Lithium aluminium oxide–carbon composites on Al metal substrates (Al/LiAl5O8/C) were successfully synthesized, and their electrical properties were characterized. Sheet-type lithium aluminium layered double hydroxide (LiAl-LDH) was grown on Al metal (Al/S-LDH) and subjected to anion exchange to introduce aliphatic dicarboxylate into the interlayers through solvothermal treatment. The interlayer spacings of dicarboxylate intercalated LiAl-LDH on Al metal (Al/DC-LDH) were expanded from 9.1 Å to 21.4 Å of the (002) reflection in XRD measurement. Remarkable thickness changes of the LiAl-LDH were also observed in SEM data, indicating a strong correlation with the intercalation reaction of long-chain dicarboxylates. The pyrolysis of Al/DC-LDH above 500 °C provides nanostructured electrodes of Al/LiAl5O8/C nanocomposites, which contain graphitic carbon and an ordered nanostructure depending on the calcination temperatures. Al/LiAl5O8/C electrodes demonstrate improved electrochemical performance with enhanced durability better than Al/S-LDH electrodes, exhibiting an areal capacitance of 0.51 mF cm−2 at a current density of 0.01 mA cm−2.
{"title":"Self-supporting electrodes of lithium aluminium oxide–carbon nanocomposites synthesized from dicarboxylate-intercalated layered double hydroxide for supercapacitors","authors":"Yongju Lee, Duk-Young Jung","doi":"10.1039/d4ta05640j","DOIUrl":"https://doi.org/10.1039/d4ta05640j","url":null,"abstract":"Lithium aluminium oxide–carbon composites on Al metal substrates (Al/LiAl<small><sub>5</sub></small>O<small><sub>8</sub></small>/C) were successfully synthesized, and their electrical properties were characterized. Sheet-type lithium aluminium layered double hydroxide (LiAl-LDH) was grown on Al metal (Al/S-LDH) and subjected to anion exchange to introduce aliphatic dicarboxylate into the interlayers through solvothermal treatment. The interlayer spacings of dicarboxylate intercalated LiAl-LDH on Al metal (Al/DC-LDH) were expanded from 9.1 Å to 21.4 Å of the (002) reflection in XRD measurement. Remarkable thickness changes of the LiAl-LDH were also observed in SEM data, indicating a strong correlation with the intercalation reaction of long-chain dicarboxylates. The pyrolysis of Al/DC-LDH above 500 °C provides nanostructured electrodes of Al/LiAl<small><sub>5</sub></small>O<small><sub>8</sub></small>/C nanocomposites, which contain graphitic carbon and an ordered nanostructure depending on the calcination temperatures. Al/LiAl<small><sub>5</sub></small>O<small><sub>8</sub></small>/C electrodes demonstrate improved electrochemical performance with enhanced durability better than Al/S-LDH electrodes, exhibiting an areal capacitance of 0.51 mF cm<small><sup>−2</sup></small> at a current density of 0.01 mA cm<small><sup>−2</sup></small>.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404959","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}
Kexin Gu, Zhepu Shi, Xiao Li, Bao Qiu, Zhaoping Liu
Correction for ‘Review on the synthesis of Li-rich layered oxide cathodes’ by Kexin Gu et al., J. Mater. Chem. A, 2024, 12, 24727–24745, https://doi.org/10.1039/D4TA03917C.
{"title":"Correction: Review on the synthesis of Li-rich layered oxide cathodes","authors":"Kexin Gu, Zhepu Shi, Xiao Li, Bao Qiu, Zhaoping Liu","doi":"10.1039/d4ta90193b","DOIUrl":"https://doi.org/10.1039/d4ta90193b","url":null,"abstract":"Correction for ‘Review on the synthesis of Li-rich layered oxide cathodes’ by Kexin Gu <em>et al.</em>, <em>J. Mater. Chem. A</em>, 2024, <strong>12</strong>, 24727–24745, https://doi.org/10.1039/D4TA03917C.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404955","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}
Graphitic carbon nitride (g-C3N4) is considered to be a promising photocatalyst for hydrogen evolution reaction (HER) due to its facile synthesis, outstanding chemical/thermal stability and suitable band structure. However, the unsatisfactory performance of pristine g-C3N4 severely restricts its its further widespread application. In this work, theoretical predictions reveal that integrating sulfur dopants and coupling vanadium carbide (V2C) MXene can significantly optimize the hydrogen adsorbed Gibbs free energy (ΔGH*) of g-C3N4 to near zero. Inspired by the theoretical predictions, an advanced HER photocatalyst of sulfur-doped g-C3N4/V2C MXene (SCN/V2C) Schottky junction is fabricated successfully by vacuum ball milling and subsequent annealing treatment. Interface-charge transfer between SCN and V2C endows a strong electron interaction, which not only improves hydrophilicity and visible-light absorption, but also facilitates the separation and migration of photoexcited carriers. Density functional theory calculations and in situ characterization results corroborate that the carrier migration of SCN/V2C adheres to the typical Schottky heterojunction mechanism. Femtosecond transientabsorption (fs-TA) spectroscopy demonstrates the favorable carrier dynamic behavior of developed SCN/V2C photocatalysts. Thus, the SCN/V2C achieves a superior H2 production rate of 8003 μmol g-1 h-1. The Schottky heterojunction established in this research provides valuable insights into the further strategic design and construction of high-performance HER photocatalysts.
{"title":"Sulfur-doped g-C3N4/V2C MXene Schottky junctions for superior photocatalytic H2 evolution","authors":"Haitao Wang, Jipeng Fan, Jing Zou, Yujie Zheng, Dingsheng Wang, Jizhou Jiang","doi":"10.1039/d4ta05929h","DOIUrl":"https://doi.org/10.1039/d4ta05929h","url":null,"abstract":"Graphitic carbon nitride (g-C3N4) is considered to be a promising photocatalyst for hydrogen evolution reaction (HER) due to its facile synthesis, outstanding chemical/thermal stability and suitable band structure. However, the unsatisfactory performance of pristine g-C3N4 severely restricts its its further widespread application. In this work, theoretical predictions reveal that integrating sulfur dopants and coupling vanadium carbide (V2C) MXene can significantly optimize the hydrogen adsorbed Gibbs free energy (ΔGH*) of g-C3N4 to near zero. Inspired by the theoretical predictions, an advanced HER photocatalyst of sulfur-doped g-C3N4/V2C MXene (SCN/V2C) Schottky junction is fabricated successfully by vacuum ball milling and subsequent annealing treatment. Interface-charge transfer between SCN and V2C endows a strong electron interaction, which not only improves hydrophilicity and visible-light absorption, but also facilitates the separation and migration of photoexcited carriers. Density functional theory calculations and in situ characterization results corroborate that the carrier migration of SCN/V2C adheres to the typical Schottky heterojunction mechanism. Femtosecond transientabsorption (fs-TA) spectroscopy demonstrates the favorable carrier dynamic behavior of developed SCN/V2C photocatalysts. Thus, the SCN/V2C achieves a superior H2 production rate of 8003 μmol g-1 h-1. The Schottky heterojunction established in this research provides valuable insights into the further strategic design and construction of high-performance HER photocatalysts.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404964","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}
Anju P Veedu, Balasurendran Jeyakumar, Akhila Maheswari Mohan, K. Satheesh, K. C. Pitchaiah, Manjula Muthurathinam, C. V. S. Brahmananda Rao, Nagarajan Sivaraman, Prabhakaran Deivasigamani
The work focuses on a pollution-free ultra-portable solid-state opto-chemosensor for sensing noxious Cd2+ from environmental, industrial and non-industrial samples. An amphiphilic heterocyclic azo-receptor, (E)-4-((4,5-dimethylthiazol-2-yl)diazenyl)-6-hexylbenzene-1,3-diol (DMTHBD) is meticulously interlaced to the mesopore honeycomb structured silica monolith framework (MHSF). The aqua-compatible optical sensor (DMTHBD@MHSF) proffers remarkable structural integrity, surface morphology and porosity. The MHSF and DMTHBD@MHSF materials are characterized using powder X-ray diffraction, X-ray photoelectron spectroscopy, Fourier Transform infrared spectroscopy, high-resolution transmission electron microscopy, field-emission scanning electron microscopy, energy dispersive X-ray analysis, selected area electron diffraction, elemental mapping analysis, thermogravimetric/differential thermal analysis, Brunauer-Emmett-Teller (surface area) and Barrett-Joyner-Halenda (pore size distribution) plot. The MHSF shows a uniform distribution of well-packed continuous mesopore channels that expedite the voluminous loading of receptor molecules on MHSF and the analyte diffusion to the receptor chelating sites. The DMTHBD@MHSF sensor exhibits exclusive selectivity for ultra-trace Cd2+, with brilliant concentration correlative color metamorphosis in ≤50 s, using a minimal sensor dose (3 mg). A distinguishable solid-state hue transition from salmon pink to intense violet is spotted in the concentration range of 1-400 microg/L, with a linear signal response between 0-150 g/L, with detection and quantification limit of 0.15 and 0.50 g/L of Cd2+, respectively. The renewable sensor demonstrates excellent stability/durability under harsh working conditions, with reliable performance even after prolonged storage. The practical applications of the proposed sensor are authenticated using diverse actual samples, with an average recovery of ≥99.43% for Cd2+ and a relative standard deviation of ≤1.65%.
{"title":"Azo-receptor conjoined mesoporous honeycomb silica framework as solid-state chromogenic sensor for capturing ultra-trace cadmium ions from environmental/industrial samples","authors":"Anju P Veedu, Balasurendran Jeyakumar, Akhila Maheswari Mohan, K. Satheesh, K. C. Pitchaiah, Manjula Muthurathinam, C. V. S. Brahmananda Rao, Nagarajan Sivaraman, Prabhakaran Deivasigamani","doi":"10.1039/d4ta04574b","DOIUrl":"https://doi.org/10.1039/d4ta04574b","url":null,"abstract":"The work focuses on a pollution-free ultra-portable solid-state opto-chemosensor for sensing noxious Cd<small><sup>2+</sup></small> from environmental, industrial and non-industrial samples. An amphiphilic heterocyclic azo-receptor, (E)-4-((4,5-dimethylthiazol-2-yl)diazenyl)-6-hexylbenzene-1,3-diol (DMTHBD) is meticulously interlaced to the mesopore honeycomb structured silica monolith framework (MHSF). The aqua-compatible optical sensor (DMTHBD@MHSF) proffers remarkable structural integrity, surface morphology and porosity. The MHSF and DMTHBD@MHSF materials are characterized using powder X-ray diffraction, X-ray photoelectron spectroscopy, Fourier Transform infrared spectroscopy, high-resolution transmission electron microscopy, field-emission scanning electron microscopy, energy dispersive X-ray analysis, selected area electron diffraction, elemental mapping analysis, thermogravimetric/differential thermal analysis, Brunauer-Emmett-Teller (surface area) and Barrett-Joyner-Halenda (pore size distribution) plot. The MHSF shows a uniform distribution of well-packed continuous mesopore channels that expedite the voluminous loading of receptor molecules on MHSF and the analyte diffusion to the receptor chelating sites. The DMTHBD@MHSF sensor exhibits exclusive selectivity for ultra-trace Cd<small><sup>2+</sup></small>, with brilliant concentration correlative color metamorphosis in ≤50 s, using a minimal sensor dose (3 mg). A distinguishable solid-state hue transition from salmon pink to intense violet is spotted in the concentration range of 1-400 microg/L, with a linear signal response between 0-150 g/L, with detection and quantification limit of 0.15 and 0.50 g/L of Cd2+, respectively. The renewable sensor demonstrates excellent stability/durability under harsh working conditions, with reliable performance even after prolonged storage. The practical applications of the proposed sensor are authenticated using diverse actual samples, with an average recovery of ≥99.43% for Cd<small><sup>2+</sup></small> and a relative standard deviation of ≤1.65%.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405062","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}
Ionogels have aroused much attention due to their unique advantages for constructing wearable devices. However, integrating the properties of strong toughness, high ion conductivity, self-healing and shape-memory into one ionogel is still challenging. Herein, we develop a polyzwitterionic ionogel through the copolymerization of zwitterionic [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) (SBMA) and acrylamide (AAm) in ionic liquid (IL) of 1-ethyl-3-methylimidazolium ethyl sulfate (EMIES). The facile ability to engage in hydrogen bonds for poly acrylamide (PAM) segments makes them easily aggregated in EMIES, resulting in the formation of polymer-rich domains. In contrast, poly[2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) (PSBMA) segments combined with EMIES form solvent-rich phase due to their good compatibility. Therefore, interpenetrating phase-separated structure is produced during the polymerization. The polymer-rich phase can dissipate energy and provide high strength, while the solvent-rich phase enables the ionogel with large stretchability. Besides, the zwitterionic groups on PSBMA can provide separate and continuous ion conductive pathways, facilitating the ion transport. Attributing to the synergy of phase separation and zwitterionic feature, the resulting ionogel presents balanced mechanical and electrical properties with high toughness of 2.7 MJ/m3 and ion conductivity of 1.3 mS/cm, as well as desirable self-healing ability. The resulting PSBMA/PAAm ionogel demonstrated excellent performance as a temperature and strain sensor. Remarkably, the ionogel possessed outstanding shape-memory property, making the ionogel can fix on the human joint or object with nonzero Gaussian curvature and maintains the sensing functions. Therefore, the morphing ionogel based sensor displays huge versatilities and potentials on detecting the signals variations for the objects with sophisticated geometries.
{"title":"Microphase separation induced polyzwitterionic ionogel with tough, highly conductive, self-healing and shape-memory properties for wearable electrical devices","authors":"Guang Zeng, Wenshuo Gao, Weicheng Qiu, Guanling Li, Shousen Chen, Xin He, Guoxing Sun, Weijia Yang, Yue Xin","doi":"10.1039/d4ta04228j","DOIUrl":"https://doi.org/10.1039/d4ta04228j","url":null,"abstract":"Ionogels have aroused much attention due to their unique advantages for constructing wearable devices. However, integrating the properties of strong toughness, high ion conductivity, self-healing and shape-memory into one ionogel is still challenging. Herein, we develop a polyzwitterionic ionogel through the copolymerization of zwitterionic [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) (SBMA) and acrylamide (AAm) in ionic liquid (IL) of 1-ethyl-3-methylimidazolium ethyl sulfate (EMIES). The facile ability to engage in hydrogen bonds for poly acrylamide (PAM) segments makes them easily aggregated in EMIES, resulting in the formation of polymer-rich domains. In contrast, poly[2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) (PSBMA) segments combined with EMIES form solvent-rich phase due to their good compatibility. Therefore, interpenetrating phase-separated structure is produced during the polymerization. The polymer-rich phase can dissipate energy and provide high strength, while the solvent-rich phase enables the ionogel with large stretchability. Besides, the zwitterionic groups on PSBMA can provide separate and continuous ion conductive pathways, facilitating the ion transport. Attributing to the synergy of phase separation and zwitterionic feature, the resulting ionogel presents balanced mechanical and electrical properties with high toughness of 2.7 MJ/m3 and ion conductivity of 1.3 mS/cm, as well as desirable self-healing ability. The resulting PSBMA/PAAm ionogel demonstrated excellent performance as a temperature and strain sensor. Remarkably, the ionogel possessed outstanding shape-memory property, making the ionogel can fix on the human joint or object with nonzero Gaussian curvature and maintains the sensing functions. Therefore, the morphing ionogel based sensor displays huge versatilities and potentials on detecting the signals variations for the objects with sophisticated geometries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404961","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}
Anjaiah Sheelam, Ariel Whitten, Carrington G Moore, Mark H Engelhard, Jean-Sabin McEwen, Jeffrey Bell
Water is an earth-abundant source for clean hydrogen production via electrochemical water electrolysis (WE). However, the surface poisoning that occurs in aqueous electrolytes drastically deactivates the electrocatalytic performance of electrodes. Here, we report an electrochemically formed In2O3-x(OH)y on the surface of a large (1–1.5 mm long, 0.5–0.6 mm wide and 0.3–0.5 mm thick) single-crystal of Weyl semimetal Co3In2S2 (Co3In2S2/In2O3-x(OH)y) as an ultra-stable and poison tolerance electrode for the oxygen evolution reaction (OER) in 1 M KOH, addressing a bottleneck in WE. The OER activity of powder form of Co3In2S2 is limited by its aerophilic nature. Remarkably, the single-crystal electrodes maintained their high activity for a continuous operational period of 5 h in 1 M KOH electrolyte with/without 10 mM of strong surface-poisoning ligands i.e., potassium cyanide, bipyridine, and ethylenediaminetetraacetate disodium salt. The electrodes exhibited stable OER activity for 1000 h at 100 mA cm−2 (1.73 V vs. RHE). The temperature-dependent OER polarization curves (10–70 °C) unambiguously revealed surface poisoning through the suppression of precatalytic Co-redox peaks on the bipyridine poisoned electrode and lead to the stabilization of surface Co-sites. The X-ray photoelectron spectroscopy analyses of pristine, poisoned and post-electrocatalytic single-crystal Co3In2S2 electrodes revealed the existence of In2O3-x(OH)y surface phase, which could be the potential heterostructure for the origin of ultra-stable and poison tolerance OER activity.
水是一种丰富的地球资源，可通过电化学水电解法（WE）生产清洁氢气。然而，在水电解质中发生的表面中毒会使电极的电催化性能严重失活。在此，我们报告了在大块（1-1.5 毫米长、0.5-0.6 毫米宽、0.3-0.5 毫米厚）Weyl 半金属 Co3In2S2（Co3In2S2/In2O3-x(OH)y）单晶表面电化学形成的 In2O3-x(OH)y，作为 1 M KOH 中氧进化反应（OER）的超稳定耐毒电极，解决了水电解中的瓶颈问题。粉末状 Co3In2S2 的 OER 活性受到其嗜气性的限制。值得注意的是，单晶电极在 1 M KOH 电解液中连续工作 5 小时，在添加/不添加 10 mM 强表面中毒配体（即氰化钾、联吡啶和乙二胺四乙酸二钠盐）的情况下，仍能保持高活性。在 100 mA cm-2 的条件下，电极在 1000 小时内表现出稳定的 OER 活性（相对于 RHE 为 1.73 V）。随温度变化的 OER 极化曲线（10-70 °C）通过抑制联吡啶中毒电极上的前催化钴氧化还原峰，明确显示了表面中毒现象，并导致表面钴位点的稳定。对原始、中毒和电催化后单晶 Co3In2S2 电极进行的 X 射线光电子能谱分析表明了 In2O3-x(OH)y 表面相的存在，这可能是超稳定耐毒 OER 活性的潜在异质结构。
{"title":"Ultra-stable and poison tolerance oxygen evolution activity enabled by surface In2O3-x(OH)y of Co3In2S2 large single-crystal","authors":"Anjaiah Sheelam, Ariel Whitten, Carrington G Moore, Mark H Engelhard, Jean-Sabin McEwen, Jeffrey Bell","doi":"10.1039/d4ta04608k","DOIUrl":"https://doi.org/10.1039/d4ta04608k","url":null,"abstract":"Water is an earth-abundant source for clean hydrogen production via electrochemical water electrolysis (WE). However, the surface poisoning that occurs in aqueous electrolytes drastically deactivates the electrocatalytic performance of electrodes. Here, we report an electrochemically formed In2O3-x(OH)y on the surface of a large (1–1.5 mm long, 0.5–0.6 mm wide and 0.3–0.5 mm thick) single-crystal of Weyl semimetal Co3In2S2 (Co3In2S2/In2O3-x(OH)y) as an ultra-stable and poison tolerance electrode for the oxygen evolution reaction (OER) in 1 M KOH, addressing a bottleneck in WE. The OER activity of powder form of Co3In2S2 is limited by its aerophilic nature. Remarkably, the single-crystal electrodes maintained their high activity for a continuous operational period of 5 h in 1 M KOH electrolyte with/without 10 mM of strong surface-poisoning ligands i.e., potassium cyanide, bipyridine, and ethylenediaminetetraacetate disodium salt. The electrodes exhibited stable OER activity for 1000 h at 100 mA cm−2 (1.73 V vs. RHE). The temperature-dependent OER polarization curves (10–70 °C) unambiguously revealed surface poisoning through the suppression of precatalytic Co-redox peaks on the bipyridine poisoned electrode and lead to the stabilization of surface Co-sites. The X-ray photoelectron spectroscopy analyses of pristine, poisoned and post-electrocatalytic single-crystal Co3In2S2 electrodes revealed the existence of In2O3-x(OH)y surface phase, which could be the potential heterostructure for the origin of ultra-stable and poison tolerance OER activity.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404957","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}
The electrocatalytic conversion of carbon dioxide (CO2) into valuable fuels offers immense promise in pursuing sustainable energy solutions. The robustness and intriguing electronic properties of Transition metal carbides (TMCs) traditionally have emerged as captivating contenders in the quest for efficient catalysts for CO2 reduction reactions (CO2RR). The presence of carbon atoms in TMC structures unlock a unique reaction mechanism for CO2RR, namely as Mars-van Krevelen (MVK) mechanism, facilitating CO2 capture and more efficient conversion to high-value-added chemicals. This work is the first report on the use of TMCs for CO2RR where comprehensive reaction pathways for different product formations are investigated. This theoretical study delves into the electronic intricacies of TMCs, unraveling their potential to drive the transformative journey toward a greener tomorrow. Here, we analyzed 11 TMCs to explore the reactivity trends toward CO, formic acid, methane, methanediol, and methanol formation. The VC is the best candidate explored to produce formic acid at 0 V onset potential. In addition, WC is the best candidate explored to produce methanol at an onset potential of -0.36 V. These results demonstrate that our studied TMCs as electrocatalysts are more promising than previously studied materials (metals and oxides) for application of CO2RR, and thus require more attention and investigation.
{"title":"Exploring reaction mechanisms for CO2 reduction on Carbides","authors":"Naveed Ashraf, Atef Iqbal, Younes Abghoui","doi":"10.1039/d4ta05592f","DOIUrl":"https://doi.org/10.1039/d4ta05592f","url":null,"abstract":"The electrocatalytic conversion of carbon dioxide (CO2) into valuable fuels offers immense promise in pursuing sustainable energy solutions. The robustness and intriguing electronic properties of Transition metal carbides (TMCs) traditionally have emerged as captivating contenders in the quest for efficient catalysts for CO2 reduction reactions (CO2RR). The presence of carbon atoms in TMC structures unlock a unique reaction mechanism for CO2RR, namely as Mars-van Krevelen (MVK) mechanism, facilitating CO2 capture and more efficient conversion to high-value-added chemicals. This work is the first report on the use of TMCs for CO2RR where comprehensive reaction pathways for different product formations are investigated. This theoretical study delves into the electronic intricacies of TMCs, unraveling their potential to drive the transformative journey toward a greener tomorrow. Here, we analyzed 11 TMCs to explore the reactivity trends toward CO, formic acid, methane, methanediol, and methanol formation. The VC is the best candidate explored to produce formic acid at 0 V onset potential. In addition, WC is the best candidate explored to produce methanol at an onset potential of -0.36 V. These results demonstrate that our studied TMCs as electrocatalysts are more promising than previously studied materials (metals and oxides) for application of CO2RR, and thus require more attention and investigation.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405569","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}
Morphology optimization of photoactive layer plays a crucial role in fabricating high-performance polymer solar cells (PSCs). When an active layer is cast from solution, the unique properties of the donor and acceptor materials often lead to either excessive or insufficient phase separation, which adversely affect the performance of the device. Specifically, all-polymer solar cells (all-PSCs) introduce an added complexity in terms of morphology regulation due to the inherently flexible and entangled nature of polymer chains. In this work, we first introduced 3,5-dichloroanisole (DCA) as a solid additive, known for its good crystallinity and volatility, to refine the active layer morphology in all-PSCs. Then, we combined 1-chloronaphthalene (CN) and DCA as dual additives, which effectively optimized the morphology of all-polymer blend. This combination favors charge transport and minimizes charge recombination, leading to higher fill factor across various systems. Notably, device based on PM6:PY-DT processed with this dual-additives approach achieved an impressive power conversion efficiency (PCE) of 17.42%, outperforming the control device without any additive, which showed a PCE of 14.34%. Besides, the dual additives were applied in the other systems, revealing its universality. This work not only took advantages of both solvent and solid additives, but also effectively improved the performance of all-PSCs.
{"title":"High Performance All-Polymer Solar Cells Enabled with Solvent and Solid Dual Additives","authors":"Misbah Sehar Abbasi, Congqi Li, Jinhua Gao, Siying Wang, Sixuan Wang, Qijie Lin, Xie Gening, Saqib Nawaz Khan, Jianqi Zhang, Xin Zhang, Yunhao Cai, Hui Huang","doi":"10.1039/d4ta06013j","DOIUrl":"https://doi.org/10.1039/d4ta06013j","url":null,"abstract":"Morphology optimization of photoactive layer plays a crucial role in fabricating high-performance polymer solar cells (PSCs). When an active layer is cast from solution, the unique properties of the donor and acceptor materials often lead to either excessive or insufficient phase separation, which adversely affect the performance of the device. Specifically, all-polymer solar cells (all-PSCs) introduce an added complexity in terms of morphology regulation due to the inherently flexible and entangled nature of polymer chains. In this work, we first introduced 3,5-dichloroanisole (DCA) as a solid additive, known for its good crystallinity and volatility, to refine the active layer morphology in all-PSCs. Then, we combined 1-chloronaphthalene (CN) and DCA as dual additives, which effectively optimized the morphology of all-polymer blend. This combination favors charge transport and minimizes charge recombination, leading to higher fill factor across various systems. Notably, device based on PM6:PY-DT processed with this dual-additives approach achieved an impressive power conversion efficiency (PCE) of 17.42%, outperforming the control device without any additive, which showed a PCE of 14.34%. Besides, the dual additives were applied in the other systems, revealing its universality. This work not only took advantages of both solvent and solid additives, but also effectively improved the performance of all-PSCs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404963","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}
Zhengyu Sun, Weiwei Sun, Shaohan Li, Zening Yang, Mutian Zhang, Yang Yang, Huayun Geng, Jin Yu
To address the challenges of high error rates and poor generalization in current deep learning models for predicting lattice thermal conductivity (LTC), we introduce CrysGraphFormer, an innovative equivariant crystal graph Transformer model tailored for this task. The model incorporates an improved multi-head self-attention mechanism and human-designed feature descriptors. Utilizing a message-passing mechanism to update node information, it introduces relative coordinate differences to represent crystal symmetry, avoiding the complex and computationally expensive higher-order representations traditionally used. We constructed a comprehensive dataset containing 5729 LTC data points (300K), including 5477 materials from AFLOW, 112 MAX and MAB phase materials calculated using VASP, and 140 for half-Heusler alloys. Experimental results demonstrate that the CrysGraphFormer model achieves state-of-the-art performance in LTC prediction tasks and excels in predicting fundamental properties. The model offers good interpretability, providing insights from chemical and materials science perspectives. Furthermore, we validated the model's application potential in the field of thermoelectric materials by predicting the LTC of 59 thermoelectric materials and 55 ternary semiconductor materials, with results consistent with DFT calculations. Finally, the uncertainty of CrysGraphFormer was assessed using Monte Carlo Dropout method.
{"title":"CrysGraphFormer: An Equivariant Graph Transformer for Prediction of Lattice Thermal Conductivity with Interpretability","authors":"Zhengyu Sun, Weiwei Sun, Shaohan Li, Zening Yang, Mutian Zhang, Yang Yang, Huayun Geng, Jin Yu","doi":"10.1039/d4ta04495a","DOIUrl":"https://doi.org/10.1039/d4ta04495a","url":null,"abstract":"To address the challenges of high error rates and poor generalization in current deep learning models for predicting lattice thermal conductivity (LTC), we introduce CrysGraphFormer, an innovative equivariant crystal graph Transformer model tailored for this task. The model incorporates an improved multi-head self-attention mechanism and human-designed feature descriptors. Utilizing a message-passing mechanism to update node information, it introduces relative coordinate differences to represent crystal symmetry, avoiding the complex and computationally expensive higher-order representations traditionally used. We constructed a comprehensive dataset containing 5729 LTC data points (300K), including 5477 materials from AFLOW, 112 MAX and MAB phase materials calculated using VASP, and 140 for half-Heusler alloys. Experimental results demonstrate that the CrysGraphFormer model achieves state-of-the-art performance in LTC prediction tasks and excels in predicting fundamental properties. The model offers good interpretability, providing insights from chemical and materials science perspectives. Furthermore, we validated the model's application potential in the field of thermoelectric materials by predicting the LTC of 59 thermoelectric materials and 55 ternary semiconductor materials, with results consistent with DFT calculations. Finally, the uncertainty of CrysGraphFormer was assessed using Monte Carlo Dropout method.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398363","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}
High-nickel layered oxides suffer from shortened cycle life due to high surface reactivity with the electrolyte. Modifications with Nb, whether doping or coating, results in improved electrochemical stability. This improvement is often at the expense of initial capacity. This study identifies the origins of this commonly reported decrease in initial capacity and the “activation” region of increasing capacity. Through the identification of the mechanisms behind the initial capacity penalty, a modified cycling schedule is employed that improves both the initial capacity output and stability by compensating for the polarization loss induced by the presence of lithium niobate (LixNbOy) phases with an increase in the cutoff charge voltage. This results in a 30% increase in initial capacity for a 2% Nb-modified sample in full cells with graphite anodes by adjusting the cycling parameters, as well as a 27% longer cycle life when half cells were cycled to 180 mAh g-1 instead of 4.4 V. Electrochemical impedance spectroscopy (EIS) identifies a decrease in cell impedance for Nb-modified samples at higher voltages (>4.4 V vs. Li / Li+) compared to those cycled to the standard 4.4 V (vs. Li / Li+) cutoff. These findings allow to realize improved electrochemical performance with Nb-modified samples synthesized with single-step calcinations. By elucidating the mechanisms behind why the lithium niobate / cathode interface results in higher impedance at 4.4 V cutoff, we suggest new cycling parameters that can improve the performance of high nickel cathode materials modified with lithium niobate phases.
高镍层状氧化物由于表面与电解液的高反应性而缩短了循环寿命。通过掺杂或镀层等方式对铌进行改性，可提高电化学稳定性。这种改善往往以牺牲初始容量为代价。本研究确定了这种普遍报道的初始容量降低的原因，以及容量增加的 "激活 "区域。通过确定初始容量损失背后的机制，采用了一种改进的循环时间表，通过提高截止充电电压来补偿铌酸锂 (LixNbOy) 相的存在所引起的极化损失，从而提高了初始容量输出和稳定性。通过调整循环参数，2% Nb 改性样品在石墨阳极全电池中的初始容量提高了 30%，当半电池循环电压为 180 mAh g-1 而不是 4.4 V 时，循环寿命延长了 27%。电化学阻抗光谱 (EIS) 发现，与在标准 4.4 V（与 Li / Li+ 相比）截止电压下循环的样品相比，Nb 改性样品在更高电压（4.4 V 与 Li / Li+）下的电池阻抗有所下降。这些发现使通过单步煅烧合成的铌改性样品的电化学性能得到改善。通过阐明铌酸锂/阴极界面在 4.4 V 截流电压下产生较高阻抗的机理，我们提出了一些新的循环参数，这些参数可以提高用铌酸锂相改性的高镍阴极材料的性能。
{"title":"Delineating the intricacies of niobium-modified high-nickel layered cathodes with a single-step synthesis","authors":"Thomas J. Watts, Arumugam Manthiram","doi":"10.1039/d4ta05544f","DOIUrl":"https://doi.org/10.1039/d4ta05544f","url":null,"abstract":"High-nickel layered oxides suffer from shortened cycle life due to high surface reactivity with the electrolyte. Modifications with Nb, whether doping or coating, results in improved electrochemical stability. This improvement is often at the expense of initial capacity. This study identifies the origins of this commonly reported decrease in initial capacity and the “activation” region of increasing capacity. Through the identification of the mechanisms behind the initial capacity penalty, a modified cycling schedule is employed that improves both the initial capacity output and stability by compensating for the polarization loss induced by the presence of lithium niobate (LixNbOy) phases with an increase in the cutoff charge voltage. This results in a 30% increase in initial capacity for a 2% Nb-modified sample in full cells with graphite anodes by adjusting the cycling parameters, as well as a 27% longer cycle life when half cells were cycled to 180 mAh g-1 instead of 4.4 V. Electrochemical impedance spectroscopy (EIS) identifies a decrease in cell impedance for Nb-modified samples at higher voltages (>4.4 V vs. Li / Li+) compared to those cycled to the standard 4.4 V (vs. Li / Li+) cutoff. These findings allow to realize improved electrochemical performance with Nb-modified samples synthesized with single-step calcinations. By elucidating the mechanisms behind why the lithium niobate / cathode interface results in higher impedance at 4.4 V cutoff, we suggest new cycling parameters that can improve the performance of high nickel cathode materials modified with lithium niobate phases.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":11.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398370","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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