ACS Materials AuPub Date : 2024-08-16DOI: 10.1021/acsmaterialsau.4c0002110.1021/acsmaterialsau.4c00021
Tom Roussel, Daniel Ferry, Artemis Kosta, Dalila Miele, Giuseppina Sandri, Felista L. Tansi, Frank Steiniger, Paul Southern, Quentin A. Pankhurst*, Ling Peng* and Suzanne Giorgio*,
{"title":"Insight into the Internal Structure of High-Performance Multicore Magnetic Nanoparticles Used in Cancer Thermotherapy","authors":"Tom Roussel, Daniel Ferry, Artemis Kosta, Dalila Miele, Giuseppina Sandri, Felista L. Tansi, Frank Steiniger, Paul Southern, Quentin A. Pankhurst*, Ling Peng* and Suzanne Giorgio*, ","doi":"10.1021/acsmaterialsau.4c0002110.1021/acsmaterialsau.4c00021","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00021https://doi.org/10.1021/acsmaterialsau.4c00021","url":null,"abstract":"<p >Multicore magnetic nanoparticles (MNPs), comprising iron oxide cores embedded in a sugar or starch matrix, are a class of nanomaterials with promising magnetic heating properties. Their internal structure, and particularly the strength of the internal core–core magnetic interactions, are believed to determine the functional properties, but there have been few detailed studies on this to date. We report here on an interlaboratory and multimodality transmission electron microscopy (TEM) and magnetic study of a high-performance MNP material (supplied by Resonant Circuits Limited, RCL) that is currently being used in a clinical study for the treatment of pancreatic cancer. TEM data were collected under a variety of conditions: conventional; high-resolution; scanning; cryogenic; and, for the first time, liquid phase. All the imaging modes showed mostly irregular dextran lamellae of lateral dimensions 30–90 nm, plus ca. 15% n/n of what appeared to be 30–60 nm long “nanorods”, and a multitude of well-dispersed ca. 3.7 nm diameter iron oxide cores. Cryogenic electron tomography indicated that the nanorods were edge-on lamellae, but in dried samples, tomography showed rod- or lath-shaped forms, possibly resulting from the collapse of lamellae during drying. High-resolution TEM (HRTEM) showed the dextran to be crystallized in the low-temperature hydrated dextran polymorph. Magnetic remanence Henkel-plot analysis indicated a weak core–core interaction field of ca. 4.8 kA/m. Theoretical estimates using a point-dipole model associated this field with a core-to-core separation distance of ca. 5 nm, which tallies well with the ca. 4–6 nm range of separation distances observed in liquid-cell TEM data. On this basis, we identify the structure–function link in the RCL nanoparticles to be the unusually well-dispersed multicore structure that leads to their strong heating capability. This insight provides an important design characteristic for the future development of bespoke nanomaterials for this significant clinical application.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 5","pages":"489–499 489–499"},"PeriodicalIF":5.7,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142161270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Efficient Microwave Irradiation-Assisted Synthesis of Benzodioxinoquinoxaline and Its Donor-Variegated Derivatives Enabling Long-Lived Emission and Efficient Bipolar Charge Carrier Transport","authors":"Liliia Deva, Mariia Stanitska, Levani Skhirtladze, Amjad Ali, Glib Baryshnikov, Dmytro Volyniuk, Stepan Kutsiy, Mykola Obushak, Monika Cekaviciute, Pavlo Stakhira, Juozas Vidas Grazulevicius","doi":"10.1021/acsmaterialsau.4c00050","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00050","url":null,"abstract":"To enhance the usually low-charge carrier mobilities of highly twisted donor–acceptor-type compounds that exhibit thermally activated delayed fluorescence, we designed a rodlike acceptor benzodioxinoquinoxaline. This acceptor and two donor–acceptor–donor derivatives were synthesized via microwave Buchwald–Hartwig cross-coupling reactions with yields of up to 91%. The compounds exhibit three different types of photoluminescence, which is well-explained by quantum chemical calculations. Benzodioxinoquinoxaline shows blue fluorescence, with a very short lifetime of 0.64 ns. Its derivatives exhibit either green solid-state-enhanced thermally activated delayed fluorescence (SSE-TADF) or room-temperature phosphorescence (RTP) with lifetimes approaching 7 ms. When molecularly dispersed in a polymeric host, the compounds show a photoluminescence quantum yield close to 60%. The derivatives containing acridine or phenoxazine moieties exhibit bipolar charge transport. At an electric field of 5.8 × 10<sup>5</sup> V/cm, hole and electron mobilities of the phenoxazine-containing compound reach 3.2 × 10<sup>–4</sup> and 1.5 × 10<sup>–4</sup> cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup>, respectively. Among the studied SSE-TADF-based organic light-emitting diodes, the device containing this compound shows the highest external quantum efficiency of 12.3% due to the good charge-transporting and SSE-TADF parameters of the emitter.","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142210944","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Materials AuPub Date : 2024-08-02DOI: 10.1021/acsmaterialsau.4c00014
Sham J. Mane, Nesta B. Joseph, Rekha Kumari, Awadhesh Narayan, Aninda J. Bhattacharyya
{"title":"Electrochemical Reduction of Nitrogen to Ammonia Using Zinc Telluride","authors":"Sham J. Mane, Nesta B. Joseph, Rekha Kumari, Awadhesh Narayan, Aninda J. Bhattacharyya","doi":"10.1021/acsmaterialsau.4c00014","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00014","url":null,"abstract":"Electrosynthesis of ammonia (NH<sub>3</sub>), an important constituent molecule of various commercial fertilizers, is a promising and sustainable alternative strategy compared with the century-old Haber-Bosch process. Herein, zinc telluride (ZnTe) is demonstrated as an efficient electrocatalyst for reducing nitrogen (N<sub>2</sub>) under ambient conditions to NH<sub>3</sub>. In this simple chemical strategy, Zn preferentially binds N<sub>2</sub> over hydrogen (H<sub>2</sub>), and Te, by virtue of its superior electronic properties, enhances the electrocatalytic activity of ZnTe. The analysis of the X-ray diffraction data using the Bravais-Friedel-Donnay-Harker (BFDH) theory predicted a crystal geometry with the active electrocatalytic sites predominantly confined to the (111) planes of ZnTe. The preferential binding of nitrogen (N<sub>2</sub>; adsorption energy = −0.043 eV) over hydrogen (H<sub>2</sub>, adsorption energy = −0.028 eV) to Zn on the (111) plane of ZnTe is further confirmed by density functional theory. The ZnTe catalyst is observed to be stable in the acidic medium and delivers a very high yield of NH<sub>3</sub> (19.85 μg/h<sup>–1</sup> mg<sub>cat</sub><sup>–1</sup>) and a Faradaic efficiency of 6.24% at −0.6 V (versus RHE). Additional verification experiments do not reveal the formation of side products (such as NH<sub>2</sub>–NH<sub>2</sub>) during N<sub>2</sub> reduction by ZnTe. Further, density functional theory calculations strongly predict that the electrocatalytic reduction of N<sub>2</sub> to NH<sub>3</sub> by ZnTe preferentially occurs via the alternate pathway.","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"28 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141933577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Realizing the Potential of Commercial E-Textiles for Wearable Glucose Biosensing Application","authors":"Moshfiq-Us-Saleheen Chowdhury, Sutirtha Roy, Krishna Prasad Aryal, Henry Leung, Richa Pandey","doi":"10.1021/acsmaterialsau.4c00033","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00033","url":null,"abstract":"Advancements in wearable technology have enabled noninvasive health monitoring using biosensors. This research focuses on developing a textile-based sweat glucose sensor using commercially available conductive textiles, evading the complexity of traditional fabrication methods. A comparative analysis of three low-cost conductive textiles, Adafruit 1364, 1167, and 4762, has been conducted for electrochemical glucose detection with glucose-specific enzymes such as glucose oxidase (GOx) and glucose dehydrogenase (GDH). Adafruit 1364 outperformed others in morphological, electrochemical, and wearable properties. Cyclic voltammetry shows that Adafruit 1364 and 4762 effectively detect glucose at the potential of 0.23 and 0.08 V using glucose oxidase and 0.1 and 0.08 V using glucose dehydrogenase enzymes, respectively. Furthermore, chronoamperometry has been conducted to confirm the presence of glucose at 1 μM concentration. Differential pulse voltammetry was conducted to assess the sensitivity of the Adafruit 1364 fabric electrode using glucose solutions with concentrations of 0.05, 0.15, 0.25, and 0.5 mM. The electrode immobilized with GOx showed a sensitivity of 0.005 μA μM<sup>−1</sup> and a limit of detection (LOD) of 41.3 μM, while the electrode immobilized with GDH exhibited a sensitivity of 0.0019 μA μM<sup>−1</sup> and an LOD of 63.1 μM. The study also highlighted the reproducibility, effect of interferents, and advantageous wearable properties of these sensors.","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"60 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141776058","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Materials AuPub Date : 2024-07-23DOI: 10.1021/acsmaterialsau.4c0004610.1021/acsmaterialsau.4c00046
Erwin Hüger*, Jochen Stahn and Harald Schmidt,
{"title":"Self-Diffusion of Ge in Amorphous GexSi1–x Films Studied In Situ by Neutron Reflectometry","authors":"Erwin Hüger*, Jochen Stahn and Harald Schmidt, ","doi":"10.1021/acsmaterialsau.4c0004610.1021/acsmaterialsau.4c00046","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00046https://doi.org/10.1021/acsmaterialsau.4c00046","url":null,"abstract":"<p >Ge<sub><i>x</i></sub>Si<sub>1–<i>x</i></sub> alloys are gaining renewed interest for many applications in electronics and optics, especially for miniaturized devices showing quantum size effects. Point defects and atomic diffusion play a crucial role in miniaturized and metastable systems. In the present work, Ge self-diffusion in sputter deposited amorphous Ge<sub><i>x</i></sub>Si<sub>1–<i>x</i></sub> alloys is studied in situ as a function of Ge content <i>x</i> = 0.13, 0.43, 0.8, and 1.0 by neutron reflectometry. The determined Ge self-diffusivities obey the Arrhenius law in the investigated temperature ranges. The higher the Ge content <i>x</i>, the higher the Ge self-diffusivity at the same temperature. The activation enthalpy decreases with <i>x</i> from 4.4 eV for self-diffusion in pure silicon films to about 2 eV self-diffusion in Ge<sub>0.8</sub>Si<sub>0.2</sub> and Ge. The decrease of the activation enthalpy for amorphous Ge<sub><i>x</i></sub>Si<sub>1–<i>x</i></sub> is similar to the case of crystalline Ge<sub><i>x</i></sub>Si<sub>1–<i>x</i></sub>. Possible explanations are discussed.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 5","pages":"537–546 537–546"},"PeriodicalIF":5.7,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Materials AuPub Date : 2024-07-23DOI: 10.1021/acsmaterialsau.4c00046
Erwin Hüger, Jochen Stahn, Harald Schmidt
{"title":"Self-Diffusion of Ge in Amorphous GexSi1–x Films Studied In Situ by Neutron Reflectometry","authors":"Erwin Hüger, Jochen Stahn, Harald Schmidt","doi":"10.1021/acsmaterialsau.4c00046","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00046","url":null,"abstract":"Ge<sub><i>x</i></sub>Si<sub>1–<i>x</i></sub> alloys are gaining renewed interest for many applications in electronics and optics, especially for miniaturized devices showing quantum size effects. Point defects and atomic diffusion play a crucial role in miniaturized and metastable systems. In the present work, Ge self-diffusion in sputter deposited amorphous Ge<sub><i>x</i></sub>Si<sub>1–<i>x</i></sub> alloys is studied in situ as a function of Ge content <i>x</i> = 0.13, 0.43, 0.8, and 1.0 by neutron reflectometry. The determined Ge self-diffusivities obey the Arrhenius law in the investigated temperature ranges. The higher the Ge content <i>x</i>, the higher the Ge self-diffusivity at the same temperature. The activation enthalpy decreases with <i>x</i> from 4.4 eV for self-diffusion in pure silicon films to about 2 eV self-diffusion in Ge<sub>0.8</sub>Si<sub>0.2</sub> and Ge. The decrease of the activation enthalpy for amorphous Ge<sub><i>x</i></sub>Si<sub>1–<i>x</i></sub> is similar to the case of crystalline Ge<sub><i>x</i></sub>Si<sub>1–<i>x</i></sub>. Possible explanations are discussed.","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"85 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141785444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"In Vitro Osteo-Immunological Responses of Bioactive Calcium Phosphate-Containing Urethane Dimethacrylate-Based Composites: A Potential Alternative to Poly(methyl methacrylate) Bone Cement","authors":"Weerachai Singhatanadgit, Piyarat Sungkhaphan, Boonlom Thavornyutikarn, Setthawut Kitpakornsanti, Anne Young, Wanida Janvikul","doi":"10.1021/acsmaterialsau.4c00037","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00037","url":null,"abstract":"This investigation developed new composite bone cements using urethane dimethacrylate (UDMA), poly(propylene glycol) dimethacrylate (PPGDMA), and hydroxyethyl methacrylate (HEMA), with micrometer-sized aluminosilicate glass filler. Monocalcium phosphate monohydrate (MCPM) and hydroxyapatite (HA) particles were added to enhance biological performance, particularly osteo-immunomodulation. Free radical polymerization was triggered by mixing two pastes containing either benzoyl peroxide (BPO, an initiator) or N-tolyglycine glycidyl methacrylate (NTGGMA, an activator). Increasing butylated hydroxytoluene (BHT, an inhibitor) enabled a suitable delay after mixing at 25 °C for placement. At 37 °C, the delay time was reduced and the final conversion was enhanced. Findings also demonstrated the biocompatibility of the developed bone cement toward osteo-immunological cell lineages, including mesenchymal stem cells (MSCs), fibroblasts, osteoclast precursor RAW 246.7 cells, and peripheral blood mononuclear cells (PBMCs). Notably, the cement with both MCPM and HA combined facilitated sufficient MSC growth, enabling subsequent mineralization while concurrently suppressing the proliferation of fibroblasts, osteoclast progenitors, and PBMCs. Furthermore, composite cement exhibited the capacity to differentially regulate osteoblast differentiation, cell-(in)dependent mineralization, osteoclastogenesis, and PBMC-mediated inflammatory responses at both cellular and molecular levels in vitro. These observations suggested their potential use for bone repair, especially in cases of inflammation-associated bone defects.","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"342 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Materials AuPub Date : 2024-07-12DOI: 10.1021/acsmaterialsau.4c0003110.1021/acsmaterialsau.4c00031
Danila Merino*,
{"title":"Embracing Nature’s Clockwork: Crafting Plastics for Degradation in Plant Agricultural Systems","authors":"Danila Merino*, ","doi":"10.1021/acsmaterialsau.4c0003110.1021/acsmaterialsau.4c00031","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00031https://doi.org/10.1021/acsmaterialsau.4c00031","url":null,"abstract":"<p >In the 21st century, global agriculture confronts the urgent challenge of increasing food production by 70% by 2050 while simultaneously addressing environmental and health concerns. Plastics, integral to agricultural innovation, present sustainability challenges due to their non-biodegradable nature and contribution to pollution. This perspective examines the transition to bioplastics, emphasizing their bio-based origin and their crucial characteristic of being readily biodegradable in the soil. Key bioplastics such as poly(lactic acid) (PLA), polyhydroxyalkanoates (PHAs), and biomass-derived polymers are discussed, particularly regarding the microplastic generation in soil resulting from their use in specific applications like mulch films, delivery systems, and soil conditioners. Embracing bioplastics signifies a significant step forward in achieving sustainable agriculture and addressing plastic waste. However, it is highlighted that while some bioplastics can be recovered and recycled, special applications where the plastic is in intimate contact with soil pose challenges for recovery. In these cases, that represent more than the 50% of plastics used in agriculture, meticulous design for biodegradation in soil synchronized with agricultural cycles is necessary. This approach ensures minimal environmental impact and promotes a circular approach to plastic use in agriculture.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 5","pages":"450–458 450–458"},"PeriodicalIF":5.7,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00031","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142161502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Materials AuPub Date : 2024-07-12DOI: 10.1021/acsmaterialsau.4c00031
Danila Merino
{"title":"Embracing Nature’s Clockwork: Crafting Plastics for Degradation in Plant Agricultural Systems","authors":"Danila Merino","doi":"10.1021/acsmaterialsau.4c00031","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00031","url":null,"abstract":"In the 21st century, global agriculture confronts the urgent challenge of increasing food production by 70% by 2050 while simultaneously addressing environmental and health concerns. Plastics, integral to agricultural innovation, present sustainability challenges due to their non-biodegradable nature and contribution to pollution. This perspective examines the transition to bioplastics, emphasizing their bio-based origin and their crucial characteristic of being readily biodegradable in the soil. Key bioplastics such as poly(lactic acid) (PLA), polyhydroxyalkanoates (PHAs), and biomass-derived polymers are discussed, particularly regarding the microplastic generation in soil resulting from their use in specific applications like mulch films, delivery systems, and soil conditioners. Embracing bioplastics signifies a significant step forward in achieving sustainable agriculture and addressing plastic waste. However, it is highlighted that while some bioplastics can be recovered and recycled, special applications where the plastic is in intimate contact with soil pose challenges for recovery. In these cases, that represent more than the 50% of plastics used in agriculture, meticulous design for biodegradation in soil synchronized with agricultural cycles is necessary. This approach ensures minimal environmental impact and promotes a circular approach to plastic use in agriculture.","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"8 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141612708","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Materials AuPub Date : 2024-07-10DOI: 10.1021/acsmaterialsau.4c0003010.1021/acsmaterialsau.4c00030
Anthony Vallace, Dhrumil R. Shah, Enerelt Burentugs, Atticus J. Tucker, Ashley E. Cavanagh and Christopher W. Jones*,
{"title":"Synthesis Route to Single-Walled Zeolite Nanotubes Enabled by Tetrabutylammonium Hydroxide","authors":"Anthony Vallace, Dhrumil R. Shah, Enerelt Burentugs, Atticus J. Tucker, Ashley E. Cavanagh and Christopher W. Jones*, ","doi":"10.1021/acsmaterialsau.4c0003010.1021/acsmaterialsau.4c00030","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00030https://doi.org/10.1021/acsmaterialsau.4c00030","url":null,"abstract":"<p >Single-walled zeolite nanotubes (ZNT) were recently synthesized in a narrow compositional window. ZNT structural features─thin zeolitic walls and large mesopores─can allow for easy access of small molecules to zeolite micropores, but they also impart processing limitations for these materials, such as challenges with conventional aqueous ion-exchange conditions. Conventional solid- and liquid-phase ion exchange of calcined NaOH-derived ZNT (NaH-ZNT) results in structural degradation to either 2D sheet-like phases, 3D nanocrystals, or amorphous phases, motivating different direct synthesis routes and unconventional ion-exchange procedures of uncalcined ZNT precursors. Here, a modified synthesis route for ZNT synthesis is introduced that facilitates facile ion exchange as well as incorporation of additional non-Al heteroatoms in the zeolite framework. Tetrabutylammonium hydroxide (TBAOH) is used as a hydroxide source and co-OSDA, enabling synthesis of new compositions of ZNT, otherwise unachievable by post-modification of previously reported NaH-ZNT. By varying the gel composition, synthesis temperature, crystallization time, hydroxide source, silicon source, and aluminum source, productive conditions for the new TBAOH synthesis are developed, leading to increased strong acid site density in the ZNT. The collected results demonstrate the sensitivity of the ZNT synthesis to many key parameters and show that the ZNT forms only when Si/(Al + T) ∼ 30 in these synthesis gels and with specific Si and Al sources, and always in the presence of trace Na<sup>+</sup>. Catalytic testing, via the tandem CO<sub>2</sub> hydrogenation to methanol and methanol to aromatics reaction, shows that ZNTs provide adequate catalytic activity (acidity), relative to their conventional 3D counterparts in converting methanol to aromatic compounds.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 5","pages":"523–536 523–536"},"PeriodicalIF":5.7,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00030","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142161460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}