Pub Date : 2025-03-25DOI: 10.1021/acs.chemmater.5c0041910.1021/acs.chemmater.5c00419
Han-Bo-Ram Lee*,
{"title":"Patterning Technology: From Supporting Role to Main Player in Materials Chemistry","authors":"Han-Bo-Ram Lee*, ","doi":"10.1021/acs.chemmater.5c0041910.1021/acs.chemmater.5c00419","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00419https://doi.org/10.1021/acs.chemmater.5c00419","url":null,"abstract":"","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 6","pages":"2071–2072 2071–2072"},"PeriodicalIF":7.2,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-21DOI: 10.1021/acs.chemmater.5c00140
Benjamin M. Oxley, Jong-Hoon Lim, Kyeong-Hyeon Lee, Jeong-Bin Cho, Saugata Sarker, Jadupati Nag, Michael J. Waters, James M. Rondinelli, Venkatraman Gopalan, Joon I. Jang, Mercouri G. Kanatzidis
We have discovered RbSbP2S6 and β-RbBiP2S6, two alkali chalcopnictates that crystallize as one-dimensional chains. These near-isostructural analogs differ primarily in the coordination environment of the central metal: Sb has a coordination number (CN) of 4, while Bi exhibits a CN of 5. Notably, β-RbBiP2S6 is another form of a Rb/Bi/P/S compound with a 1126 stoichiometry. The β-phase, detailed in this work, is synthesized via direct combination, whereas the previously reported α-phase forms through a reactive Rb/Bi salt flux. The α- and β-phases also differ primarily by the Bi coordination sphere: α-phase Bi CN = 7; β-phase Bi CN = 5. RbSbP2S6 and β-RbBiP2S6 are both semiconductors. RbSbP2S6 has a bandgap of 2.68 eV while β-RbBiP2S6 has a bandgap of 2.06 eV. Neither material is congruently melting, but both have successfully been grown into large single crystals via slow cooling of the melt. Nonlinear optical (NLO) results in powder samples show that the symmetry breaking, which leads to lower dimensionality, also leads to significantly lower second harmonic generation (SHG) intensity (∼0.1x AgGaSe2 for β-RbBiP2S6 vs ∼12x AgGaS2 for α-RbBiP2S6). Third Harmonic Generation (THG) in powder samples show similar intensities (∼0.3x AgGaSe2 for β-RbBiP2S6 and ∼0.1x AgGaSe2 for RbSbP2S6). These are corroborated by single crystal SHG results for β-RbBiP2S6 (∼0.5x AgGaSe2). The nonzero NLO coefficients d14, d25, and d36 at 1550 nm fundamental wavelength are measured to be 9.5 ± 2.4, 17.2 ± 3.2, and 3.6 ± 2.3 pm/V, respectively. β-RbBiP2S6 has a comparable laser-induced damage threshold (LIDT) to AgGaSe2 while RbSbP2S6 has a LIDT approximately 3x that of β-RbBiP2S6 attributed to its higher bandgap.
{"title":"Symmetry over Chemistry: Harmonic Generation of Low-Dimensional Alkali Chalcopnictates RbMP2S6 (M = Sb, Bi)","authors":"Benjamin M. Oxley, Jong-Hoon Lim, Kyeong-Hyeon Lee, Jeong-Bin Cho, Saugata Sarker, Jadupati Nag, Michael J. Waters, James M. Rondinelli, Venkatraman Gopalan, Joon I. Jang, Mercouri G. Kanatzidis","doi":"10.1021/acs.chemmater.5c00140","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00140","url":null,"abstract":"We have discovered RbSbP<sub>2</sub>S<sub>6</sub> and β-RbBiP<sub>2</sub>S<sub>6</sub>, two alkali chalcopnictates that crystallize as one-dimensional chains. These near-isostructural analogs differ primarily in the coordination environment of the central metal: Sb has a coordination number (CN) of 4, while Bi exhibits a CN of 5. Notably, β-RbBiP<sub>2</sub>S<sub>6</sub> is another form of a Rb/Bi/P/S compound with a 1126 stoichiometry. The β-phase, detailed in this work, is synthesized via direct combination, whereas the previously reported α-phase forms through a reactive Rb/Bi salt flux. The α- and β-phases also differ primarily by the Bi coordination sphere: α-phase Bi CN = 7; β-phase Bi CN = 5. RbSbP<sub>2</sub>S<sub>6</sub> and β-RbBiP<sub>2</sub>S<sub>6</sub> are both semiconductors. RbSbP<sub>2</sub>S<sub>6</sub> has a bandgap of 2.68 eV while β-RbBiP<sub>2</sub>S<sub>6</sub> has a bandgap of 2.06 eV. Neither material is congruently melting, but both have successfully been grown into large single crystals via slow cooling of the melt. Nonlinear optical (NLO) results in powder samples show that the symmetry breaking, which leads to lower dimensionality, also leads to significantly lower second harmonic generation (SHG) intensity (∼0.1x AgGaSe<sub>2</sub> for β-RbBiP<sub>2</sub>S<sub>6</sub> vs ∼12x AgGaS<sub>2</sub> for α-RbBiP<sub>2</sub>S<sub>6</sub>). Third Harmonic Generation (THG) in powder samples show similar intensities (∼0.3x AgGaSe<sub>2</sub> for β-RbBiP<sub>2</sub>S<sub>6</sub> and ∼0.1x AgGaSe<sub>2</sub> for RbSbP<sub>2</sub>S<sub>6</sub>). These are corroborated by single crystal SHG results for β-RbBiP<sub>2</sub>S<sub>6</sub> (∼0.5x AgGaSe<sub>2</sub>). The nonzero NLO coefficients <i>d</i><sub>14</sub>, <i>d</i><sub>25</sub>, and <i>d</i><sub>36</sub> at 1550 nm fundamental wavelength are measured to be 9.5 ± 2.4, 17.2 ± 3.2, and 3.6 ± 2.3 pm/V, respectively. β-RbBiP<sub>2</sub>S<sub>6</sub> has a comparable laser-induced damage threshold (LIDT) to AgGaSe<sub>2</sub> while RbSbP<sub>2</sub>S<sub>6</sub> has a LIDT approximately 3x that of β-RbBiP<sub>2</sub>S<sub>6</sub> attributed to its higher bandgap.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"27 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-21DOI: 10.1021/acs.chemmater.4c03281
Edita Joseph, Vaishnav Raveendran, S. Charis Caroline, Sudip K. Batabyal
Sodium antimony sulfide is a recently discovered alkali metal chalcogenide that has gained considerable attention due to its enhanced efficiency, nontoxicity, and low cost as a photoabsorber. This material exists in various phases, such as NaSbS2, NaSbS, Na3SbS4, and Na2Sb4S7, and can be obtained only by annealing at high temperatures. However, here, we report the controlled formation of two different phases of sodium antimony sulfide, NaSbS2, and a heterostructure of NaSbS2/Na2Sb4S7 achieved in a single successive ionic layer adsorption and reaction (SILAR) cycle without annealing procedures. Both phases were formed in two distinct colors, namely, orange (NaSbS2) and brown (Na2Sb4S7/NaSbS2), and were found to be two different materials with different electronic properties. The band gaps for both phases were calculated to be 2.0 and 1.6 eV, which lies in the ideal band gap region for a solar absorber. Two photodetectors were fabricated, where both phases acted as the active layers with fluorine-doped tin oxide (FTO) and carbon as the other two electrodes. Both devices produced an outstanding photocurrent and photovoltage under zero-bias conditions, proving to work as excellent self-powered photodetectors. The devices were tested under 455, 525, 632 nm, and white light-emitting diode (LED) light illumination. The rise and fall times under light irradiation were as rapid as 380 and 480 ms for the NaSbS2 device and 370 and 420 ms for the Na2Sb4S7/NaSbS2 device, respectively. The responsivity and detectivity for both the photodetectors at low intensities were found to be 0.89 and 3.5 mA/W and 8.8 × 109 and 4.7 × 1010 Jones, respectively.
{"title":"In Situ Heterostructure Formation of NaSbS2 and Na2Sb4S7 for Efficient Photogenerated Charge Separation","authors":"Edita Joseph, Vaishnav Raveendran, S. Charis Caroline, Sudip K. Batabyal","doi":"10.1021/acs.chemmater.4c03281","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03281","url":null,"abstract":"Sodium antimony sulfide is a recently discovered alkali metal chalcogenide that has gained considerable attention due to its enhanced efficiency, nontoxicity, and low cost as a photoabsorber. This material exists in various phases, such as NaSbS<sub>2</sub>, NaSbS, Na<sub>3</sub>SbS<sub>4</sub>, and Na<sub>2</sub>Sb<sub>4</sub>S<sub>7</sub>, and can be obtained only by annealing at high temperatures. However, here, we report the controlled formation of two different phases of sodium antimony sulfide, NaSbS<sub>2</sub>, and a heterostructure of NaSbS<sub>2</sub>/Na<sub>2</sub>Sb<sub>4</sub>S<sub>7</sub> achieved in a single successive ionic layer adsorption and reaction (SILAR) cycle without annealing procedures. Both phases were formed in two distinct colors, namely, orange (NaSbS<sub>2</sub>) and brown (Na<sub>2</sub>Sb<sub>4</sub>S<sub>7</sub>/NaSbS<sub>2</sub>), and were found to be two different materials with different electronic properties. The band gaps for both phases were calculated to be 2.0 and 1.6 eV, which lies in the ideal band gap region for a solar absorber. Two photodetectors were fabricated, where both phases acted as the active layers with fluorine-doped tin oxide (FTO) and carbon as the other two electrodes. Both devices produced an outstanding photocurrent and photovoltage under zero-bias conditions, proving to work as excellent self-powered photodetectors. The devices were tested under 455, 525, 632 nm, and white light-emitting diode (LED) light illumination. The rise and fall times under light irradiation were as rapid as 380 and 480 ms for the NaSbS<sub>2</sub> device and 370 and 420 ms for the Na<sub>2</sub>Sb<sub>4</sub>S<sub>7</sub>/NaSbS<sub>2</sub> device, respectively. The responsivity and detectivity for both the photodetectors at low intensities were found to be 0.89 and 3.5 mA/W and 8.8 × 10<sup>9</sup> and 4.7 × 10<sup>10</sup> Jones, respectively.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"183 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666649","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-21DOI: 10.1021/acs.chemmater.4c02625
Melanie M. Ghelardini, Chuanzhen Zhou, Birgit Urban, Martin Müller, Joseph B. Tracy
Gold nanorods (GNRs) coated with SiO2 are functionalized through thermally initiated free-radical thiol–ene click reactions, which couple vinyl groups on the SiO2 surface with thiols to form thioethers. This method of functionalization is developed as an alternative approach to thiolate functionalization of the gold surface. GNRs are synthesized using cetyltrimethylammonium bromide (CTAB), which is challenging to displace with thiols in high yield. In this work, a shell of SiO2 is instead deposited on the outer surface of the GNRs, which also maintains colloidal stability. A reaction with a vinyl silane then prepares the outer surface of the SiO2 shells for subsequent thiol–ene click reactions with five thiols that are selected to represent variations in structure and functional groups, including aliphatic and aromatic structures and acids and bases, demonstrating the versatility of the reaction. The SiO2 shell is initially 17 nm thick and further grows to 20 nm when functionalized with vinyl groups. Deposition of vinyl groups and the formation of thioethers are confirmed by Fourier-transform infrared (FTIR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS). While FTIR spectroscopy is well-known for characterizing the surface of nanoparticles, ToF-SIMS has been applied less for this purpose and strongly complements analysis by FTIR spectroscopy.
{"title":"Thiol–Ene Click Chemistry for Functionalizing Silica-Overcoated Gold Nanorods","authors":"Melanie M. Ghelardini, Chuanzhen Zhou, Birgit Urban, Martin Müller, Joseph B. Tracy","doi":"10.1021/acs.chemmater.4c02625","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02625","url":null,"abstract":"Gold nanorods (GNRs) coated with SiO<sub>2</sub> are functionalized through thermally initiated free-radical thiol–ene click reactions, which couple vinyl groups on the SiO<sub>2</sub> surface with thiols to form thioethers. This method of functionalization is developed as an alternative approach to thiolate functionalization of the gold surface. GNRs are synthesized using cetyltrimethylammonium bromide (CTAB), which is challenging to displace with thiols in high yield. In this work, a shell of SiO<sub>2</sub> is instead deposited on the outer surface of the GNRs, which also maintains colloidal stability. A reaction with a vinyl silane then prepares the outer surface of the SiO<sub>2</sub> shells for subsequent thiol–ene click reactions with five thiols that are selected to represent variations in structure and functional groups, including aliphatic and aromatic structures and acids and bases, demonstrating the versatility of the reaction. The SiO<sub>2</sub> shell is initially 17 nm thick and further grows to 20 nm when functionalized with vinyl groups. Deposition of vinyl groups and the formation of thioethers are confirmed by Fourier-transform infrared (FTIR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS). While FTIR spectroscopy is well-known for characterizing the surface of nanoparticles, ToF-SIMS has been applied less for this purpose and strongly complements analysis by FTIR spectroscopy.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672499","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tellurium-free BiSbSe3 has emerged as a promising candidate for medium-temperature n-type thermoelectric (TE) materials, which is attributed to its low lattice thermal conductivity and high performance-cost ratio. However, the intrinsically poor electrical properties restrict the enhancement of TE properties. Herein, the versatile CuI is introduced into BiSbSe3. The synergistic effects of iodine substituting for selenium and copper occupying the intercalation position collectively increase the carrier concentration. Concurrently, microstructure analysis results reveal that multiscale defects such as dislocations, (Bi,Sb)SeI nanoprecipitates, elemental segregation, and subgrain boundaries are introduced into BiSbSe3 via CuI compositing, which enhances the multifrequency phonon scattering. Ultimately, benefiting from the trade-off between the power factor and thermal conductivity, BiSbSe3+0.02CuI parallel to the hot-pressing direction attains an excellent ZT value of ∼ 0.64 at 673 K, representing approximately a 12-fold improvement over that of pristine BiSbSe3. These results demonstrate a viable compositing strategy for designing high-performance BiSbSe3 materials.
无碲 BiSbSe3 因其低晶格热导率和高性价比而成为中温 n 型热电（TE）材料的理想候选材料。然而，其本身较差的电性能限制了 TE 性能的提高。在此，我们在 BiSbSe3 中引入了多功能的 CuI。碘取代硒和铜占据插层位置的协同效应共同提高了载流子浓度。同时，微观结构分析结果表明，通过 CuI 复合，位错、（Bi,Sb）SeI 纳米沉淀物、元素偏析和亚晶界等多尺度缺陷被引入 BiSbSe3，从而增强了多频声子散射。最终，受益于功率因数和热导率之间的权衡，平行于热压方向的 BiSbSe3+0.02CuI 在 673 K 时达到了 ∼ 0.64 的优异 ZT 值，与原始 BiSbSe3 相比提高了约 12 倍。这些结果证明了设计高性能 BiSbSe3 材料的可行复合策略。
{"title":"Boosting the Thermoelectric Properties of Textured BiSbSe3 via Versatile CuI Compositing","authors":"Xiaowei Shi, Quanwei Jiang, Yu Yan, Zhen Tian, Erkuo Yang, Jianbo Zhu, Huijun Kang, Enyu Guo, Zongning Chen, Fengkai Guo, Rongchun Chen, Tongmin Wang","doi":"10.1021/acs.chemmater.5c00195","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00195","url":null,"abstract":"Tellurium-free BiSbSe<sub>3</sub> has emerged as a promising candidate for medium-temperature n-type thermoelectric (TE) materials, which is attributed to its low lattice thermal conductivity and high performance-cost ratio. However, the intrinsically poor electrical properties restrict the enhancement of TE properties. Herein, the versatile CuI is introduced into BiSbSe<sub>3</sub>. The synergistic effects of iodine substituting for selenium and copper occupying the intercalation position collectively increase the carrier concentration. Concurrently, microstructure analysis results reveal that multiscale defects such as dislocations, (Bi,Sb)SeI nanoprecipitates, elemental segregation, and subgrain boundaries are introduced into BiSbSe<sub>3</sub> via CuI compositing, which enhances the multifrequency phonon scattering. Ultimately, benefiting from the trade-off between the power factor and thermal conductivity, BiSbSe<sub>3</sub>+0.02CuI parallel to the hot-pressing direction attains an excellent <i>ZT</i> value of ∼ 0.64 at 673 K, representing approximately a 12-fold improvement over that of pristine BiSbSe<sub>3</sub>. These results demonstrate a viable compositing strategy for designing high-performance BiSbSe<sub>3</sub> materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-21DOI: 10.1021/acs.chemmater.5c00152
Shinhyo Bang, Juejing Liu, Bipeng Wang, Carlos Mora Perez, Ting-Ran Liu, Kyle D. Crans, Zhaohong Sun, Andrew Strzelecki, Oleg V. Prezhdo, Yu-Tsun Shao, Xiaofeng Guo, Richard L. Brutchey
Ternary I–III–VI2 semiconductors, such as CuInSe2, exhibit diverse polymorphs with unique structural characteristics and optoelectronic properties. This study investigates the pressure-induced phase transitions of metastable wurtzite-like CuInSe2 nanocrystals. Using a combination of synchrotron X-ray diffraction, pair distribution function analysis, and density functional theory calculations, we reveal a transition from cation-ordered wurtzite-like (Pmc21) to cation-disordered NaCl-like (Fm3̅m) structures at 7.7 GPa. The cation-disordered NaCl-like phase persists upon decompression. Bulk modulus calculations highlight size-dependent deviations from bulk material behavior. These findings deepen our understanding of phase stability in colloidal I–III–VI2 semiconductor nanocrystals, with implications for tailoring functional materials under extreme conditions.
{"title":"High-Pressure Phase Transition of Metastable Wurtzite-Like CuInSe2 Nanocrystals","authors":"Shinhyo Bang, Juejing Liu, Bipeng Wang, Carlos Mora Perez, Ting-Ran Liu, Kyle D. Crans, Zhaohong Sun, Andrew Strzelecki, Oleg V. Prezhdo, Yu-Tsun Shao, Xiaofeng Guo, Richard L. Brutchey","doi":"10.1021/acs.chemmater.5c00152","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00152","url":null,"abstract":"Ternary I–III–VI<sub>2</sub> semiconductors, such as CuInSe<sub>2</sub>, exhibit diverse polymorphs with unique structural characteristics and optoelectronic properties. This study investigates the pressure-induced phase transitions of metastable wurtzite-like CuInSe<sub>2</sub> nanocrystals. Using a combination of synchrotron X-ray diffraction, pair distribution function analysis, and density functional theory calculations, we reveal a transition from cation-ordered wurtzite-like (<i>Pmc</i>2<sub>1</sub>) to cation-disordered NaCl-like (<i>Fm</i>3̅<i>m</i>) structures at 7.7 GPa. The cation-disordered NaCl-like phase persists upon decompression. Bulk modulus calculations highlight size-dependent deviations from bulk material behavior. These findings deepen our understanding of phase stability in colloidal I–III–VI<sub>2</sub> semiconductor nanocrystals, with implications for tailoring functional materials under extreme conditions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666650","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-20DOI: 10.1021/acs.chemmater.5c00452
Jieyuan Du, Fei Jin, Guoping Jiang, Zhiliang Jin
The rapid recombination of charges severely limits the activity of photocatalysis. In this article, a polarized electric field and an internal electric field are formed between catalysts by constructing an interface engineering strategy. Through the synergistic effect of double electric fields, the above problems have been effectively resolved . The granular Cd0.5Zn0.5S was attached to the LaCoO3 network structure by electrostatics, and the composite catalyst Cd0.5Zn0.5S/LaCoO3 (CL) was formed. In situ characterization by XPS, EPR, and KFAM confirmed the formation of an S-scheme heterojunction between the composite catalysts. At the same time, electrochemical and fluorescence characterization confirmed that the photogenerated carrier separation efficiency of the CL-25 composite catalyst was significantly improved. This is because the built-in electric field at the interface of the composite catalyst exerts the polarizing electric field between the individual catalysts to an extreme degree, greatly reducing the recombination rate of photogenerated carriers and effectively improving the hydrogen evolution efficiency of the composite photocatalyst. DFT theoretical calculations prove that the existence of a double electric field can greatly reduce the Gibbs free energy of hydrogen adsorption.
{"title":"Synergistically Regulating D-Band Centers of Cd0.5Zn0.5S/LaCoO3 Heterojunction by Dual Electric Fields for Enhanced Photocatalytic Hydrogen Evolution","authors":"Jieyuan Du, Fei Jin, Guoping Jiang, Zhiliang Jin","doi":"10.1021/acs.chemmater.5c00452","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00452","url":null,"abstract":"The rapid recombination of charges severely limits the activity of photocatalysis. In this article, a polarized electric field and an internal electric field are formed between catalysts by constructing an interface engineering strategy. Through the synergistic effect of double electric fields, the above problems have been effectively resolved . The granular Cd<sub>0.5</sub>Zn<sub>0.5</sub>S was attached to the LaCoO<sub>3</sub> network structure by electrostatics, and the composite catalyst Cd<sub>0.5</sub>Zn<sub>0.5</sub>S/LaCoO<sub>3</sub> (CL) was formed. In situ characterization by XPS, EPR, and KFAM confirmed the formation of an S-scheme heterojunction between the composite catalysts. At the same time, electrochemical and fluorescence characterization confirmed that the photogenerated carrier separation efficiency of the CL-25 composite catalyst was significantly improved. This is because the built-in electric field at the interface of the composite catalyst exerts the polarizing electric field between the individual catalysts to an extreme degree, greatly reducing the recombination rate of photogenerated carriers and effectively improving the hydrogen evolution efficiency of the composite photocatalyst. DFT theoretical calculations prove that the existence of a double electric field can greatly reduce the Gibbs free energy of hydrogen adsorption.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"44 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rising CO2 emissions, particularly from industrial sectors, are driving climate change and causing severe environmental and energy crises that demand immediate action. The electrochemical CO2 reduction reaction (eCO2RR) provides a sustainable approach by converting waste CO2 into value-added products. However, achieving a high selectivity for multicarbon products in the eCO2RR requires advanced catalysts with large surface areas, accessible active sites, and strong synergistic interactions. Here, we introduce a dual-atom Fe/Cu-NC catalyst synthesized through a metal–organic framework (MOF)-derived method where Fe and Cu atoms are uniformly dispersed on a porous nitrogen-doped carbon matrix, forming dual heteroactive Fe–N4 and Cu–N3 sites. The strategic combination of these active sites significantly enhances catalytic performance, achieving a 67.4% Faradaic efficiency (FE) for ethanol at −0.8 V vs RHE in CO2-saturated 0.5 M KHCO3. In situ spectroscopic analysis confirms the formation of major *CO and *CHO intermediates during CO2 electrolysis on the Fe/Cu-NC electrode, which are crucial for C–C coupling and ethanol production. DFT studies reveal that Fe–N4 and Cu–N3 sites synergistically lower the *CO intermediate energy barriers. Fe–N4 enriches the local CO concentration, which migrates to Cu–N3, enhancing ethanol production. This highlights MOF-derived dual-atom catalysts as a promising strategy for efficient CO2 conversion into ecofriendly products with zero emissions.
{"title":"Selective Electrochemical Reduction of CO2 to Ethanol on a Heteroatom-Coordinated Dual-Atom Catalyst of Fe/Cu-NC","authors":"Fikiru Temesgen Angerasa, Endalkachew Asefa Moges, Chia-Yu Chang, Keseven Lakshmanan, Tesfaye Alamirew Dessie, Wei-Hsiang Huang, Habib Gemechu Edao, Woldesenbet Bafe Dilebo, Chemeda Barasa Guta, Chun-Chi Chang, Wei-Sheng Liao, Jung Shen, Nigus Gabbiye Habtu, Meng-Che Tsai, Wei-Nien Su, Bing Joe Hwang","doi":"10.1021/acs.chemmater.4c02803","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02803","url":null,"abstract":"Rising CO<sub>2</sub> emissions, particularly from industrial sectors, are driving climate change and causing severe environmental and energy crises that demand immediate action. The electrochemical CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR) provides a sustainable approach by converting waste CO<sub>2</sub> into value-added products. However, achieving a high selectivity for multicarbon products in the eCO<sub>2</sub>RR requires advanced catalysts with large surface areas, accessible active sites, and strong synergistic interactions. Here, we introduce a dual-atom Fe/Cu-NC catalyst synthesized through a metal–organic framework (MOF)-derived method where Fe and Cu atoms are uniformly dispersed on a porous nitrogen-doped carbon matrix, forming dual heteroactive Fe–N<sub>4</sub> and Cu–N<sub>3</sub> sites. The strategic combination of these active sites significantly enhances catalytic performance, achieving a 67.4% Faradaic efficiency (FE) for ethanol at −0.8 V <i>vs</i> RHE in CO<sub>2</sub>-saturated 0.5 M KHCO<sub>3</sub>. In situ spectroscopic analysis confirms the formation of major *CO and *CHO intermediates during CO<sub>2</sub> electrolysis on the Fe/Cu-NC electrode, which are crucial for C–C coupling and ethanol production. DFT studies reveal that Fe–N<sub>4</sub> and Cu–N<sub>3</sub> sites synergistically lower the *CO intermediate energy barriers. Fe–N<sub>4</sub> enriches the local CO concentration, which migrates to Cu–N<sub>3</sub>, enhancing ethanol production. This highlights MOF-derived dual-atom catalysts as a promising strategy for efficient CO<sub>2</sub> conversion into ecofriendly products with zero emissions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"26 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-19DOI: 10.1021/acs.chemmater.4c01049
Sokseiha Muy, Thierry Le Mercier, Marion Dufour, Marc-David Braida, Antoine A. Emery, Nicola Marzari
Li-containing argyrodites represent a promising family of Li-ion conductors, with several derived compounds exhibiting room-temperature ionic conductivity >1 mS/cm, making them attractive as potential candidates for electrolytes in solid-state Li-ion batteries. Starting from the parent phase Li7PS6, several cation and anion substitution strategies have been attempted to increase the conductivity of the Li ions. Nonetheless, a detailed understanding of the thermodynamics of native defects and doping of Li argyrodite and their effect on the ionic conductivity of Li is missing. Here, we report a comprehensive computational study of the defect chemistry of the parent phase Li7PS6 in both intrinsic and extrinsic regimes, using a newly developed workflow to automate the computations of several defect formation energies in a thermodynamically consistent framework. Our findings agree with known experimental findings, rule out several unfavorable aliovalent dopants, and narrow down the potential promising candidates that can be tested experimentally. We also find that cation–anion codoping can provide a powerful strategy to further optimize the composition of argyrodite. In particular, Si–F codoping is predicted to be thermodynamically favorable; this could lead to the synthesis of the first F-doped Li-containing argyrodite. Finally, using DeePMD neural networks, we have mapped the ionic conductivity landscape as a function of the concentration of the most promising cation and anion dopants identified from the defect calculations, and identified the most promising region in the compositional space with high Li conductivity that can be explored experimentally.
{"title":"Optimizing Ionic Conductivity of Lithium in Li7PS6 Argyrodite via Dopant Engineering","authors":"Sokseiha Muy, Thierry Le Mercier, Marion Dufour, Marc-David Braida, Antoine A. Emery, Nicola Marzari","doi":"10.1021/acs.chemmater.4c01049","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01049","url":null,"abstract":"Li-containing argyrodites represent a promising family of Li-ion conductors, with several derived compounds exhibiting room-temperature ionic conductivity >1 mS/cm, making them attractive as potential candidates for electrolytes in solid-state Li-ion batteries. Starting from the parent phase Li<sub>7</sub>PS<sub>6</sub>, several cation and anion substitution strategies have been attempted to increase the conductivity of the Li ions. Nonetheless, a detailed understanding of the thermodynamics of native defects and doping of Li argyrodite and their effect on the ionic conductivity of Li is missing. Here, we report a comprehensive computational study of the defect chemistry of the parent phase Li<sub>7</sub>PS<sub>6</sub> in both intrinsic and extrinsic regimes, using a newly developed workflow to automate the computations of several defect formation energies in a thermodynamically consistent framework. Our findings agree with known experimental findings, rule out several unfavorable aliovalent dopants, and narrow down the potential promising candidates that can be tested experimentally. We also find that cation–anion codoping can provide a powerful strategy to further optimize the composition of argyrodite. In particular, Si–F codoping is predicted to be thermodynamically favorable; this could lead to the synthesis of the first F-doped Li-containing argyrodite. Finally, using DeePMD neural networks, we have mapped the ionic conductivity landscape as a function of the concentration of the most promising cation and anion dopants identified from the defect calculations, and identified the most promising region in the compositional space with high Li conductivity that can be explored experimentally.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Despite vast potential, silicon chemistry has taken a back foot in the recent past as compared to its counterpart, carbon. Recently, silicon-based inorganic compounds containing silicon and oxygen have attracted significant attention. Of these, one intriguing nanostructure is Siloxene, a 2D oxide of silicon. Its close structural resemblance to 2D carbon compounds provides an opportunity to explore chemistries similar to carbon in silicon. Here, we have investigated the stability and reduction of Si═O bonds in 2D-Siloxene using hydrazine in potassium hydroxide. The reduction of 2D Siloxene shows striking similarity to Wolff–Kishner reduction, which is well-known in carbon chemistry. Specifically, the polarization of the Si═O bond in Siloxene results in charge separation between the silicon and oxygen atoms. This significantly enhances the reactivity of the Si═O bond and renders it susceptible to reduction. Mulliken charge analysis within the framework of density functional theory calculations suggests the electronegative behavior of O atoms, when attached to Si both as Si═O and Si–OH. The electropositive Si atom in Si═O is attacked by hydrazine hydrate, subsequently, when treated with a strong base, typically potassium hydroxide, affects the reduction of the hydrazone. Our study provides strong theoretical and experimental evidence for a reduction mechanism analogous to the Wolff–Kishner reduction, in 2D silicon, enabling developing insights in silicon reduction.
{"title":"Silicon Caught Carbon Copying Wolff–Kishner Reduction in Two Dimensional Siloxene Nanosheets","authors":"Nav Deepak, Rahul Kumar Das, Dhara Raval, Shobha Shukla, Sumit Saxena","doi":"10.1021/acs.chemmater.4c02642","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02642","url":null,"abstract":"Despite vast potential, silicon chemistry has taken a back foot in the recent past as compared to its counterpart, carbon. Recently, silicon-based inorganic compounds containing silicon and oxygen have attracted significant attention. Of these, one intriguing nanostructure is Siloxene, a 2D oxide of silicon. Its close structural resemblance to 2D carbon compounds provides an opportunity to explore chemistries similar to carbon in silicon. Here, we have investigated the stability and reduction of Si═O bonds in 2D-Siloxene using hydrazine in potassium hydroxide. The reduction of 2D Siloxene shows striking similarity to Wolff–Kishner reduction, which is well-known in carbon chemistry. Specifically, the polarization of the Si═O bond in Siloxene results in charge separation between the silicon and oxygen atoms. This significantly enhances the reactivity of the Si═O bond and renders it susceptible to reduction. Mulliken charge analysis within the framework of density functional theory calculations suggests the electronegative behavior of O atoms, when attached to Si both as Si═O and Si–OH. The electropositive Si atom in Si═O is attacked by hydrazine hydrate, subsequently, when treated with a strong base, typically potassium hydroxide, affects the reduction of the hydrazone. Our study provides strong theoretical and experimental evidence for a reduction mechanism analogous to the Wolff–Kishner reduction, in 2D silicon, enabling developing insights in silicon reduction.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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