Pub Date : 2025-11-29DOI: 10.1016/j.jssc.2025.125757
Yulin Zhang , Cuiying Pei , Ning Guo , Feiyu Li , Longlong Fan , Mingxin Zhang , Lingzhen Wang , Gongting Zhang , Yunong Wang , Chao Ma , Wenyong Cheng , Shanpeng Wang , Qiang Zheng , Yanpeng Qi , Junjie Zhang
The discovery of superconductivity with an onset temperature of ∼80 K in pressurized bilayer Ruddlesden-Popper La3Ni2O7-δ has attracted much attention. Despite intense research, determination of the exact oxygen content and understanding of the relationship between superconductivity and oxygen content remain a big challenge. Here, we report a systematical study on the structure and physical properties of La3Ni2O7-δ polycrystalline powders which were prepared using the sol-gel method at ambient pressure and then annealed under high oxygen pressure (pO2) or in ozone. The superconducting transition of La3Ni2O7-δ at ∼80 K under high pressure is suppressed for high pO2 and ozone annealed samples. We attribute this to the combination of the following two reasons: (i) damage of the bilayer structure, as revealed by powder X-ray diffraction, scanning transmission electron microscopy and pair distribution function measurements, and (ii) hole overdoping due to the increasing of oxygen content. Our results reveal that the bilayer structure in La3Ni2O7-δ is fragile and post-annealing under mild oxidization is suitable for maintaining the integrity of the bilayer structure and increasing oxygen content.
{"title":"Strong oxidizing annealing of bilayer La3Ni2O7-δ results in suppression of superconductivity under high pressure","authors":"Yulin Zhang , Cuiying Pei , Ning Guo , Feiyu Li , Longlong Fan , Mingxin Zhang , Lingzhen Wang , Gongting Zhang , Yunong Wang , Chao Ma , Wenyong Cheng , Shanpeng Wang , Qiang Zheng , Yanpeng Qi , Junjie Zhang","doi":"10.1016/j.jssc.2025.125757","DOIUrl":"10.1016/j.jssc.2025.125757","url":null,"abstract":"<div><div>The discovery of superconductivity with an onset temperature of ∼80 K in pressurized bilayer Ruddlesden-Popper La<sub>3</sub>Ni<sub>2</sub>O<sub>7-δ</sub> has attracted much attention. Despite intense research, determination of the exact oxygen content and understanding of the relationship between superconductivity and oxygen content remain a big challenge. Here, we report a systematical study on the structure and physical properties of La<sub>3</sub>Ni<sub>2</sub>O<sub>7-δ</sub> polycrystalline powders which were prepared using the sol-gel method at ambient pressure and then annealed under high oxygen pressure (pO<sub>2</sub>) or in ozone. The superconducting transition of La<sub>3</sub>Ni<sub>2</sub>O<sub>7-δ</sub> at ∼80 K under high pressure is suppressed for high pO<sub>2</sub> and ozone annealed samples. We attribute this to the combination of the following two reasons: (i) damage of the bilayer structure, as revealed by powder X-ray diffraction, scanning transmission electron microscopy and pair distribution function measurements, and (ii) hole overdoping due to the increasing of oxygen content. Our results reveal that the bilayer structure in La<sub>3</sub>Ni<sub>2</sub>O<sub>7-δ</sub> is fragile and post-annealing under mild oxidization is suitable for maintaining the integrity of the bilayer structure and increasing oxygen content.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125757"},"PeriodicalIF":3.5,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734433","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}
We report a detailed investigation of the magnetic, transport, magneto-transport, and thermodynamic properties of the synthesized compound SmSbSe, a new member of the ZrSiS-type topological material family. Magnetic susceptibility measurements reveal an antiferromagnetic (AFM) ground state below T 3.2 K, corroborated by a pronounced -shaped anomaly in the specific heat. Deviation from Curie–Weiss behavior indicates mixing of the ground state with an excited state multiplet above 1001 K, further supported by (T) data, where crystalline electric field (CEF) effects are manifested as a splitting of the ground state into a low-lying doublet and a higher excited level. Isothermal magnetization curves exhibit signatures of field-induced metamagnetic transition. Electrical resistivity measurements showed a nonmetallic temperature dependence with a noticeable change in slope near the Néel temperature, suggesting strong coupling between magnetic and transport properties. Remarkably, SmSbSe exhibits a large, non-saturating magnetoresistance (55% at 2 K) with a significant crossover from quadratic to linear field dependence, indicative of Dirac-like band dispersion. Further, the deviation from Kohler’s scaling along with nonlinearity in Hall resistivity data indicates the presence of multiple charge carriers. The electronic band structure calculations confirm the presence of Dirac nodal-line semimetallic state in SmSbSe.
{"title":"Experimental and theoretical evidence of nodal line semimetallic state in SmSbSe","authors":"Aarti Gautam , Haribrahma Singh , Pabitra Kumar Nayak , Prabuddha Kant Mishra , Rie Y. Umetsu , Dibyajyoti Ghosh , Ashok Kumar Ganguli","doi":"10.1016/j.jssc.2025.125740","DOIUrl":"10.1016/j.jssc.2025.125740","url":null,"abstract":"<div><div>We report a detailed investigation of the magnetic, transport, magneto-transport, and thermodynamic properties of the synthesized compound SmSbSe, a new member of the ZrSiS-type topological material family. Magnetic susceptibility measurements reveal an antiferromagnetic (AFM) ground state below T<span><math><mrow><msub><mrow></mrow><mrow><mi>N</mi></mrow></msub><mo>=</mo></mrow></math></span> 3.2 K, corroborated by a pronounced <span><math><mi>λ</mi></math></span>-shaped anomaly in the specific heat. Deviation from Curie–Weiss behavior indicates mixing of the ground state with an excited state multiplet above 1001 K, further supported by <span><math><msub><mrow><mi>C</mi></mrow><mrow><mi>p</mi></mrow></msub></math></span>(T) data, where crystalline electric field (CEF) effects are manifested as a splitting of the ground state into a low-lying doublet and a higher excited level. Isothermal magnetization curves exhibit signatures of field-induced metamagnetic transition. Electrical resistivity measurements showed a nonmetallic temperature dependence with a noticeable change in slope near the Néel temperature, suggesting strong coupling between magnetic and transport properties. Remarkably, SmSbSe exhibits a large, non-saturating magnetoresistance <span><math><mo>≈</mo></math></span> (55% at 2 K) with a significant crossover from quadratic to linear field dependence, indicative of Dirac-like band dispersion. Further, the deviation from Kohler’s scaling along with nonlinearity in Hall resistivity data indicates the presence of multiple charge carriers. The electronic band structure calculations confirm the presence of Dirac nodal-line semimetallic state in SmSbSe.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125740"},"PeriodicalIF":3.5,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614923","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}
Pub Date : 2025-11-28DOI: 10.1016/j.jssc.2025.125755
Geeta Patkare , Muhammed Shafeeq , Rohan Phatak , Bal Govind Vats , Meera Keskar
Structural and thermal properties of ternary barium tungstates were investigated using powder X-ray diffraction (XRD) and thermogravimetric (TG) techniques. BaWO4, Ba3W2O9, Ba2WO5 and Ba3WO6 compounds were synthesized using solid state route. BaWO4 is stable in air whereas other tungstates are unstable when stored under normal atmospheric conditions. XRD and TG analysis of the stored samples confirmed that except BaWO4 all other tungstates decompose to a mixture of BaWO4 and BaO. The decomposed BaO readily converts into BaCO3 and never observed as BaO in the decomposed product. Decomposition of these tungstates is a function of storage time at ambient condition and barium content in the compounds. Almost complete decomposition was observed in case of Ba3WO6 and Ba2WO5 when stored for 160 days at ambient conditions. The fraction (mole%) of decomposed products i.e. BaWO4 and BaCO3 (in turn BaO) in Ba2WO5 and Ba3WO6 were calculated from Rietveld refinement of XRD patterns which ascertains that Ba3WO6 decomposes faster than Ba2WO5. Thermal expansion coefficients of all freshly synthesized tungstates were calculated from high temperature XRD data from ambient to 1273 K in argon atmosphere. All the synthesized tungstates showed positive expansion in the range of 30–44 × 10−6 K−1 without any degradation under inert atmosphere. This study clearly shows that on storage under ambient conditions, stability of multiple stoichiometric compounds in alkaline earth tungstate has to be ascertained before the proposed applications.
{"title":"Stability studies of barium tungstates: A combined thermogravimetric and X-ray diffraction investigation","authors":"Geeta Patkare , Muhammed Shafeeq , Rohan Phatak , Bal Govind Vats , Meera Keskar","doi":"10.1016/j.jssc.2025.125755","DOIUrl":"10.1016/j.jssc.2025.125755","url":null,"abstract":"<div><div>Structural and thermal properties of ternary barium tungstates were investigated using powder X-ray diffraction (XRD) and thermogravimetric (TG) techniques. BaWO<sub>4</sub>, Ba<sub>3</sub>W<sub>2</sub>O<sub>9</sub>, Ba<sub>2</sub>WO<sub>5</sub> and Ba<sub>3</sub>WO<sub>6</sub> compounds were synthesized using solid state route. BaWO<sub>4</sub> is stable in air whereas other tungstates are unstable when stored under normal atmospheric conditions. XRD and TG analysis of the stored samples confirmed that except BaWO<sub>4</sub> all other tungstates decompose to a mixture of BaWO<sub>4</sub> and BaO. The decomposed BaO readily converts into BaCO<sub>3</sub> and never observed as BaO in the decomposed product. Decomposition of these tungstates is a function of storage time at ambient condition and barium content in the compounds. Almost complete decomposition was observed in case of Ba<sub>3</sub>WO<sub>6</sub> and Ba<sub>2</sub>WO<sub>5</sub> when stored for 160 days at ambient conditions. The fraction (mole%) of decomposed products i.e. BaWO<sub>4</sub> and BaCO<sub>3</sub> (in turn BaO) in Ba<sub>2</sub>WO<sub>5</sub> and Ba<sub>3</sub>WO<sub>6</sub> were calculated from Rietveld refinement of XRD patterns which ascertains that Ba<sub>3</sub>WO<sub>6</sub> decomposes faster than Ba<sub>2</sub>WO<sub>5</sub>. Thermal expansion coefficients of all freshly synthesized tungstates were calculated from high temperature XRD data from ambient to 1273 K in argon atmosphere. All the synthesized tungstates showed positive expansion in the range of 30–44 × 10<sup>−6</sup> K<sup>−1</sup> without any degradation under inert atmosphere. This study clearly shows that on storage under ambient conditions, stability of multiple stoichiometric compounds in alkaline earth tungstate has to be ascertained before the proposed applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125755"},"PeriodicalIF":3.5,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614992","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}
Pub Date : 2025-11-26DOI: 10.1016/j.jssc.2025.125754
S. El Bidaoui , L.V.B. Diop , O. Isnard
The crystal and magnetic structures of ScFe2 and its deuteride ScFe2D3.2 have been investigated by neutron powder diffraction. The C14 hexagonal MgZn2-type crystal structure of the initial alloy ScFe2 is maintained upon the insertion of 3.2 D/f.u. Deuterium localization within the crystal lattice reveals occupancy of four tetrahedral interstitial sites, each coordinated by two Sc and two Fe atoms. Among these, the 6h2 and 12k1 sites are filled at 77 % and 27 % respectively, while the 24l and 6h1 are less than 20 % occupy. The magnetic moment magnitudes have been determined for the two inequivalent Fe sites (2a and 6h) using Rietveld analysis of the magnetic structure; both increase with deuterium insertion. It is found that the magnetic moment orientation at low temperature changes upon deuterium absorption. For ScFe2, the Fe magnetic moments are aligned at an angle of 30° with respect of the c-axis, whereas for ScFe2D3.2 they lie within the basal plane of the hexagonal structure. We also report the thermal evolution of the lattice parameters for both compounds over the temperature range of 2 K–300 K. ScFe2 exhibits typical thermal expansion behavior bellow 300 K, while ScFe2D3.2 displays unusual lattice parameters variations with temperature.
用中子粉末衍射法研究了ScFe2及其氘化物ScFe2D3.2的晶体结构和磁性结构。当加入3.2 D/f.u时，初始合金ScFe2仍保持C14六方mgzn2型晶体结构。氘在晶格内的定位表明占据了四个四面体间隙位，每个空位由两个Sc和两个Fe原子配位。其中6h2和12k1位点的填充率分别为77%和27%，而24l和6h1的填充率不到20%。利用磁性结构的Rietveld分析确定了两个不相等的Fe位点（2a和6h）的磁矩大小；两者都随着氘的加入而增加。发现在低温下磁矩取向随着氘的吸收而发生变化。对于ScFe2， Fe磁矩与c轴呈30°角排列，而对于ScFe2D3.2，它们位于六边形结构的基面上。我们还报道了两种化合物的晶格参数在2 K - 300 K温度范围内的热演化。ScFe2在300 K以下表现出典型的热膨胀行为，而ScFe2D3.2晶格参数随温度变化不寻常。
{"title":"Neutron diffraction study of ScFe2Dx compounds","authors":"S. El Bidaoui , L.V.B. Diop , O. Isnard","doi":"10.1016/j.jssc.2025.125754","DOIUrl":"10.1016/j.jssc.2025.125754","url":null,"abstract":"<div><div>The crystal and magnetic structures of ScFe<sub>2</sub> and its deuteride ScFe<sub>2</sub>D<sub>3.2</sub> have been investigated by neutron powder diffraction. The C14 hexagonal MgZn<sub>2</sub>-type crystal structure of the initial alloy ScFe<sub>2</sub> is maintained upon the insertion of 3.2 D/f.u. Deuterium localization within the crystal lattice reveals occupancy of four tetrahedral interstitial sites, each coordinated by two Sc and two Fe atoms. Among these, the 6<em>h</em><sub>2</sub> and 12<em>k</em><sub>1</sub> sites are filled at 77 % and 27 % respectively, while the 24<em>l</em> and 6<em>h</em><sub>1</sub> are less than 20 % occupy. The magnetic moment magnitudes have been determined for the two inequivalent Fe sites (2<em>a</em> and 6<em>h</em>) using Rietveld analysis of the magnetic structure; both increase with deuterium insertion. It is found that the magnetic moment orientation at low temperature changes upon deuterium absorption. For ScFe<sub>2</sub>, the Fe magnetic moments are aligned at an angle of 30° with respect of the <em>c</em>-axis, whereas for ScFe<sub>2</sub>D<sub>3.2</sub> they lie within the basal plane of the hexagonal structure. We also report the thermal evolution of the lattice parameters for both compounds over the temperature range of 2 K–300 K. ScFe<sub>2</sub> exhibits typical thermal expansion behavior bellow 300 K, while ScFe<sub>2</sub>D<sub>3.2</sub> displays unusual lattice parameters variations with temperature.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125754"},"PeriodicalIF":3.5,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614492","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}
Producing clean energy like hydrogen using solar-driven catalysis is an appealing prospective solution to fulfill worldwide demand. Due to unique structural features and wide range of application these Cs3Bi2Br9-xIx (x = 0, 3, 6, 9) perovskites are thoroughly investigated. The study demonstrate that at x = 3 phase transition occurs from the P63/mmc to P3m1 symmetry addition to electronic phase transition from indirect to direct band gap. The photocatalytic investigation determines that these compounds evolve H2O/O2 to O2, H+ to H2, CO2 to CO, HCHO, CH4OH and CH4 and N2 to 4H+/N2H4 and H+5/N2H+5 and evaluate oxygen as O2/O∗2. The study exhibit the prospective of 0D and 2D perovskites as optoelectronic, photovoltaic and photocatalytic materials, particularly for visible-light-driven water splitting, CO2 reduction and N2 fixation. They also pave the way for future research to produce entirely inorganic lead free halides photovoltaics and photocatalysts for remarkable improvement.
{"title":"Anion-induced dimensional and bandgap engineering in Cs3Bi2Br9-xIx perovskites for enhanced solar to energy conversion","authors":"Shahid Mehmood , Shah Rukh Khan , Haifa A. Alyousef , Shaimaa A.M. Abdelmohsen , Areej Saleh Alqarny , Najla Alotaibi","doi":"10.1016/j.jssc.2025.125756","DOIUrl":"10.1016/j.jssc.2025.125756","url":null,"abstract":"<div><div>Producing clean energy like hydrogen using solar-driven catalysis is an appealing prospective solution to fulfill worldwide demand. Due to unique structural features and wide range of application these Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9-x</sub>I<sub>x</sub> (x = 0, 3, 6, 9) perovskites are thoroughly investigated. The study demonstrate that at x = 3 phase transition occurs from the <em>P</em>6<sub>3</sub>/<em>mmc</em> to <em>P</em>3<em>m</em>1 symmetry addition to electronic phase transition from indirect to direct band gap. The photocatalytic investigation determines that these compounds evolve H<sub>2</sub>O/O<sub>2</sub> to O<sub>2</sub>, H<sup>+</sup> to H<sub>2</sub>, CO<sub>2</sub> to CO, HCHO, CH<sub>4</sub>OH and CH<sub>4</sub> and N<sub>2</sub> to 4H<sup>+</sup>/N<sub>2</sub>H<sub>4</sub> and H<sup>+</sup><sub>5</sub>/N<sub>2</sub>H<sup>+</sup><sub>5</sub> and evaluate oxygen as O<sub>2</sub>/O∗<sub>2</sub>. The study exhibit the prospective of 0D and 2D perovskites as optoelectronic, photovoltaic and photocatalytic materials, particularly for visible-light-driven water splitting, CO<sub>2</sub> reduction and N<sub>2</sub> fixation. They also pave the way for future research to produce entirely inorganic lead free halides photovoltaics and photocatalysts for remarkable improvement.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125756"},"PeriodicalIF":3.5,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614924","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}
Pub Date : 2025-11-26DOI: 10.1016/j.jssc.2025.125753
Shoulei Zhang , Xinyi Qu , Jingnan Hu , Zicheng Shuai , Xiaojie Gu , Shaoxu Wang , Fen Xu , Yalin Xi , Yu Wang
This study demonstrates a green synthesis strategy for zeolite omega via hydroxyl radical (·OH)-assisted transformation of a layered silicate, magadiite. By employing sodium persulfate (Na2S2O8) as a radical initiator and tetramethylammonium bromide (TMABr) as a structure-directing agent, we achieved high-purity zeolite omega with reduced template usage by 75 % and shortened crystallization time to 30 h compared to traditional method. Key influencing factors were systematically investigated. Characterization techniques (XRD, SEM, FT-IR, Raman, 27Al MAS NMR, and ESI-MS) and DFT calculations elucidated a transformation mechanism wherein magadiite served as precursors for zeolite omega nucleation and growth with parts of 6-membered rings (6Rs) and 5-membered rings (5Rs) preserved from magadiite to MAZ-type framework. ·OH preferentially stabilized along the a-axis of the MAZ-type framework, facilitating 4R formation via Si–O–Si bond condensation. This work demonstrates a newly green synthesis strategies for zeolites via layered silicate transformation, combining efficiency and sustainability.
本研究展示了一种绿色合成策略，通过羟基自由基（·OH）辅助层状硅酸盐，镁硬岩化转化。以过硫酸钠（Na2S2O8）为自由基引发剂，四甲基溴化铵（TMABr）为结构导向剂，制备出高纯度的omega分子筛，与传统方法相比，模板用量减少75%，结晶时间缩短至30 h。系统地研究了主要影响因素。表征技术（XRD， SEM, FT-IR, Raman， 27Al MAS NMR和ESI-MS）和DFT计算阐明了一种转变机制，其中magadiite作为沸石omega成核和生长的前驱体，部分6元环（6Rs）和5元环（5Rs）从magadiite保留到maz型框架。·OH优先沿maz型骨架的a轴稳定，有利于通过Si-O-Si键缩合形成4R。这项工作展示了一种新的绿色合成策略，通过层状硅酸盐转化沸石，结合效率和可持续性。
{"title":"Investigation of novel synthesis of zeolite omega via hydroxyl radical-assisted magadiite transformation","authors":"Shoulei Zhang , Xinyi Qu , Jingnan Hu , Zicheng Shuai , Xiaojie Gu , Shaoxu Wang , Fen Xu , Yalin Xi , Yu Wang","doi":"10.1016/j.jssc.2025.125753","DOIUrl":"10.1016/j.jssc.2025.125753","url":null,"abstract":"<div><div>This study demonstrates a green synthesis strategy for zeolite omega via hydroxyl radical (·OH)-assisted transformation of a layered silicate, magadiite. By employing sodium persulfate (Na<sub>2</sub>S<sub>2</sub>O<sub>8</sub>) as a radical initiator and tetramethylammonium bromide (TMABr) as a structure-directing agent, we achieved high-purity zeolite omega with reduced template usage by 75 % and shortened crystallization time to 30 h compared to traditional method. Key influencing factors were systematically investigated. Characterization techniques (XRD, SEM, FT-IR, Raman, <sup>27</sup>Al MAS NMR, and ESI-MS) and DFT calculations elucidated a transformation mechanism wherein magadiite served as precursors for zeolite omega nucleation and growth with parts of 6-membered rings (6Rs) and 5-membered rings (5Rs) preserved from magadiite to MAZ-type framework. ·OH preferentially stabilized along the a-axis of the MAZ-type framework, facilitating 4R formation via Si–O–Si bond condensation. This work demonstrates a newly green synthesis strategies for zeolites via layered silicate transformation, combining efficiency and sustainability.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125753"},"PeriodicalIF":3.5,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614495","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}
Pub Date : 2025-11-24DOI: 10.1016/j.jssc.2025.125751
Pratap K. Pawar , Lahu D. Namade , Harshada C. Yadav , Amruta A. Yadav , Tejas R. Bodake , Rupesh S. Pedanekar , Keshav Y. Rajpure
In this study, cobalt phosphate hydrate Co3(PO4)2.8H2O (CPH) is successfully deposited onto a nickel foam (NF) substrate using a single-step hydrothermal route. Electrode morphology comprises microflowers composed of seed-like structures, which then organize into radial or bundle-like patterns influenced by the synthesis temperatures. The electrode synthesized at 140 °C characterized by low overpotential and minimal Tafel slope value towards OER (312 mV and 212 mV/dec) and HER (320 mV and 164 mV/dec) at the minimum current density of 100 mA/cm2 and 50 mA/cm2, respectively. As a bifunctional catalyst for the overall water splitting, it shows a 1.62 V cell voltage at 10 mA/cm2. Additionally, same electrodes exhibited outstanding supercapacitor properties, including a high specific capacitance of 2901 F/g and a capacity of 560 mAh/g at 5 mA/cm2 current density, leading to energy and power densities of 112 Wh/kg and 956 W/kg, respectively. An asymmetric aqueous supercapacitor device, utilizing CPH as the cathode and carbon black as the anode, delivers a specific capacitance of 56.29 F/g at 5 mV/s, with energy and power densities of 7 Wh/kg and 1500 W/kg, respectively. The device retains 65.56 % of its initial performance after 5000 cycles, highlighting the practical functionality of CPH for energy storage applications.
{"title":"Hydrothermally synthesized hierarchically cobalt phosphate hydrate for water splitting and supercapacitor","authors":"Pratap K. Pawar , Lahu D. Namade , Harshada C. Yadav , Amruta A. Yadav , Tejas R. Bodake , Rupesh S. Pedanekar , Keshav Y. Rajpure","doi":"10.1016/j.jssc.2025.125751","DOIUrl":"10.1016/j.jssc.2025.125751","url":null,"abstract":"<div><div>In this study, cobalt phosphate hydrate Co<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>.8H<sub>2</sub>O (CPH) is successfully deposited onto a nickel foam (NF) substrate using a single-step hydrothermal route. Electrode morphology comprises microflowers composed of seed-like structures, which then organize into radial or bundle-like patterns influenced by the synthesis temperatures. The electrode synthesized at 140 °C characterized by low overpotential and minimal Tafel slope value towards OER (312 mV and 212 mV/dec) and HER (320 mV and 164 mV/dec) at the minimum current density of 100 mA/cm<sup>2</sup> and 50 mA/cm<sup>2</sup>, respectively. As a bifunctional catalyst for the overall water splitting, it shows a 1.62 V cell voltage at 10 mA/cm<sup>2</sup>. Additionally, same electrodes exhibited outstanding supercapacitor properties, including a high specific capacitance of 2901 F/g and a capacity of 560 mAh/g at 5 mA/cm<sup>2</sup> current density, leading to energy and power densities of 112 Wh/kg and 956 W/kg, respectively. An asymmetric aqueous supercapacitor device, utilizing CPH as the cathode and carbon black as the anode, delivers a specific capacitance of 56.29 F/g at 5 mV/s, with energy and power densities of 7 Wh/kg and 1500 W/kg, respectively. The device retains 65.56 % of its initial performance after 5000 cycles, highlighting the practical functionality of CPH for energy storage applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125751"},"PeriodicalIF":3.5,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614491","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}
Pub Date : 2025-11-24DOI: 10.1016/j.jssc.2025.125750
Abhay Singh
Polynanocrystalline AlFeO3 samples were synthesized in two batches via Sol–Gel method at fixed pH 9 with varying calcination conditions and precursor concentrations. Rietveld refinement of powder X-ray diffraction (PXRD) data revealed the coexistence of three rhombohedral AlFeO3 phases in both samples: a polar, non-centrosymmetric R3c phase and two nonpolar, centrosymmetric phases: R-3 and R-3c. Phase quantification analyses reveals that variation in precursor concentration along with calcination conditions significantly influences the relative phase fractions. DFT + U calculations using experimentally refined structures showed that the antiferromagnetic R3c phase is the most thermodynamically stable, followed by the R-3 phase with similar magnetic ordering and then R-3c phase, which stabilizes in a ferrimagnetic configuration. Electronic structure analysis confirmed semiconducting behavior for R-3 and R3c phases while R-3c phase exhibit metallic nature. Tunability of electronic conductivity from p to n-type as well as band gaps is evident in the range of 0.86–2.42 eV, because of structural variations across different phases and samples. Characterization using UV-VIS-NIR and FTIR spectroscopy revealed strong absorption in the 200–800 nm spectral region and IR-active modes corresponding to Al–O and Fe–O vibrations in AlFeO3 phases. Polar R3c phase demonstrate spontaneous polarization in range: 19.41–55.86 μC/cm2 with a large electronic contribution. These findings suggest that structural polymorphism—driven by symmetry breaking and crystallographic reordering—can be exploited to tune material functionality. By controlling phase composition through solution chemistry and thermal processing, we can tailor the magnetic, ferroelectric, and optoelectronic properties of AlFeO3-based materials for multifunctional ceramic applications.
{"title":"Coexistence of multiple rhombohedral phases in sol-gel synthesized polynanocrystalline AlFeO3 samples","authors":"Abhay Singh","doi":"10.1016/j.jssc.2025.125750","DOIUrl":"10.1016/j.jssc.2025.125750","url":null,"abstract":"<div><div>Polynanocrystalline AlFeO<sub>3</sub> samples were synthesized in two batches via Sol–Gel method at fixed pH 9 with varying calcination conditions and precursor concentrations. Rietveld refinement of powder X-ray diffraction (PXRD) data revealed the coexistence of three rhombohedral AlFeO<sub>3</sub> phases in both samples: a polar, non-centrosymmetric R3c phase and two nonpolar, centrosymmetric phases: R-3 and R-3c. Phase quantification analyses reveals that variation in precursor concentration along with calcination conditions significantly influences the relative phase fractions. DFT + U calculations using experimentally refined structures showed that the antiferromagnetic R3c phase is the most thermodynamically stable, followed by the R-3 phase with similar magnetic ordering and then R-3c phase, which stabilizes in a ferrimagnetic configuration. Electronic structure analysis confirmed semiconducting behavior for R-3 and R3c phases while R-3c phase exhibit metallic nature. Tunability of electronic conductivity from p to n-type as well as band gaps is evident in the range of 0.86–2.42 eV, because of structural variations across different phases and samples. Characterization using UV-VIS-NIR and FTIR spectroscopy revealed strong absorption in the 200–800 nm spectral region and IR-active modes corresponding to Al–O and Fe–O vibrations in AlFeO<sub>3</sub> phases. Polar R3c phase demonstrate spontaneous polarization in range: 19.41–55.86 μC/cm<sup>2</sup> with a large electronic contribution. These findings suggest that structural polymorphism—driven by symmetry breaking and crystallographic reordering—can be exploited to tune material functionality. By controlling phase composition through solution chemistry and thermal processing, we can tailor the magnetic, ferroelectric, and optoelectronic properties of AlFeO<sub>3</sub>-based materials for multifunctional ceramic applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125750"},"PeriodicalIF":3.5,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614493","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}
Pub Date : 2025-11-24DOI: 10.1016/j.jssc.2025.125752
Jinmin Zhang , Yiqi Yu , Liuzhen Feng , Renfu Li , Zhiwen Ao , Ying Yang , Yijian Sun , Jinsheng Liao
Optical temperature sensing materials have advanced significantly with scientific and technological progress. However, developing optical temperature sensing materials capable of high sensitivity under extreme conditions, such as high-temperature environments, remains a formidable challenge. Herein, a series of upconversion luminescence (UCL) phosphors (KMg)0·4In1·6Mo3O12: Yb3+/Er3+ with negative thermal quenching properties were prepared by high temperature solid-state method. The phase structure, microstructure, thermal stability and optical properties of the samples were characterized by temperature-dependent in-situ synchrotron radiation X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and photoluminescence (PL) spectroscopy. Excited by a 980 nm laser,the optimal sample (KMg)0·4In1·6Mo3O12: 45 %Yb3+/1 %Er3+ shows two strong green emission bands at 524/559 nm, corresponding to the 2H11/2/4S3/2 → 4I15/2 characteristic emissions of Er3+. There are also relatively weak red emission peaks corresponding to the 4F9/2 → 4I15/2 transition. The fluorescence intensity ratio (FIR) of the thermal coupled levels (TCLs) of Er3+(2H11/2/4S3/2) is adopted for optical temperature sensing, the maximum absolute sensitivity (Sa) and relative sensitivity (Sr) are determined to be 0.71 %K−1 and 0.45 %K−1 at 303 K respectively. Notably, this phosphor exhibits UCL achieves thermal enhancement of nearly 64 times at 573K. We utilized this property to design a PDMS film capable of temperature measurement and load temperature warning, demonstrating its potential for application in automated equipment.
{"title":"Thermal enhanced upconversion luminescence and optical temperature sensing of (KMg)0·4In1·6Mo3O12: Yb3+/Er3+ phosphors","authors":"Jinmin Zhang , Yiqi Yu , Liuzhen Feng , Renfu Li , Zhiwen Ao , Ying Yang , Yijian Sun , Jinsheng Liao","doi":"10.1016/j.jssc.2025.125752","DOIUrl":"10.1016/j.jssc.2025.125752","url":null,"abstract":"<div><div>Optical temperature sensing materials have advanced significantly with scientific and technological progress. However, developing optical temperature sensing materials capable of high sensitivity under extreme conditions, such as high-temperature environments, remains a formidable challenge. Herein, a series of upconversion luminescence (UCL) phosphors (KMg)<sub>0</sub><sub>·</sub><sub>4</sub>In<sub>1</sub><sub>·</sub><sub>6</sub>Mo<sub>3</sub>O<sub>12</sub>: Yb<sup>3+</sup>/Er<sup>3+</sup> with negative thermal quenching properties were prepared by high temperature solid-state method. The phase structure, microstructure, thermal stability and optical properties of the samples were characterized by temperature-dependent <em>in-situ</em> synchrotron radiation X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and photoluminescence (PL) spectroscopy. Excited by a 980 nm laser,the optimal sample (KMg)<sub>0</sub><sub>·</sub><sub>4</sub>In<sub>1</sub><sub>·</sub><sub>6</sub>Mo<sub>3</sub>O<sub>12</sub>: 45 %Yb<sup>3+</sup>/1 %Er<sup>3+</sup> shows two strong green emission bands at 524/559 nm, corresponding to the <sup>2</sup>H<sub>11/2</sub>/<sup>4</sup>S<sub>3/2</sub> → <sup>4</sup>I<sub>15/2</sub> characteristic emissions of Er<sup>3+</sup>. There are also relatively weak red emission peaks corresponding to the <sup>4</sup>F<sub>9/2</sub> → <sup>4</sup>I<sub>15/2</sub> transition. The fluorescence intensity ratio (FIR) of the thermal coupled levels (TCLs) of Er<sup>3+</sup>(<sup>2</sup>H<sub>11/2</sub>/<sup>4</sup>S<sub>3/2</sub>) is adopted for optical temperature sensing, the maximum absolute sensitivity (<em>S</em><sub><em>a</em></sub>) and relative sensitivity (<em>S</em><sub><em>r</em></sub>) are determined to be 0.71 %K<sup>−1</sup> and 0.45 %K<sup>−1</sup> at 303 K respectively. Notably, this phosphor exhibits UCL achieves thermal enhancement of nearly 64 times at 573K. We utilized this property to design a PDMS film capable of temperature measurement and load temperature warning, demonstrating its potential for application in automated equipment.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125752"},"PeriodicalIF":3.5,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614990","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}
Pub Date : 2025-11-21DOI: 10.1016/j.jssc.2025.125749
Ao Zhou , Jia Luo , Lesen Ma , Xiangfei Kong , Zhenguang Hu , Rongyang Fan , Peipei Zhang , Haijun Tan
The development of novel porous organic polymers (POPs) for efficient removal of radioactive iodine and high sensitivity detection of trace iron ions is vital for safeguarding environmental protection. Herein, a novel nitrogen-rich POPs (POP-En) with a conjugated π backbone was constructed as a multifunctional material for iodine trapping and fluorescence sensing. The specific surface area of BET of POP-En is 338.6 m2 g−1, and its pore structure is dominated by mesopores. POP-En adsorbed toxic iodine with capacities of 231.7 mg/g in hexane solution and 3.51 g/g in vapor phase. Recyclability experiments confirmed its good reusability. Additionally, the excellent conjugation properties and nitrogen-rich structure of POP-En enable it to be used not only for iodine trapping, but also as a sensitive sensor exhibiting fluorescence “turn-off” responses to Fe3+ and Fe2+ ions, with detection limits of 5.94 × 10−7 M and 1.51 × 10−7 M, respectively. In the presence of Fe3+ and Fe2+, the fluorescence intensity of POP-En was turned off due to the electron transfer mechanism. Theoretical calculations show that charge transfer occurs during fluorescence quenching. Currently, there are few reports in the literature of POPs being used as multifunctional materials for the capture of radioactive iodine and the detection of heavy metal ions.
{"title":"A novel anthracene-based porous organic polymer containing pyridine rings for efficient iodine capture and rapid fluorescence detection of iron ions","authors":"Ao Zhou , Jia Luo , Lesen Ma , Xiangfei Kong , Zhenguang Hu , Rongyang Fan , Peipei Zhang , Haijun Tan","doi":"10.1016/j.jssc.2025.125749","DOIUrl":"10.1016/j.jssc.2025.125749","url":null,"abstract":"<div><div>The development of novel porous organic polymers (POPs) for efficient removal of radioactive iodine and high sensitivity detection of trace iron ions is vital for safeguarding environmental protection. Herein, a novel nitrogen-rich POPs (<strong>POP-En</strong>) with a conjugated π backbone was constructed as a multifunctional material for iodine trapping and fluorescence sensing. The specific surface area of BET of <strong>POP-En</strong> is 338.6 m<sup>2</sup> g<sup>−1</sup>, and its pore structure is dominated by mesopores. <strong>POP-En</strong> adsorbed toxic iodine with capacities of 231.7 mg/g in hexane solution and 3.51 g/g in vapor phase. Recyclability experiments confirmed its good reusability. Additionally, the excellent conjugation properties and nitrogen-rich structure of <strong>POP-En</strong> enable it to be used not only for iodine trapping, but also as a sensitive sensor exhibiting fluorescence “turn-off” responses to Fe<sup>3+</sup> and Fe<sup>2+</sup> ions, with detection limits of 5.94 × 10<sup>−7</sup> M and 1.51 × 10<sup>−7</sup> M, respectively. In the presence of Fe<sup>3+</sup> and Fe<sup>2+</sup>, the fluorescence intensity of <strong>POP-En</strong> was turned off due to the electron transfer mechanism. Theoretical calculations show that charge transfer occurs during fluorescence quenching. Currently, there are few reports in the literature of POPs being used as multifunctional materials for the capture of radioactive iodine and the detection of heavy metal ions.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125749"},"PeriodicalIF":3.5,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614496","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}
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