carbon nitride.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113543"},"PeriodicalIF":4.9,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mn-doped Y3Al5O12 (YAG) single crystals were synthesized using the floating zone technique, and the optical and scintillation properties were investigated. Photoluminescence (PL) and X-ray-induced scintillation spectra revealed that emission peaks, attributed to the 3d-3d transitions of Mn2+, were observed at 600 and 730 nm. Among the samples, the 0.1 % Mn-doped sample exhibited the highest emission intensity and the most favorable lower detection limit (2.9 mGy/h). The calculated decay time constants were 1.1–2.2 and 20–30 ms, which indicated that the decay components were attributed to 3d-3d transitions of Mn2+.
{"title":"Development of Mn-doped Y3Al5O12 single crystal scintillators","authors":"Naoki Hayashi, Toshiaki Kunikata, Daisuke Nakauchi, Takeshi Ubukata, Kensei Ichiba, Takumi Kato, Noriaki Kawaguchi, Takayuki Yanagida","doi":"10.1016/j.jpcs.2026.113547","DOIUrl":"10.1016/j.jpcs.2026.113547","url":null,"abstract":"<div><div>Mn-doped Y<sub>3</sub>Al<sub>5</sub>O<sub>12</sub> (YAG) single crystals were synthesized using the floating zone technique, and the optical and scintillation properties were investigated. Photoluminescence (PL) and X-ray-induced scintillation spectra revealed that emission peaks, attributed to the 3d-3d transitions of Mn<sup>2+</sup>, were observed at 600 and 730 nm. Among the samples, the 0.1 % Mn-doped sample exhibited the highest emission intensity and the most favorable lower detection limit (2.9 mGy/h). The calculated decay time constants were 1.1–2.2 and 20–30 ms, which indicated that the decay components were attributed to 3d-3d transitions of Mn<sup>2+</sup>.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113547"},"PeriodicalIF":4.9,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-17DOI: 10.1016/j.jpcs.2026.113540
Faiza Bibi , Abdul Hanan , Ong Gerard , Fayaz Khan , Arshid Numan , Mohammad Khalid
Efficient electrodes are critical in the development of advanced electrochemical energy storage systems (EESs), such as supercapattery. Although various materials have been reported in the literature, the keen focus remained on high-figured performance metrics such as specific capacities. In this scenario, the exploration of potential electrode materials in terms of high stability and promising energy/power densities remains undermined. Metal phosphates, despite their excellent electrochemical stability, are intrinsically limited by poor electrical conductivity, which restricts their broader applicability. To address this challenge, we report the fabrication of a cobalt phosphate hydrate composited with an emerging double transition metal (DTM) MXene (Mo2Ti2C3Tx), synthesized via a facile hydrothermal approach within just 2 h, using multiple elemental weights (1, 2, and 4 wt% Mo2Ti2C3Tx). The self-assembled flowery morphologies, essential compositional bonding, and reference crystallographic phases confirmed the successful formation of pure Co3(PO4)2·8H2O, and Co3(PO4)2·8H2O-Mo2Ti2C3Tx composites. In a three-electrode configuration, the optimized composite electrode (CD1) delivered a specific capacity of 105.83 C/g from cyclic voltammetry (CV) and 78.8 C/g from galvanostatic charge-discharge (GCD). Additionally, the CD1//AC device (AC denotes activated carbon) demonstrated promising energy and power densities of 10.81 Wh/kg and 224.94 W/kg, respectively, with remarkable capacity retention of 97 % after 5000 cycles. The electrochemical performance of Co3(PO4)2·8H2O-Mo2Ti2C3Tx highlighted the potential of metal phosphates-based DTM MXene composites for highly stable supercapattery applications.
{"title":"Optimization of flower-like cobalt phosphate hydrate-double transition metal MXene composite electrodes for supercapattery","authors":"Faiza Bibi , Abdul Hanan , Ong Gerard , Fayaz Khan , Arshid Numan , Mohammad Khalid","doi":"10.1016/j.jpcs.2026.113540","DOIUrl":"10.1016/j.jpcs.2026.113540","url":null,"abstract":"<div><div>Efficient electrodes are critical in the development of advanced electrochemical energy storage systems (EESs), such as supercapattery. Although various materials have been reported in the literature, the keen focus remained on high-figured performance metrics such as specific capacities. In this scenario, the exploration of potential electrode materials in terms of high stability and promising energy/power densities remains undermined. Metal phosphates, despite their excellent electrochemical stability, are intrinsically limited by poor electrical conductivity, which restricts their broader applicability. To address this challenge, we report the fabrication of a cobalt phosphate hydrate composited with an emerging double transition metal (DTM) MXene (Mo<sub>2</sub>Ti<sub>2</sub>C<sub>3</sub>T<sub>x</sub>), synthesized via a facile hydrothermal approach within just 2 h, using multiple elemental weights (1, 2, and 4 wt% Mo<sub>2</sub>Ti<sub>2</sub>C<sub>3</sub>T<sub>x</sub>). The self-assembled flowery morphologies, essential compositional bonding, and reference crystallographic phases confirmed the successful formation of pure Co<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>·8H<sub>2</sub>O, and Co<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>·8H<sub>2</sub>O-Mo<sub>2</sub>Ti<sub>2</sub>C<sub>3</sub>T<sub>x</sub> composites. In a three-electrode configuration, the optimized composite electrode (CD1) delivered a specific capacity of 105.83 C/g from cyclic voltammetry (CV) and 78.8 C/g from galvanostatic charge-discharge (GCD). Additionally, the CD1//AC device (AC denotes activated carbon) demonstrated promising energy and power densities of 10.81 Wh/kg and 224.94 W/kg, respectively, with remarkable capacity retention of 97 % after 5000 cycles. The electrochemical performance of Co<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>·8H<sub>2</sub>O-Mo<sub>2</sub>Ti<sub>2</sub>C<sub>3</sub>T<sub>x</sub> highlighted the potential of metal phosphates-based DTM MXene composites for highly stable supercapattery applications.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113540"},"PeriodicalIF":4.9,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-17DOI: 10.1016/j.jpcs.2026.113542
Malla Balakrishna , Bittu Singh , Channamsetti Sushma , Y. Subbareddy , D.V. Satish , M. GnanaKiran , T. Srinivasa Rao , Anchal Aneja , Ramu Boddepalli , Malla Ramanaiah
Bi4Ti3O12 (BIT) nanoparticles were successfully synthesized via a sol–gel method, with a well-defined orthorhombic Aurivillius structure and nanocrystallite sizes of 40–60 nm. Raman spectroscopy confirmed the presence of characteristic Ti–O and Bi–O vibrational modes, indicating octahedral distortion critical for functional properties. X-ray photoelectron spectroscopy (XPS) revealed Bi 4f peaks at 158.7 eV and 164.0 eV, confirming the Bi3+ oxidation state, Ti 2p doublets at 458.5 eV and 464.2 eV corresponding to Ti4+, and an O 1s peak at 529.6 eV associated with lattice oxygen. Field-emission scanning electron microscopy (FESEM) showed nanoplate-like morphology with an average particle size of ∼270 nm and homogeneous elemental distribution. The BIT nanoparticles exhibited excellent visible-light photocatalytic activity, degrading ∼90 % of methylene blue within 120 min. The degradation followed pseudo-first-order kinetics, with rate constants decreasing from 0.1414 to 0.0363 min-1 as dye concentration increased. The combination of high crystallinity, chemical purity, nanoscale morphology, and strong photocatalytic performance highlights BIT nanoparticles as promising candidates for multifunctional applications including wastewater treatment, environmental remediation, photovoltaic devices, and ferroelectric memory technologies.
{"title":"Aurivillius-phase Bi4Ti3O12 nanoparticles structural, surface, and photocatalytic properties for advanced environmental applications","authors":"Malla Balakrishna , Bittu Singh , Channamsetti Sushma , Y. Subbareddy , D.V. Satish , M. GnanaKiran , T. Srinivasa Rao , Anchal Aneja , Ramu Boddepalli , Malla Ramanaiah","doi":"10.1016/j.jpcs.2026.113542","DOIUrl":"10.1016/j.jpcs.2026.113542","url":null,"abstract":"<div><div>Bi<sub>4</sub>Ti<sub>3</sub>O<sub>12</sub> (BIT) nanoparticles were successfully synthesized via a sol–gel method, with a well-defined orthorhombic Aurivillius structure and nanocrystallite sizes of 40–60 nm. Raman spectroscopy confirmed the presence of characteristic Ti–O and Bi–O vibrational modes, indicating octahedral distortion critical for functional properties. X-ray photoelectron spectroscopy (XPS) revealed Bi 4f peaks at 158.7 eV and 164.0 eV, confirming the Bi<sup>3+</sup> oxidation state, Ti 2p doublets at 458.5 eV and 464.2 eV corresponding to Ti<sup>4+</sup>, and an O 1s peak at 529.6 eV associated with lattice oxygen. Field-emission scanning electron microscopy (FESEM) showed nanoplate-like morphology with an average particle size of ∼270 nm and homogeneous elemental distribution. The BIT nanoparticles exhibited excellent visible-light photocatalytic activity, degrading ∼90 % of methylene blue within 120 min. The degradation followed pseudo-first-order kinetics, with rate constants decreasing from 0.1414 to 0.0363 min-1 as dye concentration increased. The combination of high crystallinity, chemical purity, nanoscale morphology, and strong photocatalytic performance highlights BIT nanoparticles as promising candidates for multifunctional applications including wastewater treatment, environmental remediation, photovoltaic devices, and ferroelectric memory technologies.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"212 ","pages":"Article 113542"},"PeriodicalIF":4.9,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023985","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号