Pub Date : 2024-12-13DOI: 10.1016/j.jssc.2024.125144
Defa Gu , Yue Yao , Xin Zhang , Yuanjing Cui, Guodong Qian
Iron-based metal-organic frameworks (MOFs) have been applied for oxygen evolution reaction (OER) due to their unique physicochemical properties. The relatively poor activity and conductivity limit the further development and use of iron-based MOFs. Here, regulating the electronic structure and the spin state through ion-induced skeleton reconstruction method to improve the catalytic performance is developed. The experimental and DFT calculation show that the introduction of indium ions promotes the iron active site from low spin state to high spin state, and the d-band center of the catalyst is significantly improved, which can enhance the oxygen adsorption and the conductivity of the catalyst to improve the OER performance. The MIL-88b-Fe0.950In0.050 shows the best catalytic performance, with an overpotential of only 243 mV at a current density of 100 mA cm−2. The catalytic activity of the catalyst remains undecayed after 110 h of continuous use.
{"title":"Regulating the electronic structure and spin state of iron-based metal-organic frameworks for efficient oxygen evolution electrocatalysis","authors":"Defa Gu , Yue Yao , Xin Zhang , Yuanjing Cui, Guodong Qian","doi":"10.1016/j.jssc.2024.125144","DOIUrl":"10.1016/j.jssc.2024.125144","url":null,"abstract":"<div><div>Iron-based metal-organic frameworks (MOFs) have been applied for oxygen evolution reaction (OER) due to their unique physicochemical properties. The relatively poor activity and conductivity limit the further development and use of iron-based MOFs. Here, regulating the electronic structure and the spin state through ion-induced skeleton reconstruction method to improve the catalytic performance is developed. The experimental and DFT calculation show that the introduction of indium ions promotes the iron active site from low spin state to high spin state, and the d-band center of the catalyst is significantly improved, which can enhance the oxygen adsorption and the conductivity of the catalyst to improve the OER performance. The MIL-88b-Fe<sub>0.950</sub>In<sub>0.050</sub> shows the best catalytic performance, with an overpotential of only 243 mV at a current density of 100 mA cm<sup>−2</sup>. The catalytic activity of the catalyst remains undecayed after 110 h of continuous use.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125144"},"PeriodicalIF":3.2,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143097769","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}
Na-Cu-Ge ternary clathrate films with about 0.5 μm in thickness were prepared on sapphire substrates by vacuum evaporation of Na on Cu–Ge composite films followed by lamp heating under vacuum. XRD measurements confirmed the syntheses of type II (Nax (CuzGe1-z)136) and type I (Na8(CuzGe1-z)46) clathrates. The former was obtained as a single phase from the Cu–Ge film with Cu inclusion of 4∼5 %, whereas the latter was earned as the phase of mixture of type II clathrate and Cu0.85Ge0.15 alloy from the films with Cu inclusion of 14 % or higher. Rietveld analyses of XRD data and Raman measurements indicated expansions of lattice constants by Cu inclusions in type I and II clathrate structures. The complete opacity observed in optical transmission indicates that Nax (CuzGe1-z)136 exhibit metallic behavior.
{"title":"Synthesis of Na-Cu-Ge ternary clathrates with type I and II structures in film form","authors":"Tun Naing Aye , Yuma Fukuda , Fumitaka Ohashi , Himanshu Shekhar Jha , Rahul Kumar , Pratima Agarwal , Tetsuji Kume","doi":"10.1016/j.jssc.2024.125155","DOIUrl":"10.1016/j.jssc.2024.125155","url":null,"abstract":"<div><div>Na-Cu-Ge ternary clathrate films with about 0.5 μm in thickness were prepared on sapphire substrates by vacuum evaporation of Na on Cu–Ge composite films followed by lamp heating under vacuum. XRD measurements confirmed the syntheses of type II (Na<sub><em>x</em></sub> (Cu<sub><em>z</em></sub>Ge<sub>1-<em>z</em></sub>)<sub>136</sub>) and type I (Na<sub>8</sub>(Cu<sub><em>z</em></sub>Ge<sub>1-<em>z</em></sub>)<sub>46</sub>) clathrates. The former was obtained as a single phase from the Cu–Ge film with Cu inclusion of 4∼5 %, whereas the latter was earned as the phase of mixture of type II clathrate and Cu<sub>0.85</sub>Ge<sub>0.15</sub> alloy from the films with Cu inclusion of 14 % or higher. Rietveld analyses of XRD data and Raman measurements indicated expansions of lattice constants by Cu inclusions in type I and II clathrate structures. The complete opacity observed in optical transmission indicates that Na<sub><em>x</em></sub> (Cu<sub><em>z</em></sub>Ge<sub>1-<em>z</em></sub>)<sub>136</sub> exhibit metallic behavior.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125155"},"PeriodicalIF":3.2,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143097768","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 : 2024-12-12DOI: 10.1016/j.jssc.2024.125152
Zunaira Shafiq , Nadia Akram , Saba Jamil , Khalid Mahmood Zia , Muhammad Ramzan Saeed Ashraf Janjua
The advancement of organic solar cell (OSC) technology depends on the creation of photovoltaic (PV) materials with enhanced conduction band characteristics electrochemical qualities, and power conversion efficiency (PCE). When constructing high-performance organic photovoltaics (OPVs) and optoelectronics, quantum chemical modelling is essential. In order to determine the most promising materials for OSCs, this study focuses on simulating and characterizing different novel non-fullerene donor-acceptor complexes (PYIT01–PYIT06), which are based on the PYIT molecule. The study assesses these compound's electrical properties, charge transport kinetics, and molecular structures using DFT and TD-DFT using the B3LYP/6-31G (d,p) basis set. Charge transfer studies, open-circuit voltage (Voc), density of states (DOS), transition density matrix (TDM), natural bond orbital (NBO) study, and molecular electrostatic potential (MEP) are all included in the investigation. The developed compounds have improved λmax values (769 nm in chloroform and 714.23 nm in the gas phase) and a lower electronic gap (Eg) of 0.577 eV and binding energy (Eb) of 1.03 eV when compared to the reference PY-IT molecule. Additionally, the designed molecule i.e. PY-IT06 have an open-circuit voltage (Voc) of 1.03 V and a fill factor (FF) of 88.54 %. Because of its higher exciton dissociation rate, PYIT06 exhibits the greatest promise for solar energy applications among them. These findings show that customized PYIT06-based non-fullerene materials are superior to conventional fullerene-based systems, opening the door to more effective and sustainable organic electronic devices. Our findings offer crucial insights into the design and the concept of guiding the overall stability, effectiveness, and performance of optoelectronic and solar energy conversion devices.
{"title":"Quantum chemical modelling of non-fullerene donor and acceptor compounds for high performance organic photovoltaics and optoelectronics","authors":"Zunaira Shafiq , Nadia Akram , Saba Jamil , Khalid Mahmood Zia , Muhammad Ramzan Saeed Ashraf Janjua","doi":"10.1016/j.jssc.2024.125152","DOIUrl":"10.1016/j.jssc.2024.125152","url":null,"abstract":"<div><div>The advancement of organic solar cell (OSC) technology depends on the creation of photovoltaic (PV) materials with enhanced conduction band characteristics electrochemical qualities, and power conversion efficiency (PCE). When constructing high-performance organic photovoltaics (OPVs) and optoelectronics, quantum chemical modelling is essential. In order to determine the most promising materials for OSCs, this study focuses on simulating and characterizing different novel non-fullerene donor-acceptor complexes (PYIT01–PYIT06), which are based on the PYIT molecule. The study assesses these compound's electrical properties, charge transport kinetics, and molecular structures using DFT and TD-DFT using the B3LYP/6-31G (d,p) basis set. Charge transfer studies, open-circuit voltage (Voc), density of states (DOS), transition density matrix (TDM), natural bond orbital (NBO) study, and molecular electrostatic potential (MEP) are all included in the investigation. The developed compounds have improved <em>λ</em><sub>max</sub> values (769 nm in chloroform and 714.23 nm in the gas phase) and a lower electronic gap (Eg) of 0.577 eV and binding energy (Eb) of 1.03 eV when compared to the reference PY-IT molecule. Additionally, the designed molecule i.e. PY-IT06 have an open-circuit voltage (Voc) of 1.03 V and a fill factor (FF) of 88.54 %. Because of its higher exciton dissociation rate, PYIT06 exhibits the greatest promise for solar energy applications among them. These findings show that customized PYIT06-based non-fullerene materials are superior to conventional fullerene-based systems, opening the door to more effective and sustainable organic electronic devices. Our findings offer crucial insights into the design and the concept of guiding the overall stability, effectiveness, and performance of optoelectronic and solar energy conversion devices.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125152"},"PeriodicalIF":3.2,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143097779","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 : 2024-12-12DOI: 10.1016/j.jssc.2024.125147
Shuai Deng , Yaxin Feng , Sai Zhang , Yi-Ning Li , Shengdong Zhang , Suning Ma , Anyuan Hu , Yi Liu
In this study, iodosodalite was successfully synthesized through subcritical hydrothermal synthesis and sintering, achieving lower sintering temperatures and reaction times compared to traditional methods, with the hydrothermal reaction lasting 1 h and the sintering temperature set at 600 °C. A series of tests were conducted to characterize the microstructure and chemical state of the material, as well as to analyze the conversion process between analcime and iodosodalite, revealing that analcime transforms into iodosodalite at sintering temperatures around 360–370 °C. The synthesized samples exhibited an even distribution of elements, and it was observed that higher hydrothermal temperatures and greater pressures resulted in finer grain sizes. Ultimately, the leaching rate of the synthesized iodosodalite was measured at 0.4 × 10−3 gm−2 d−1 on the seventh day.
{"title":"Immobilization of iodine waste via iodosodalite through subcritical hydrothermal method","authors":"Shuai Deng , Yaxin Feng , Sai Zhang , Yi-Ning Li , Shengdong Zhang , Suning Ma , Anyuan Hu , Yi Liu","doi":"10.1016/j.jssc.2024.125147","DOIUrl":"10.1016/j.jssc.2024.125147","url":null,"abstract":"<div><div>In this study, iodosodalite was successfully synthesized through subcritical hydrothermal synthesis and sintering, achieving lower sintering temperatures and reaction times compared to traditional methods, with the hydrothermal reaction lasting 1 h and the sintering temperature set at 600 °C. A series of tests were conducted to characterize the microstructure and chemical state of the material, as well as to analyze the conversion process between analcime and iodosodalite, revealing that analcime transforms into iodosodalite at sintering temperatures around 360–370 °C. The synthesized samples exhibited an even distribution of elements, and it was observed that higher hydrothermal temperatures and greater pressures resulted in finer grain sizes. Ultimately, the leaching rate of the synthesized iodosodalite was measured at 0.4 × 10<sup>−3</sup> gm<sup>−2</sup> d<sup>−1</sup> on the seventh day.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125147"},"PeriodicalIF":3.2,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093594","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 : 2024-12-12DOI: 10.1016/j.jssc.2024.125149
Heng Lin , Jiehong Chen , Yifan Yao , Gaojie Lu , Weiwei Huan , Na Ma , Wei Dai
Due to the limited Cd(II) absorption capacity and stability of single and simple metal-organic frameworks (MOFs), combining two MOF building blocks to create a core-shell MOF-in-MOF composite material offers a promising approach for efficiently capturing Cd(II) from aqueous solutions. Utilizing the epitaxial growth method, we successfully fabricated a core-shell structured (NH2-MIL-125)-in-(ZIF-67) (M-in-Z) composite material. The material underwent comprehensive characterization employing SEM, XRD, FT-IR, N2 adsorption-desorption, and diverse testing methods to evaluate its Cd(II) adsorption and removal capabilities in water environments. The Cd(II) adsorption capacities exhibited the sequence NH2-MIL-125 < ZIF-67 < M-in-Z(54). Adsorption isotherm results adhered to the Langmuir model, indicating a relatively ideal single-molecule layer adsorption process for Cd(II) on M-in-Z(54). The adsorption kinetics conformed to the pseudo-second-order model, indicating that equilibrium was reached in 30 min. Thermodynamic studies unveiled the spontaneous, exothermic nature of the M-in-Z(54) adsorption process, associated with an increase in degrees of freedom. Physical adsorption emerged as the primary driving force, complemented by chemical adsorption. Following five adsorption cycles, M-in-Z(54) sustained its Cd(II) adsorption performance at 92.56 % of the initial capacity, showcasing outstanding regeneration capability. Moreover, the structure and morphology of M-in-Z(54) remained intact after regeneration, demonstrating superior stability compared to the core-satellite structure. This conclusion highlights the promising potential of M-in-Z(54) as an environmentally friendly material for efficient Cd(II) removal.
{"title":"Enhancement capture capability of cadmium ions using a MOF-in-MOF composite","authors":"Heng Lin , Jiehong Chen , Yifan Yao , Gaojie Lu , Weiwei Huan , Na Ma , Wei Dai","doi":"10.1016/j.jssc.2024.125149","DOIUrl":"10.1016/j.jssc.2024.125149","url":null,"abstract":"<div><div>Due to the limited Cd(II) absorption capacity and stability of single and simple metal-organic frameworks (MOFs), combining two MOF building blocks to create a core-shell MOF-in-MOF composite material offers a promising approach for efficiently capturing Cd(II) from aqueous solutions. Utilizing the epitaxial growth method, we successfully fabricated a core-shell structured (NH<sub>2</sub>-MIL-125)-in-(ZIF-67) (M-in-Z) composite material. The material underwent comprehensive characterization employing SEM, XRD, FT-IR, N<sub>2</sub> adsorption-desorption, and diverse testing methods to evaluate its Cd(II) adsorption and removal capabilities in water environments. The Cd(II) adsorption capacities exhibited the sequence NH<sub>2</sub>-MIL-125 < ZIF-67 < M-in-Z(54). Adsorption isotherm results adhered to the Langmuir model, indicating a relatively ideal single-molecule layer adsorption process for Cd(II) on M-in-Z(54). The adsorption kinetics conformed to the pseudo-second-order model, indicating that equilibrium was reached in 30 min. Thermodynamic studies unveiled the spontaneous, exothermic nature of the M-in-Z(54) adsorption process, associated with an increase in degrees of freedom. Physical adsorption emerged as the primary driving force, complemented by chemical adsorption. Following five adsorption cycles, M-in-Z(54) sustained its Cd(II) adsorption performance at 92.56 % of the initial capacity, showcasing outstanding regeneration capability. Moreover, the structure and morphology of M-in-Z(54) remained intact after regeneration, demonstrating superior stability compared to the core-satellite structure. This conclusion highlights the promising potential of M-in-Z(54) as an environmentally friendly material for efficient Cd(II) removal.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125149"},"PeriodicalIF":3.2,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093597","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 : 2024-12-12DOI: 10.1016/j.jssc.2024.125150
Dapeng Li , Jinqiang Wu , Jiangtao Duan , Xiaoxu Liu , Jingjing Gong , Suxiang Ge
Exploring the practical method to grow high quality metal phthalocyanine (MPc) crystals and understanding their growth mechanism is significant for their applications. In this study, manganese phthalocyanine (MnPc) crystals were successfully synthesized using simple substance Mn and dicyanobenzene in the reaction medium of ethanediol without any other chemical reagents. The well shaped quadrangular MnPc crystals more than 500 μm were in situ grown on Mn slice surfaces via a simple solvothermal reaction. XPS analyses show that Mn has the mixed chemical state of +3 and + 4 in MnPc. Ethanediol acted as not only the solvent but also acidic catalyst to boost the ionization of dicyanobenzene. Different from the reported synthesis of MPc crystals, MnPc crystals could be formed at a wide temperature range of 100–190 °C. The reaction time is the only experimental parameter to regulate the crystal growth. To the best of our knowledge, this is the first report on in situ synthesis of the high quality MnPc crystals on Mn substrate by using a simple solvothermal method.
{"title":"Solvothermal growth of manganese phthalocyanine quadrangular crystals on Mn slice in ethanediol medium","authors":"Dapeng Li , Jinqiang Wu , Jiangtao Duan , Xiaoxu Liu , Jingjing Gong , Suxiang Ge","doi":"10.1016/j.jssc.2024.125150","DOIUrl":"10.1016/j.jssc.2024.125150","url":null,"abstract":"<div><div>Exploring the practical method to grow high quality metal phthalocyanine (MPc) crystals and understanding their growth mechanism is significant for their applications. In this study, manganese phthalocyanine (MnPc) crystals were successfully synthesized using simple substance Mn and dicyanobenzene in the reaction medium of ethanediol without any other chemical reagents. The well shaped quadrangular MnPc crystals more than 500 μm were in situ grown on Mn slice surfaces via a simple solvothermal reaction. XPS analyses show that Mn has the mixed chemical state of +3 and + 4 in MnPc. Ethanediol acted as not only the solvent but also acidic catalyst to boost the ionization of dicyanobenzene. Different from the reported synthesis of MPc crystals, MnPc crystals could be formed at a wide temperature range of 100–190 °C. The reaction time is the only experimental parameter to regulate the crystal growth. To the best of our knowledge, this is the first report on in situ synthesis of the high quality MnPc crystals on Mn substrate by using a simple solvothermal method.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125150"},"PeriodicalIF":3.2,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143149429","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 : 2024-12-11DOI: 10.1016/j.jssc.2024.125137
Sandesh K. Divekar , Vishnu R. Ajgaonkar , S. Nagabhusan Achary
Herein, the structure, vibrational and optical properties and thermal stability of [(CH3)2NH2][Pr(H2O) (SeO4)2], a double selenate of dimethylammonium and Pr(III) is reported. The double selenate was crystallized from the aqueous solution under controlled atmosphere and temperature. Crystal structure of the double salt was studied by single crystal X-ray diffraction studies. The compound has monoclinic (P21/n) lattice with bicapped trigonal prism [PrO7(OH2)], and tetrahedral (CH3)2NH2+ and SeO42─ entities as structure building units. The [PrO7(OH2)] unit share five of its vertex oxygen with five different selenate groups, one of its edges with a SeO42─ unit and one corner with one water molecule. These units are extended along a-direction as zig-zag chain of composition [Pr(H2O) (SeO4)2]─. This arrangement also leads to two O-μ bonds with two different SeO42─ units. These chains are linked together through the hydrogen bonds between coordinated water and SeO42─ oxygens forming negatively charged sheet of [Pr(H2O) (SeO4)2]─. These sheets are stacked along the [010] direction with an interlayer space of about 5.99 Å. The charge neutralization in the unit cell is attained by dimethylammonium ions occupied in between these sheets. The FTIR, Raman spectroscopic investigations indicated the characteristic vibrations of selenate, water, hydrated praseodymium and dimethylammonium groups. The compound was found to be thermally stable up to 373 K, and beyond it collapsed due to loss of coordinated water molecules. Subsequently, the (CH3)2NH2+, and SeO42─ ions are lost as (CH3)2NH, and SeO2. Diffused reflectance ultraviolet spectroscopic studies on powdered samples revealed band edge absorption at 4.9 eV. The photoluminescence studies showed the characteristic emission at 390 nm due to charge transfer fluorescence and other characteristics emission from Pr3+ ions.
{"title":"Preparation, crystal structure, thermal studies and optical properties of layered dimethylammonium praseodymium double selenate: [(CH3)2NH2][Pr(H2O) (SeO4)2]","authors":"Sandesh K. Divekar , Vishnu R. Ajgaonkar , S. Nagabhusan Achary","doi":"10.1016/j.jssc.2024.125137","DOIUrl":"10.1016/j.jssc.2024.125137","url":null,"abstract":"<div><div>Herein, the structure, vibrational and optical properties and thermal stability of [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Pr(H<sub>2</sub>O) (SeO<sub>4</sub>)<sub>2</sub>], a double selenate of dimethylammonium and Pr(III) is reported. The double selenate was crystallized from the aqueous solution under controlled atmosphere and temperature. Crystal structure of the double salt was studied by single crystal X-ray diffraction studies. The compound has monoclinic (<em>P</em>2<sub>1</sub><em>/n</em>) lattice with bicapped trigonal prism [PrO<sub>7</sub>(OH<sub>2</sub>)], and tetrahedral (CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub><sup>+</sup> and SeO<sub>4</sub><sup>2─</sup> entities as structure building units. The [PrO<sub>7</sub>(OH<sub>2</sub>)] unit share five of its vertex oxygen with five different selenate groups, one of its edges with a SeO<sub>4</sub><sup>2─</sup> unit and one corner with one water molecule. These units are extended along <em>a-</em>direction as zig-zag chain of composition [Pr(H<sub>2</sub>O) (SeO<sub>4</sub>)<sub>2</sub>]<sup>─</sup>. This arrangement also leads to two <em>O</em>-μ bonds with two different SeO<sub>4</sub><sup>2─</sup> units. These chains are linked together through the hydrogen bonds between coordinated water and SeO<sub>4</sub><sup>2─</sup> oxygens forming negatively charged sheet of [Pr(H<sub>2</sub>O) (SeO<sub>4</sub>)<sub>2</sub>]<sup>─</sup>. These sheets are stacked along the [010] direction with an interlayer space of about 5.99 Å. The charge neutralization in the unit cell is attained by dimethylammonium ions occupied in between these sheets. The FTIR, Raman spectroscopic investigations indicated the characteristic vibrations of selenate, water, hydrated praseodymium and dimethylammonium groups. The compound was found to be thermally stable up to 373 K, and beyond it collapsed due to loss of coordinated water molecules. Subsequently, the (CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub><sup>+</sup>, and SeO<sub>4</sub><sup>2─</sup> ions are lost as (CH<sub>3</sub>)<sub>2</sub>NH, and SeO<sub>2</sub>. Diffused reflectance ultraviolet spectroscopic studies on powdered samples revealed band edge absorption at 4.9 eV. The photoluminescence studies showed the characteristic emission at 390 nm due to charge transfer fluorescence and other characteristics emission from Pr<sup>3+</sup> ions.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125137"},"PeriodicalIF":3.2,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143097772","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}
The development of efficient p-type transparent conducting films is important for solar cell applications. P-type semiconductors tend to have higher resistivities, lower carrier concentrations, and lower mobilities than n-type transparent conductive oxides. To improve the quality of CuBr1-xIx (CuBrI) as a transparent p-type semiconductor, a CuBrI film fabricated by spin-coating was soaked in a potassium bromide solution up to three times. Bromination increased the number of Br atoms in the film and decreased the resistivity. However, bromination increased the surface precipitation and roughness while reducing the film thickness. Photoluminescence (PL) spectroscopy demonstrated strong blue emission and weak red emission around 2.83 eV and 1.8 eV, respectively. A Gaussian analysis of the strong blue emission resolved the emission at 2.83 eV (P1) from free exciton recombination luminescence and a new emission at 2.75 eV (P2). The intensity of the exciton luminescence increased after bromination. P2 was inferred to originate from Cu defects, and the area ratio of P2 to P1 increased with the number of bromination cycles. The results of the PL and resistivity measurements indicated that bromination improved the quality of the CuBrI thin films; however, excessive bromination was counterproductive because it deteriorated the films. These findings demonstrate the importance of the halogen ratio on CuBrI film performance in transparent solar cell applications.
{"title":"Improvement of CuBr1–xIx absorption layers in transparent solar cells by halide-solution soaking","authors":"Daikichi Tamai, Kotaro Yukinaga, Koya Ochiai, Ayaka Kanai, Kunihiko Tanaka","doi":"10.1016/j.jssc.2024.125148","DOIUrl":"10.1016/j.jssc.2024.125148","url":null,"abstract":"<div><div>The development of efficient p-type transparent conducting films is important for solar cell applications. P-type semiconductors tend to have higher resistivities, lower carrier concentrations, and lower mobilities than n-type transparent conductive oxides. To improve the quality of CuBr<sub>1-<em>x</em></sub>I<sub><em>x</em></sub> (CuBrI) as a transparent p-type semiconductor, a CuBrI film fabricated by spin-coating was soaked in a potassium bromide solution up to three times. Bromination increased the number of Br atoms in the film and decreased the resistivity. However, bromination increased the surface precipitation and roughness while reducing the film thickness. Photoluminescence (PL) spectroscopy demonstrated strong blue emission and weak red emission around 2.83 eV and 1.8 eV, respectively. A Gaussian analysis of the strong blue emission resolved the emission at 2.83 eV (P1) from free exciton recombination luminescence and a new emission at 2.75 eV (P2). The intensity of the exciton luminescence increased after bromination. P2 was inferred to originate from Cu defects, and the area ratio of P2 to P1 increased with the number of bromination cycles. The results of the PL and resistivity measurements indicated that bromination improved the quality of the CuBrI thin films; however, excessive bromination was counterproductive because it deteriorated the films. These findings demonstrate the importance of the halogen ratio on CuBrI film performance in transparent solar cell applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125148"},"PeriodicalIF":3.2,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093598","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 : 2024-12-08DOI: 10.1016/j.jssc.2024.125143
Jie Ling , Oluwasegun Yusuf Raji , Hailong Peng , Zhehui Weng , Isabelle Bao , Chloe Jones , Addison Malone , Tyler L. Spano , Andrew Miskowiec , Mohammed Al-Fahdi , Ming Hu
Four new d0 transition metal tellurites, namely InVTeO6 (1), β-InVTe2O8 (2), FeVTe2O8 (3), and Fe2MoTe2O10 (4), were synthesized under hydrothermal conditions, and their crystal structures were determined using single-crystal X-ray diffraction. Compound 1 crystallizes in the noncentrosymmetric space group P212121 (No. 19), with unit cell parameters of a = 5.0759(2) Å, b = 8.5030(3) Å, c = 11.6376(5) Å, V = 502.28(3) Å3, and Z = 4, while the other three compounds crystallize in centrosymmetric structures, with space group Cmca and unit cell parameters of a = 7.0633(7) Å, b = 8.962(1) Å, c = 20.162(2) Å, V = 1276.3(2) Å3, and Z = 8 for compound 2, space group P21/n and unit cell parameters of a = 7.8901(2) Å, b = 4.9617(1) Å, c = 16.4290(3) Å, β = 93.6198(8)°, V = 641.88(2) Å3, and Z = 4 for compound 3, and space group Pnma and unit cell parameters of a = 8.7878(2) Å, b = 6.1327(2) Å, c = 15.2423(4) Å, V = 821.45(4) Å3, and Z = 4 for compound 4. Compound 3 adopts a two-dimensional (2D) sheet structure composed of FeO6 octahedra, VO4 tetrahedra, and TeO4 polyhedra. The other three compounds exhibit three-dimensional (3D) framework structures: Compound 1 is built from InO6 octahedra, VO4 tetrahedra, TeO4 polyhedra; Compound 2 consists of InO6 octahedra, VO5 square pyramids, and TeO3 polyhedra; and Compound 4 is composed of FeO6 octahedra, MoO6 octahedra, and TeO3 polyhedra. The band structures, density of states, and electron localization functions of all four compounds were calculated. The vibrational spectra were examined for compounds 1, 2, and 4. Additionally, powder X-ray diffraction, element analysis, and thermogravimetric analysis were conducted for compound 4.
{"title":"Syntheses and crystal structures of four new d0 transition metal tellurites","authors":"Jie Ling , Oluwasegun Yusuf Raji , Hailong Peng , Zhehui Weng , Isabelle Bao , Chloe Jones , Addison Malone , Tyler L. Spano , Andrew Miskowiec , Mohammed Al-Fahdi , Ming Hu","doi":"10.1016/j.jssc.2024.125143","DOIUrl":"10.1016/j.jssc.2024.125143","url":null,"abstract":"<div><div>Four new d<sup>0</sup> transition metal tellurites, namely InVTeO<sub>6</sub> (<strong>1</strong>), <em>β</em>-InVTe<sub>2</sub>O<sub>8</sub> (<strong>2</strong>), FeVTe<sub>2</sub>O<sub>8</sub> (<strong>3</strong>), and Fe<sub>2</sub>MoTe<sub>2</sub>O<sub>10</sub> (<strong>4</strong>), were synthesized under hydrothermal conditions, and their crystal structures were determined using single-crystal X-ray diffraction. Compound 1 crystallizes in the noncentrosymmetric space group <em>P</em>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub> (No. 19), with unit cell parameters of a = 5.0759(2) Å, b = 8.5030(3) Å, c = 11.6376(5) Å, V = 502.28(3) Å<sup>3</sup>, and Z = 4, while the other three compounds crystallize in centrosymmetric structures, with space group <em>Cmca</em> and unit cell parameters of a = 7.0633(7) Å, b = 8.962(1) Å, c = 20.162(2) Å, V = 1276.3(2) Å<sup>3</sup>, and Z = 8 for compound 2, space group <em>P</em>2<sub>1</sub>/n and unit cell parameters of a = 7.8901(2) Å, b = 4.9617(1) Å, c = 16.4290(3) Å, β = 93.6198(8)°, V = 641.88(2) Å<sup>3</sup>, and Z = 4 for compound 3, and space group <em>Pnma</em> and unit cell parameters of a = 8.7878(2) Å, b = 6.1327(2) Å, c = 15.2423(4) Å, V = 821.45(4) Å<sup>3</sup>, and Z = 4 for compound 4. Compound 3 adopts a two-dimensional (2D) sheet structure composed of FeO<sub>6</sub> octahedra, VO<sub>4</sub> tetrahedra, and TeO<sub>4</sub> polyhedra. The other three compounds exhibit three-dimensional (3D) framework structures: Compound 1 is built from InO<sub>6</sub> octahedra, VO<sub>4</sub> tetrahedra, TeO<sub>4</sub> polyhedra; Compound 2 consists of InO<sub>6</sub> octahedra, VO<sub>5</sub> square pyramids, and TeO<sub>3</sub> polyhedra; and Compound 4 is composed of FeO<sub>6</sub> octahedra, MoO<sub>6</sub> octahedra, and TeO<sub>3</sub> polyhedra. The band structures, density of states, and electron localization functions of all four compounds were calculated. The vibrational spectra were examined for compounds 1, 2, and 4. Additionally, powder X-ray diffraction, element analysis, and thermogravimetric analysis were conducted for compound 4.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125143"},"PeriodicalIF":3.2,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093588","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 : 2024-12-06DOI: 10.1016/j.jssc.2024.125136
Fengling Luo, Ling Guo, Jinji Li
Electrocatalytic co-reduction of carbon dioxide (CO2) and nitrate (NO3−) to methylamine (MMA) has been recognized as a promising pathway for the electrochemical synthesis of MMA. However, the catalytic mechanism of electrosynthesis of methylamine is still unclear, making this study challenging. In this paper, the performance of phthalocyanine-porphyrin tandem catalysts for the electrocatalytic synthesis of methylamine by the co-reduction of NO3− and CO2 was studied by Density Functional Theory (DFT). The FeZr-Pc-Co–N3O–Por COFs catalyst was found to have efficient performance for the electrosynthesis of methylamine with a limiting potential of −0.56 eV. Meanwhile, we found that the high catalytic activity of FeZr-Pc•Co–N3O-Por COFs catalysts originates from the “donate-back” mechanism of electrons between the active sites of the catalyst substrate and the reactants CO2 and NO3− molecules. The theoretical understanding of electrocatalytic NO3− and CO2 co-reduction for methylamine synthesis over tandem catalysts is provided by this paper. It creates new opportunities for the logical development of effective catalysts for methylamine electrosynthesis.
{"title":"Theoretical study on the synthesis of methylamine by electrocatalytic CO2 and NO3− co-reduction","authors":"Fengling Luo, Ling Guo, Jinji Li","doi":"10.1016/j.jssc.2024.125136","DOIUrl":"10.1016/j.jssc.2024.125136","url":null,"abstract":"<div><div>Electrocatalytic co-reduction of carbon dioxide (CO<sub>2</sub>) and nitrate (NO<sub>3</sub><sup>−</sup>) to methylamine (MMA) has been recognized as a promising pathway for the electrochemical synthesis of MMA. However, the catalytic mechanism of electrosynthesis of methylamine is still unclear, making this study challenging. In this paper, the performance of phthalocyanine-porphyrin tandem catalysts for the electrocatalytic synthesis of methylamine by the co-reduction of NO<sub>3</sub><sup>−</sup> and CO<sub>2</sub> was studied by Density Functional Theory (DFT). The FeZr-<em>Pc</em>-Co–N<sub>3</sub>O–Por COFs catalyst was found to have efficient performance for the electrosynthesis of methylamine with a limiting potential of −0.56 eV. Meanwhile, we found that the high catalytic activity of FeZr-<em>Pc</em>•Co–N<sub>3</sub>O-Por COFs catalysts originates from the “donate-back” mechanism of electrons between the active sites of the catalyst substrate and the reactants CO<sub>2</sub> and NO<sub>3</sub><sup>−</sup> molecules. The theoretical understanding of electrocatalytic NO<sub>3</sub><sup>−</sup> and CO<sub>2</sub> co-reduction for methylamine synthesis over tandem catalysts is provided by this paper. It creates new opportunities for the logical development of effective catalysts for methylamine electrosynthesis.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125136"},"PeriodicalIF":3.2,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093593","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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