Pub Date : 2024-10-28DOI: 10.1021/acs.cgd.4c0106710.1021/acs.cgd.4c01067
Bomi Kim, and , Kitae Kim*,
Cryoprotective polyols play a crucial role in inhibiting ice crystal growth, reducing the size of bulk ice crystals in polycrystalline structures, and increasing the volume of ice grain boundaries relative to the total solution volume. This study suggests that these properties enable cryoprotective polyols to accelerate the reduction of hexavalent chromium (Cr(VI)) in ice despite the reducing agents being limited to aqueous environments. This reaction is mainly caused by the accumulation of cryoprotective polyols and Cr(VI) at the ice grain boundaries formed during freezing (i.e., the freeze concentration effect). Upon freezing a mixture of cryoprotective polyols and a 20 μM Cr(VI) solution, over 90% reduction in Cr(VI) concentration was achieved within 24 h. Higher concentrations of cryoprotective polyols in Cr(VI) enhanced the reduction kinetics of Cr(VI) over the same reaction time, implying that the cryoprotective polyols function as reducing agents under freezing conditions. Confocal Raman spectroscopy confirmed cryoprotective polyols bind to ice crystal surfaces and concentrate Cr(VI) at the ice grain boundaries. Notably, the reductive capability of cryoprotective polyols toward Cr(VI) was observed under freezing conditions, using an electroplating wastewater sample contaminated with Cr(VI) as a model system, whereas negligible reduction was observed in the aqueous phase. Enhanced Cr(VI) reduction by cryoprotective polyols in frozen solutions presents a viable approach for treating contaminated wastewater and contributes to understanding the self-purification mechanism in natural environments where these polyols are present.
{"title":"Cryoprotective Polyol-Induced Ice Microstructure Development and Enhanced Chromium(VI) Reduction in Polycrystalline Structures","authors":"Bomi Kim, and , Kitae Kim*, ","doi":"10.1021/acs.cgd.4c0106710.1021/acs.cgd.4c01067","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01067https://doi.org/10.1021/acs.cgd.4c01067","url":null,"abstract":"<p >Cryoprotective polyols play a crucial role in inhibiting ice crystal growth, reducing the size of bulk ice crystals in polycrystalline structures, and increasing the volume of ice grain boundaries relative to the total solution volume. This study suggests that these properties enable cryoprotective polyols to accelerate the reduction of hexavalent chromium (Cr(VI)) in ice despite the reducing agents being limited to aqueous environments. This reaction is mainly caused by the accumulation of cryoprotective polyols and Cr(VI) at the ice grain boundaries formed during freezing (i.e., the freeze concentration effect). Upon freezing a mixture of cryoprotective polyols and a 20 μM Cr(VI) solution, over 90% reduction in Cr(VI) concentration was achieved within 24 h. Higher concentrations of cryoprotective polyols in Cr(VI) enhanced the reduction kinetics of Cr(VI) over the same reaction time, implying that the cryoprotective polyols function as reducing agents under freezing conditions. Confocal Raman spectroscopy confirmed cryoprotective polyols bind to ice crystal surfaces and concentrate Cr(VI) at the ice grain boundaries. Notably, the reductive capability of cryoprotective polyols toward Cr(VI) was observed under freezing conditions, using an electroplating wastewater sample contaminated with Cr(VI) as a model system, whereas negligible reduction was observed in the aqueous phase. Enhanced Cr(VI) reduction by cryoprotective polyols in frozen solutions presents a viable approach for treating contaminated wastewater and contributes to understanding the self-purification mechanism in natural environments where these polyols are present.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585755","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-25DOI: 10.1021/acs.cgd.4c0122010.1021/acs.cgd.4c01220
Xiaoming Wang, Li Li, Yan Lin, Jin Xu, Jiatao Zhao, Xiaoguang Zhang*, Fei Wang* and Xiaolin Wang,
The use of porous media as a fixed bed for promoting methane hydrate formation has been endowed with great potential in hydrate-based energy storage. In this work, a graphene aerogel (GA) with a one-piece structure and ultralight weight was prepared and adopted for the first time as a fixed bed for methane hydrate formation. In particular, the effects of the filling ratio and hydrophobic–hydrophilic properties of GA on the promotion efficiency were comprehensively investigated. In the range of 84–95%, a lower filling ratio resulted in higher promotion efficiency, which at 84% increased the methane storage capacity and apparent storage capacity from 114.4 ± 7.6 and 52.4 ± 6.7 V/V to 146.3 ± 6.5 and 91.1 ± 13.0 V/V, respectively. Cryo-scanning electron microscopy (Cryo-SEM) demonstrated that the hydrates formed in the inner pores of GA but also revealed the existence of empty pores, indicating that part of the reaction solution migrated out of the GA. Fortunately, by regulating the hydrophilic–hydrophobic properties of GA, the migration of the reaction solution during hydrate growth could be controlled, and the methane storage capacity could be optimized. More importantly, GA produced excellent advantages in terms of gravimetric storage capacity over traditional media and, therefore, produced great potential in serving as an ultralight fixed bed for the industrial application of hydrate-based energy storage.
将多孔介质用作促进甲烷水合物形成的固定床在基于水合物的能源储存方面具有巨大潜力。本研究首次制备并采用了具有一体式结构和超轻重量的石墨烯气凝胶(GA)作为甲烷水合物形成的固定床。特别是全面研究了石墨烯气凝胶的填充率和疏水亲水特性对促进效率的影响。在 84-95% 的范围内,填充率越低,促进效率越高,当填充率为 84% 时,甲烷储存量和表观储存量分别从 114.4 ± 7.6 和 52.4 ± 6.7 V/V 提高到 146.3 ± 6.5 和 91.1 ± 13.0 V/V。低温扫描电子显微镜(Cryo-SEM)显示,水合物形成于 GA 的内孔,但同时也发现了空孔的存在,表明部分反应溶液从 GA 中迁移出来。幸运的是,通过调节 GA 的亲水疏水特性,可以控制水合物生长过程中反应溶液的迁移,从而优化甲烷的储存能力。更重要的是,与传统介质相比,GA 在重力储存能力方面具有卓越的优势,因此在作为超轻固定床用于水合物储能的工业应用方面具有巨大潜力。
{"title":"Methane Hydrates Formed in a Porous Graphene Aerogel for Energy Storage","authors":"Xiaoming Wang, Li Li, Yan Lin, Jin Xu, Jiatao Zhao, Xiaoguang Zhang*, Fei Wang* and Xiaolin Wang, ","doi":"10.1021/acs.cgd.4c0122010.1021/acs.cgd.4c01220","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01220https://doi.org/10.1021/acs.cgd.4c01220","url":null,"abstract":"<p >The use of porous media as a fixed bed for promoting methane hydrate formation has been endowed with great potential in hydrate-based energy storage. In this work, a graphene aerogel (GA) with a one-piece structure and ultralight weight was prepared and adopted for the first time as a fixed bed for methane hydrate formation. In particular, the effects of the filling ratio and hydrophobic–hydrophilic properties of GA on the promotion efficiency were comprehensively investigated. In the range of 84–95%, a lower filling ratio resulted in higher promotion efficiency, which at 84% increased the methane storage capacity and apparent storage capacity from 114.4 ± 7.6 and 52.4 ± 6.7 V/V to 146.3 ± 6.5 and 91.1 ± 13.0 V/V, respectively. Cryo-scanning electron microscopy (Cryo-SEM) demonstrated that the hydrates formed in the inner pores of GA but also revealed the existence of empty pores, indicating that part of the reaction solution migrated out of the GA. Fortunately, by regulating the hydrophilic–hydrophobic properties of GA, the migration of the reaction solution during hydrate growth could be controlled, and the methane storage capacity could be optimized. More importantly, GA produced excellent advantages in terms of gravimetric storage capacity over traditional media and, therefore, produced great potential in serving as an ultralight fixed bed for the industrial application of hydrate-based energy storage.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585597","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-25DOI: 10.1021/acs.cgd.4c0100210.1021/acs.cgd.4c01002
Yongjian Ma, Jiheon Kwon, Rui Ji and Rosa M. Espinosa-Marzal*,
Bone mineralization relies on the interaction between collagen and minerals to control bone growth and multiscale hierarchical structure. Urged by the increasing need for bone defect repairs, tissue engineering searches for biocompatible materials to assist and enhance repairs. One potential avenue is to use hydrogels as organic scaffolds to control nucleation and growth of bonelike minerals. Here, two biocompatible polymers, polyacrylamide and agarose, were selected for the mineralization of hydroxyapatite, and the mineralization kinetics was investigated in the presence of calcium carbonate (to simulate early bone formation conditions) and in its absence. The results of this work show that agarose and polyacrylamide lead to different polymer–mineral interactions, which influence the stabilization of carbonate and phosphate precursors and thereby the onset of the crystallization of hydroxyapatite and more so in the presence of carbonate. In both hydrogels, amorphous calcium carbonate and hydroxyapatite are noncongruent, and amorphous calcium phosphate forms as a precursor. This distinct interaction between the mineral and agarose vs polyacrylamide leads to different microstructures and thereby mechanical responses. This research not only advances our understanding of the influence of mineral–polymer interactions on hydroxyapatite mineralization but also provides new opportunities for designing biomaterials for specific applications.
{"title":"Polymer–Mineral Interaction Influences the Mineralization of Hydroxyapatite in Hydrogels","authors":"Yongjian Ma, Jiheon Kwon, Rui Ji and Rosa M. Espinosa-Marzal*, ","doi":"10.1021/acs.cgd.4c0100210.1021/acs.cgd.4c01002","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01002https://doi.org/10.1021/acs.cgd.4c01002","url":null,"abstract":"<p >Bone mineralization relies on the interaction between collagen and minerals to control bone growth and multiscale hierarchical structure. Urged by the increasing need for bone defect repairs, tissue engineering searches for biocompatible materials to assist and enhance repairs. One potential avenue is to use hydrogels as organic scaffolds to control nucleation and growth of bonelike minerals. Here, two biocompatible polymers, polyacrylamide and agarose, were selected for the mineralization of hydroxyapatite, and the mineralization kinetics was investigated in the presence of calcium carbonate (to simulate early bone formation conditions) and in its absence. The results of this work show that agarose and polyacrylamide lead to different polymer–mineral interactions, which influence the stabilization of carbonate and phosphate precursors and thereby the onset of the crystallization of hydroxyapatite and more so in the presence of carbonate. In both hydrogels, amorphous calcium carbonate and hydroxyapatite are noncongruent, and amorphous calcium phosphate forms as a precursor. This distinct interaction between the mineral and agarose vs polyacrylamide leads to different microstructures and thereby mechanical responses. This research not only advances our understanding of the influence of mineral–polymer interactions on hydroxyapatite mineralization but also provides new opportunities for designing biomaterials for specific applications.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585787","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-24DOI: 10.1021/acs.cgd.4c0119710.1021/acs.cgd.4c01197
Paulina Kalle*, Stanislav I. Bezzubov, Lyudmila G. Kuzmina and Andrei V. Churakov,
Potassium, sodium, and calcium salts of sorbic acid (CH3–CH═CH–CH═CH–COOH) are widely used food preservatives. Despite the industrial relevance, their solid-state chemistry associated with photoreactivity and heat-induced transformations of double bonds remains misunderstood, mostly because of the lack of structural information. Herein, we report a comprehensive structural, thermal, and spectroscopic study of the above sorbates along with previously unknown normal and acid ammonium sorbates for comparison. Although all of the crystal structures exhibit a similar layered motif and carboxylate coordination, in potassium sorbate, there is an additional noncovalent interaction between K+ and the Cα═Cβ bond that bestows the salt with unique thermal properties. In turn, only the acid ammonium sorbate has a preorganization for [2 + 2] photocycloaddition, as reflected by its fast amorphization under soft UV irradiation, opposite to the other salts. The experimental results are discussed in the context of related metal carboxylates and the application and analysis of the studied salts in food industry.
{"title":"New Insights into the Structure, Thermal Properties, and Photostability of Industrially Relevant Salts of Sorbic Acid","authors":"Paulina Kalle*, Stanislav I. Bezzubov, Lyudmila G. Kuzmina and Andrei V. Churakov, ","doi":"10.1021/acs.cgd.4c0119710.1021/acs.cgd.4c01197","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01197https://doi.org/10.1021/acs.cgd.4c01197","url":null,"abstract":"<p >Potassium, sodium, and calcium salts of sorbic acid (CH<sub>3</sub>–CH═CH–CH═CH–COOH) are widely used food preservatives. Despite the industrial relevance, their solid-state chemistry associated with photoreactivity and heat-induced transformations of double bonds remains misunderstood, mostly because of the lack of structural information. Herein, we report a comprehensive structural, thermal, and spectroscopic study of the above sorbates along with previously unknown normal and acid ammonium sorbates for comparison. Although all of the crystal structures exhibit a similar layered motif and carboxylate coordination, in potassium sorbate, there is an additional noncovalent interaction between K<sup>+</sup> and the C<sub>α</sub>═C<sub>β</sub> bond that bestows the salt with unique thermal properties. In turn, only the acid ammonium sorbate has a preorganization for [2 + 2] photocycloaddition, as reflected by its fast amorphization under soft UV irradiation, opposite to the other salts. The experimental results are discussed in the context of related metal carboxylates and the application and analysis of the studied salts in food industry.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-24DOI: 10.1021/acs.cgd.4c0094510.1021/acs.cgd.4c00945
Zhuohao Jiao, Jiale Mu, Ruiquan Guo, Xuechuan Huang, Yan Fu, Fu Hao, Lei Nie*, Lei Wang* and Yuheng Liu*,
Organic azides are extensively utilized in organic synthesis and clinical drug development. However, the commonly employed catalysts for the preparation of organic azides, such as inorganic salts and simple metal complexes, often suffer from low yields and the production of byproducts. In this study, we report the rational synthesis of a porous, cluster-based bimetallic metal–organic framework (MOF) with a large nanocage of 1 nm in diameter, termed compound 1, designed for this specific reaction. Compound 1 exhibits exceptional solvent stability, remaining stable even in the presence of corrosive triethylamine. Catalytic investigations revealed that compound 1 serves as an effective catalyst for the reaction of primary amines with TfN3, yielding various organic azides under mild conditions. Moreover, this MOF catalyst demonstrates significant catalytic activity for the aminoglycoside drug kanamycin A. The reaction proceeds smoothly with compound 1, producing fewer byproducts and exhibiting good regioselectivity. Additionally, the catalyst can be reused at least five times without a noticeable decrease in catalytic activity. Notably, this represents the first application of MOF materials in the amino diazotization reaction.
{"title":"Cluster-Based Bimetallic 3d–4s {CuIn} Metal–Organic Framework for Efficiently Catalyzing Diazotization of Primary Amines","authors":"Zhuohao Jiao, Jiale Mu, Ruiquan Guo, Xuechuan Huang, Yan Fu, Fu Hao, Lei Nie*, Lei Wang* and Yuheng Liu*, ","doi":"10.1021/acs.cgd.4c0094510.1021/acs.cgd.4c00945","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00945https://doi.org/10.1021/acs.cgd.4c00945","url":null,"abstract":"<p >Organic azides are extensively utilized in organic synthesis and clinical drug development. However, the commonly employed catalysts for the preparation of organic azides, such as inorganic salts and simple metal complexes, often suffer from low yields and the production of byproducts. In this study, we report the rational synthesis of a porous, cluster-based bimetallic metal–organic framework (MOF) with a large nanocage of 1 nm in diameter, termed compound <b>1</b>, designed for this specific reaction. Compound <b>1</b> exhibits exceptional solvent stability, remaining stable even in the presence of corrosive triethylamine. Catalytic investigations revealed that compound <b>1</b> serves as an effective catalyst for the reaction of primary amines with TfN<sub>3</sub>, yielding various organic azides under mild conditions. Moreover, this MOF catalyst demonstrates significant catalytic activity for the aminoglycoside drug kanamycin A. The reaction proceeds smoothly with compound <b>1</b>, producing fewer byproducts and exhibiting good regioselectivity. Additionally, the catalyst can be reused at least five times without a noticeable decrease in catalytic activity. Notably, this represents the first application of MOF materials in the amino diazotization reaction.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymorphism is widespread in energetic materials and has an important influence on the properties of energy materials. 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a typical representative of third-generation energetic materials and the most advanced non-nuclear single explosive currently available, with great potential and application prospects in the charge of new weapons and equipment. In this article, the polymorphic phenomenon and the structure and property of energetic materials are briefly elaborated. Meanwhile, the thermodynamic relationship and phase transition mechanism of the polymorphs are deeply analyzed. Moreover, the research progress of CL-20 polymorphic transformation and its effect on performance is reviewed. The modification and inhibition strategies of CL-20 polymorphic transformation such as coating technology, additive technology, and cocrystal technology are mainly introduced. Furthermore, based on the control method of drug polymorphs, the development trend and the promising perspectives of energetic crystal materials, especially CL-20, are also discussed and proposed.
{"title":"Polymorphism of CL-20 and the Modification and Inhibition Strategies for Its Crystal Transformation","authors":"Hui Wang, Shifan Xu, Hongtu Zhao, Wenbo Wu, Na Wang*, Ting Wang, Xin Huang, Lina Zhou, Ying Bao* and Hongxun Hao, ","doi":"10.1021/acs.cgd.4c0106010.1021/acs.cgd.4c01060","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01060https://doi.org/10.1021/acs.cgd.4c01060","url":null,"abstract":"<p >Polymorphism is widespread in energetic materials and has an important influence on the properties of energy materials. 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a typical representative of third-generation energetic materials and the most advanced non-nuclear single explosive currently available, with great potential and application prospects in the charge of new weapons and equipment. In this article, the polymorphic phenomenon and the structure and property of energetic materials are briefly elaborated. Meanwhile, the thermodynamic relationship and phase transition mechanism of the polymorphs are deeply analyzed. Moreover, the research progress of CL-20 polymorphic transformation and its effect on performance is reviewed. The modification and inhibition strategies of CL-20 polymorphic transformation such as coating technology, additive technology, and cocrystal technology are mainly introduced. Furthermore, based on the control method of drug polymorphs, the development trend and the promising perspectives of energetic crystal materials, especially CL-20, are also discussed and proposed.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-23DOI: 10.1021/acs.cgd.4c0026410.1021/acs.cgd.4c00264
R. Corey White*, Morgan Bergthold, Aaron Muhowski, Leland Nordin, Iris Okoro, Hussein Hijazi, Leonard Feldman, Daniel Wasserman and Seth R. Bank,
InSb-based dilute-bismide alloys present a unique opportunity to span the entirety of the long-wave infrared with a bulk, lattice-matched III–V alloy that boasts greatly reduced toxicity compared to the current state-of-the-art, Hg1–xCdxTe. By incorporating both bismuth and arsenic in the appropriate proportions, we demonstrated InAs0.004Sb0.983Bi0.013 lattice-matched to commercially available InSb substrates. A kinetically limited growth regime that combined low substrate temperatures, V/III flux ratios near unity, and a relatively fast growth rate, mitigated phase separation and resulted in films with excellent structural and optical quality. In particular, the bismuth incorporation was estimated to be approximately 95% substitutional and photoluminescence from the alloy was observed at elevated temperatures up to 400 K exhibiting significant wavelength extension beyond that of InSb, out to 7.6 μm at room temperature. Furthermore, the first antimony-rich InAsySb1–x–yBix photodetector was fabricated and showed a longer cutoff wavelength than that of an InSb control detector due to the bandgap reduction caused by bismuth and arsenic incorporation. This highlights that emission and detection from InAs0.004Sb0.983Bi0.013 have accessed the longest wavelengths of any lattice-matched, bulk III–V alloy to date. Altogether, these results demonstrate the strong potential of InAsySb1–x–yBix for high-performance optoelectronic devices operating across the long-wave infrared.
{"title":"Molecular Beam Epitaxy of InAsSbBi Lattice-Matched to InSb toward Long-Wave Infrared Sensing","authors":"R. Corey White*, Morgan Bergthold, Aaron Muhowski, Leland Nordin, Iris Okoro, Hussein Hijazi, Leonard Feldman, Daniel Wasserman and Seth R. Bank, ","doi":"10.1021/acs.cgd.4c0026410.1021/acs.cgd.4c00264","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00264https://doi.org/10.1021/acs.cgd.4c00264","url":null,"abstract":"<p >InSb-based dilute-bismide alloys present a unique opportunity to span the entirety of the long-wave infrared with a bulk, lattice-matched III–V alloy that boasts greatly reduced toxicity compared to the current state-of-the-art, Hg<sub>1–<i>x</i></sub>Cd<sub><i>x</i></sub>Te. By incorporating both bismuth and arsenic in the appropriate proportions, we demonstrated InAs<sub>0.004</sub>Sb<sub>0.983</sub>Bi<sub>0.013</sub> lattice-matched to commercially available InSb substrates. A kinetically limited growth regime that combined low substrate temperatures, V/III flux ratios near unity, and a relatively fast growth rate, mitigated phase separation and resulted in films with excellent structural and optical quality. In particular, the bismuth incorporation was estimated to be approximately 95% substitutional and photoluminescence from the alloy was observed at elevated temperatures up to 400 K exhibiting significant wavelength extension beyond that of InSb, out to 7.6 μm at room temperature. Furthermore, the first antimony-rich InAs<sub><i>y</i></sub>Sb<sub>1–<i>x</i>–</sub><i><sub>y</sub></i>Bi<sub><i>x</i></sub> photodetector was fabricated and showed a longer cutoff wavelength than that of an InSb control detector due to the bandgap reduction caused by bismuth and arsenic incorporation. This highlights that emission and detection from InAs<sub>0.004</sub>Sb<sub>0.983</sub>Bi<sub>0.013</sub> have accessed the longest wavelengths of any lattice-matched, bulk III–V alloy to date. Altogether, these results demonstrate the strong potential of InAs<sub><i>y</i></sub>Sb<sub>1–<i>x</i>–</sub><i><sub>y</sub></i>Bi<sub><i>x</i></sub> for high-performance optoelectronic devices operating across the long-wave infrared.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-23DOI: 10.1021/acs.cgd.4c0094410.1021/acs.cgd.4c00944
Qinyu Cao, Jinlun Liang, Liangchen Zhang, Junying Wu, Teng Gao, Xiaolin Hu* and Naifeng Zhuang*,
A BiFeO3 crystal has both antiferromagnetism and piezoelectricity at room temperature. Unfortunately, it is difficult to grow a larger-size and high-quality BiFeO3 single crystal. By a top-seeded solution growth method using Bi2O3 as a solvent, centimeter-size Bi1–xSrxFe1–yTiyO3 crystals were successfully grown in this paper. Moreover, the lattice symmetry of the Bi1–xSrxFe1–yTiyO3 crystals changes from rhombohedra to cube with the increase in Sr2+ and Ti4+ doping concentration. The magnetization of a Bi0.6Sr0.4Fe0.6Ti0.4O3 crystal reaches 0.25 emu/g at room temperature, which is about 3.1 times as large as that of a BiFeO3 single crystal, in an applied magnetic field of 10,000 Oe. The piezoelectric effect is observed on all Bi0.8Sr0.2Fe0.8Ti0.2O3-2 wafers; especially, strong response was observed on the ⟨111⟩-oriented wafer. By optimizing the type and the concentration of doped ions, it is expected to obtain large-size doped BiFeO3 single crystals with better magnetic and piezoelectric properties.
{"title":"Growth and Piezoelectric Properties of Centimeter-Size BiFeO3 Single Crystals Codoped with Sr and Ti Ions","authors":"Qinyu Cao, Jinlun Liang, Liangchen Zhang, Junying Wu, Teng Gao, Xiaolin Hu* and Naifeng Zhuang*, ","doi":"10.1021/acs.cgd.4c0094410.1021/acs.cgd.4c00944","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00944https://doi.org/10.1021/acs.cgd.4c00944","url":null,"abstract":"<p >A BiFeO<sub>3</sub> crystal has both antiferromagnetism and piezoelectricity at room temperature. Unfortunately, it is difficult to grow a larger-size and high-quality BiFeO<sub>3</sub> single crystal. By a top-seeded solution growth method using Bi<sub>2</sub>O<sub>3</sub> as a solvent, centimeter-size Bi<sub>1–<i>x</i></sub>Sr<sub><i>x</i></sub>Fe<sub>1–<i>y</i></sub>Ti<sub><i>y</i></sub>O<sub>3</sub> crystals were successfully grown in this paper. Moreover, the lattice symmetry of the Bi<sub>1–<i>x</i></sub>Sr<sub><i>x</i></sub>Fe<sub>1–<i>y</i></sub>Ti<sub><i>y</i></sub>O<sub>3</sub> crystals changes from rhombohedra to cube with the increase in Sr<sup>2+</sup> and Ti<sup>4+</sup> doping concentration. The magnetization of a Bi<sub>0.6</sub>Sr<sub>0.4</sub>Fe<sub>0.6</sub>Ti<sub>0.4</sub>O<sub>3</sub> crystal reaches 0.25 emu/g at room temperature, which is about 3.1 times as large as that of a BiFeO<sub>3</sub> single crystal, in an applied magnetic field of 10,000 Oe. The piezoelectric effect is observed on all Bi<sub>0.8</sub>Sr<sub>0.2</sub>Fe<sub>0.8</sub>Ti<sub>0.2</sub>O<sub>3</sub>-2 wafers; especially, strong response was observed on the ⟨111⟩-oriented wafer. By optimizing the type and the concentration of doped ions, it is expected to obtain large-size doped BiFeO<sub>3</sub> single crystals with better magnetic and piezoelectric properties.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-23DOI: 10.1021/acs.cgd.4c0013210.1021/acs.cgd.4c00132
Rui Zhang, Yubo Wang, Yao Geng, Huxiao Xian, Lipiao Bao* and Xing Lu*,
Fundamental understanding of the growth mechanism of reactive metal nanomaterials at the atomic level in solutions remains challenging due to the difficulty in observing the growth dynamics of nanoparticles directly through ex situ synthesis methods. Herein, we explore the growth mechanism of hexagonal Zn nanocrystals formed from aqueous precursors using in situ liquid cell transmission electron microscopy for the first time. Real-time observation of growth trajectories of typical Zn nanoparticles reveals the coexistence of classical and nonclassical crystallization mechanisms. Quantitative analysis of the interparticle coalescence suggests that surface diffusion (SD) and grain boundary migration (GBM) are responsible for the shape evolution of coalesced nanoparticles. Analysis of the growth/dissolution kinetics during the Ostwald ripening (OR) process implies that a depletion zone (diffusion layer) around the nanocrystals is present. This study provides fundamental insights into the different stages of the growth mechanism for an important class of reactive metal nanomaterials and is instructive for the controlled synthesis of reactive metal nanomaterials useful in various fields.
{"title":"Growth Mechanism of Hexagonal Zinc Nanocrystals via Liquid Cell Transmission Electron Microscopic","authors":"Rui Zhang, Yubo Wang, Yao Geng, Huxiao Xian, Lipiao Bao* and Xing Lu*, ","doi":"10.1021/acs.cgd.4c0013210.1021/acs.cgd.4c00132","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00132https://doi.org/10.1021/acs.cgd.4c00132","url":null,"abstract":"<p >Fundamental understanding of the growth mechanism of reactive metal nanomaterials at the atomic level in solutions remains challenging due to the difficulty in observing the growth dynamics of nanoparticles directly through <i>ex situ</i> synthesis methods. Herein, we explore the growth mechanism of hexagonal Zn nanocrystals formed from aqueous precursors using <i>in situ</i> liquid cell transmission electron microscopy for the first time. Real-time observation of growth trajectories of typical Zn nanoparticles reveals the coexistence of classical and nonclassical crystallization mechanisms. Quantitative analysis of the interparticle coalescence suggests that surface diffusion (SD) and grain boundary migration (GBM) are responsible for the shape evolution of coalesced nanoparticles. Analysis of the growth/dissolution kinetics during the Ostwald ripening (OR) process implies that a depletion zone (diffusion layer) around the nanocrystals is present. This study provides fundamental insights into the different stages of the growth mechanism for an important class of reactive metal nanomaterials and is instructive for the controlled synthesis of reactive metal nanomaterials useful in various fields.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585777","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-22DOI: 10.1021/acs.cgd.4c0113010.1021/acs.cgd.4c01130
Manish Ranjan Sarkar, and , Deepak Chopra*,
Noncovalent interactions play a pivotal role in chemistry, offering versatile tools for manipulating and enhancing various material properties. Among these interactions, the relatively weak, fluorine-centered interactions have emerged as an important contributor in the formation of different crystalline phases and thus hold immense potential in different scientific domains. This comprehensive Perspective delves into the supramolecular chemistry of fluorine-involved interactions, and in particular C–H···F interactions, and explores the evolution in the understanding of the nature of noncovalent interactions, involving fluorine. This is of relevance, as it has implications in the structure and properties of compounds. It has been more than three decades since research began in this area, and it is now well realized that “fluorine does indeed form a hydrogen bond” and also it indeed is “polarizable”. This Perspective elucidates their role in nanotechnology, optical, biological, mechanical, catalytic, and electronic properties as well. Futuristic research could lead to the development of innovative materials and technologies with implications in science and industry. However, it is also important to note that while the potential in different applications exists, much of it is yet to be realized and requires further study.
{"title":"Evolution in the Understanding of Noncovalent Interactions Involving Fluorine: From Inception to Maturity to Properties","authors":"Manish Ranjan Sarkar, and , Deepak Chopra*, ","doi":"10.1021/acs.cgd.4c0113010.1021/acs.cgd.4c01130","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01130https://doi.org/10.1021/acs.cgd.4c01130","url":null,"abstract":"<p >Noncovalent interactions play a pivotal role in chemistry, offering versatile tools for manipulating and enhancing various material properties. Among these interactions, the relatively weak, fluorine-centered interactions have emerged as an important contributor in the formation of different crystalline phases and thus hold immense potential in different scientific domains. This comprehensive Perspective delves into the supramolecular chemistry of fluorine-involved interactions, and in particular C–H···F interactions, and explores the evolution in the understanding of the nature of noncovalent interactions, involving fluorine. This is of relevance, as it has implications in the structure and properties of compounds. It has been more than three decades since research began in this area, and it is now well realized that “fluorine does indeed form a hydrogen bond” and also it indeed is “polarizable”. This Perspective elucidates their role in nanotechnology, optical, biological, mechanical, catalytic, and electronic properties as well. Futuristic research could lead to the development of innovative materials and technologies with implications in science and industry. However, it is also important to note that while the potential in different applications exists, much of it is yet to be realized and requires further study.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}