ACS Earth and Space Chemistry最新文献

{"title":"Triggering Ion Diffusion and Electron Transport Dual Pathways for High Efficiency Electrochemical Li+ Extraction","authors":"Honglong Zhan,&nbsp;Zhiqiang Qian,&nbsp;Yingjun Qiao,&nbsp;Baoliang Lv,&nbsp;Ruirui Liu,&nbsp;Hong Chen* and Zhong Liu*,&nbsp;","doi":"10.1021/acsnano.4c0937910.1021/acsnano.4c09379","DOIUrl":"https://doi.org/10.1021/acsnano.4c09379https://doi.org/10.1021/acsnano.4c09379","url":null,"abstract":"<p >Efficient electrochemical Li⁺ adsorption holds significant promise for lithium extraction, while the mismatched rate between Li⁺ diffusion and electron transport within the electrode material impedes the electrochemical activity and restricts the adsorption efficiency. To address this challenge, herein, we rationally design and integrate the ion and electron dual-conducting poly(vinyl alcohol)–polyaniline (PVA-PANI) copolymer (CP) within the H_1.6Mn_1.6O₄ (HMO) electrode matrix to facilitate Li⁺ diffusion and electron transport. The Li⁺ diffusion coefficient (<i>D</i>_Li+) increased from 3.03 × 10^–10 to 5.92 × 10^–10 cm²/s, while the charge transfer resistance (<i>R</i>_ct) decreased from 53.73 to 29.57 ohm. Consequently, the HMO@CP electrode exhibits superior adsorption kinetics and a state-of-the-art high adsorption capacity of up to 49.48 mg/g. Comprehensive mechanistic studies reveal that the negatively charged hydroxyl groups (−OH) in PVA accelerate Li⁺ diffusion and that the conjugated structure and redox-active quinoid sites in PANI offer denser electron distribution and promote electron transport. This synergistic effect in CP significantly enhanced Li⁺ diffusion and electron transport, leading to electrochemical activity and adsorption efficiency. Our work highlights the critical role of simultaneously regulating the ion diffusion and electron transport dual pathways for optimizing Li⁺ adsorption performance and inspires development of the next generation electrochemical adsorption electrodes.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31204–31214 31204–31214"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Versatile Hydrogel Based on a Controlled Microphase-Separation Strategy for Both Liquid- and Solid-Phase 3D Printing","authors":"Qirui Wu,&nbsp;Yidan Xu,&nbsp;Songjiu Han,&nbsp;Anbang Chen,&nbsp;Jiayu Zhang,&nbsp;Yujia Chen,&nbsp;Xiaoxiang Yang and Lunhui Guan*,&nbsp;","doi":"10.1021/acsnano.4c0889610.1021/acsnano.4c08896","DOIUrl":"https://doi.org/10.1021/acsnano.4c08896https://doi.org/10.1021/acsnano.4c08896","url":null,"abstract":"<p >Hydrogels are considered indispensable materials for fabricating flexible devices with their excellent flexibility and workability. To efficiently transform hydrogels into flexible devices, three-dimensional printing technology offers a powerful approach. However, hydrogels suitable for a single printing strategy have proven inadequate for fabricating flexible integrated devices. Herein, we report a simple and two-phase 3D-printed hydrogel (TP-3DPgel) achieved through a controlled microphase-separation strategy. The microphase-separation regions can undergo reversible changes through pH adjustment, giving TP-3DPgel an extremely broad viscosity tuning range from liquid to solid states. This overcomes limitations imposed by extreme rheological properties in different 3D printing processes, making this ink suitable for both liquid-phase digital light processing (DLP) 3D printing and solid-phase direct ink writing (DIW) 3D printing. Simultaneously, the TP-3DPgel exhibits excellent mechanical properties, including high stretchability (&gt;1100%), high strength (0.82 MPa), low hysteresis (∼5.4%), and fatigue resistance. Moreover, TP-3DPgel exhibits high-resolution 3D printing capabilities, making it suitable for both DLP and DIW-3D printing to achieve high-quality fabrication from 2D filaments to 3D structures. Interestingly, we utilized both DIW and DLP-3D printing to fabricate various functional flexible devices, including energy storage devices, sensors, and electronic skins, showing in detail the outstanding compatibility and processability of TP-3DPgel, which offered a reliable strategy for 3D printing functional devices.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31148–31159 31148–31159"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609346","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Atomistic Insights on Prebiotic Phosphorylation of Methanol from Schreibersite (Fe2NiP) Corrosion: Ab Initio Computational Study","authors":"Stefano Pantaleone*,&nbsp;Giulia De Gasperis,&nbsp;Marta Corno,&nbsp;Albert Rimola,&nbsp;Nadia Balucani and Piero Ugliengo*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0022610.1021/acsearthspacechem.4c00226","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00226https://doi.org/10.1021/acsearthspacechem.4c00226","url":null,"abstract":"<p >The prebiotic history of phosphorus is a matter of debate in the scientific community: its origin, how it landed on Earth, the selective speciation of the phosphate, and its inclusion in the organic matrix are the main unsolved issues. In this regard, Schreibersite ((Fe,Ni)₃P), a mineral present in iron meteorites, can play a fundamental role as a carrier of reactive P which, as a result of the weathering processes, produces oxygenated phosphorus compounds, even the phosphate among others. In the present paper, we studied the interaction of methanol (alone and mixed with water) with the Schreibersite surfaces throughout periodic density functional theory calculations at the PBE level. The results indicate that Schreibersite promotes the deprotonation of methanol and water both from thermodynamic and kinetic points of view, thus enabling the first step toward corrosion. We have simulated advanced stages of the corrosion process up to the formation of the phosphate and the phosphorylated form of methanol (methyl phosphate), showing that the formation of both products is thermodynamically favored, as well as its solubilization, which allows other water molecules to proceed with further corrosion of Schreibersite.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2310–2317 2310–2317"},"PeriodicalIF":2.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Boosting the Photoresponse of Azobenzene Single-Molecule Junctions via Mechanical Interlock and Dynamic Anchor","authors":"Shun-Da Wu,&nbsp;Zi-Zhen Chen,&nbsp;Wen-Jing Sun,&nbsp;Li-Yu-Yang Shi,&nbsp;An-Kang Shen,&nbsp;Jing-Jing Cao,&nbsp;Zitong Liu*,&nbsp;Colin J. Lambert* and Hao-Li Zhang*,&nbsp;","doi":"10.1021/acsnano.4c1301010.1021/acsnano.4c13010","DOIUrl":"https://doi.org/10.1021/acsnano.4c13010https://doi.org/10.1021/acsnano.4c13010","url":null,"abstract":"<p >As the most classic photoisomerization system, azobenzene has been widely utilized as a building unit in various photoswitching applications. However, attempts to build azobenzene-based single-molecule photoswitches have met with limited success, giving low on/off ratios. Herein, we demonstrate two designs of azobenzene-based photoresponsive single-molecule junctions, based on mechanically interlocked diazocine and azobenzene-based dynamic anchors, respectively. Molecular conductance measurements using the scanning tunneling microscope breaking junction (STMBJ) technique revealed dramatic conductance changes upon photoillumination, achieving a high on/off ratio of ∼3.7. Using density functional theory (DFT), we revealed peculiar quantum interference (QI) effects in the diazocine molecular switch, indicating that diazocine is an excellent candidate for molecular photoswitches. The asymmetric azobenzene devices with a dynamic anchor exhibit switching behavior between a fully off state and a highly conductive state associated with the <i>trans</i>/<i>cis</i> conformation transition. The findings of this work not only present the design and development of functional molecular devices based on azobenzene units but also provide insight into the fundamental properties of light-induced quantum interference in azobenzene-based molecular devices.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31547–31558 31547–31558"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multi-Lasso Peptide-Based Synergistic Nanocomposite: A High-Stability, Broad-Spectrum Antimicrobial Agent with Potential for Combined Antibacterial Therapy","authors":"Yu Li,&nbsp;Jinyu Zhang,&nbsp;Ke Wei,&nbsp;Di Zhou,&nbsp;Zepeng Wang,&nbsp;Zhiwei Zeng,&nbsp;Yu Han and Weisheng Cao*,&nbsp;","doi":"10.1021/acsnano.4c1144310.1021/acsnano.4c11443","DOIUrl":"https://doi.org/10.1021/acsnano.4c11443https://doi.org/10.1021/acsnano.4c11443","url":null,"abstract":"<p >Lasso peptides, natural biological microcins composed of small molecules, have demonstrated efficient bactericidal activity. However, a single lasso peptide is characterized by a narrow and targeted bactericidal spectrum. In this study, a chitosan (CN) derivative-based polymer nanomaterial incorporating three lasso peptides (MccY, MccJ25, and Klebsidin) was designed and synthesized to broaden its antimicrobial spectrum. To enhance resistance to acid and alkali conditions, arginine was appended to the terminus of conjugates, resulting in Chitosan-Lasso-Peptides-Arg (CN-LPs-Arg), and the nanomaterial biocompatibility and bactericidal activity were characterized. Chemical stability test results demonstrate that CN-LPs-Arg effectively buffered the acid–base effect of the compound. Notably, CN-LPs-Arg extended the antimicrobial spectrum of Gram-negative and Gram-positive strains including <i>Klebsiella</i>, <i>Salmonella</i>, and <i>Staphylococcus</i> (MIC = 0.01–1.0 μM). CN-LPs-Arg exerts its destructive effects on bacteria via a series of mechanisms; it adheres to and then penetrates the membrane, causes rupture, and leads to bacterial death. Transcriptomic data revealed that CN-LPs-Arg produced a distinct inhibitory effect on ribosomal protein subunits synthesis pathways and membrane metabolic inhibition. Furthermore, CN-LPs-Arg was nontoxic to cells and exhibited excellent biocompatibility. CN-LPs-Arg reduced bacterial burden in organs and the levels of inflammatory factors IL-6, IL-8, and TNF-α in tissues of mice with acute bacterial infections. Furthermore, it promoted the recovery of <i>Klebsiella</i>-infected C57BL/6 mice, demonstrating a favorable therapeutic effect in vivo. The multilasso peptide-based synergistic nanocomposite of CN-LPs-Arg exhibited high stability as a broad-spectrum antimicrobial agent with potential for combined antibacterial therapy and utilization in the fields of food, biomedicine, and public health.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31435–31450 31435–31450"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Targeted Positron Emission Tomography-Tracked Biomimetic Codelivery Synergistically Amplifies Ferroptosis and Pyroptosis for Inducing Lung Cancer Regression and Anti-PD-L1 Immunotherapy Efficacy","authors":"Jinyu Zhu,&nbsp;Wenyuan Zhou,&nbsp;Yuan Yao,&nbsp;Xin Zhou,&nbsp;Xiaokun Ma,&nbsp;Baohui Zhang,&nbsp;Zhi Yang,&nbsp;Bufu Tang*,&nbsp;Hua Zhu* and Nan Li*,&nbsp;","doi":"10.1021/acsnano.4c1127810.1021/acsnano.4c11278","DOIUrl":"https://doi.org/10.1021/acsnano.4c11278https://doi.org/10.1021/acsnano.4c11278","url":null,"abstract":"<p >The chemoresistance and systemic toxicity of cisplatin (CDDP) severely limit its application in the treatment of non-small cell lung cancer (NSCLC). Here, I-124 labeled cancer cell membrane biomimetic nanovesicles loading Polyphyllin VI (PPVI) and CDDP (termed ¹²⁴I–P/C@CMLvs) were constructed to enhance the sensitivity and efficacy of CDDP. The radiochemical purity (RCP) of ¹²⁴I–P/C@CMLvs reached more than 99% and maintained reliable stability in vitro. Micro-positron emission tomography (micro-PET) imaging of I-124 quantitatively revealed the distribution and specific homologous tumor targeting ability of ¹²⁴I–P/C@CMLvs in vivo with superior diagnosis performance, beneficial for dynamically monitoring the efficacy against NSCLC. Loaded PPVI significantly strengthened the sensitivity of NSCLC to CDDP therapy and exerted synergistic anti-tumor effect in vitro and in vivo, which was achieved by PPVI promoting p53 deubiquitination and stimulating reactive oxygen species (ROS) production to trigger the crosstalk between the amplification of GPX4 signaling-mediated ferroptosis and NLRP3/GSDMD/Caspase-1 axis-mediated pyroptosis. ¹²⁴I–P/C@CMLvs also significantly stimulated the infiltration of immune cells including dendritic cells, CD8⁺ T cells, and CD4⁺ T cells in tumor tissues (<i>P</i> &lt; 0.05). The combination of ¹²⁴I–P/C@CMLvs and anti-PD-L1 therapy further synergistically promoted NSCLC regression. Altogether, ¹²⁴I–P/C@CMLvs provide a transformational solution to the challenge of improving CDDP sensitivity and realizing the integration of diagnosis, treatment, and monitoring of NSCLC.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31401–31420 31401–31420"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Emerging Era of Molecular Medicine","authors":"Heming Tang,&nbsp;Ying Zhang,&nbsp;Yanyuan Wu,&nbsp;Ting Fu,&nbsp;Cheng Cui,&nbsp;Zongping Wang,&nbsp;Sitao Xie*,&nbsp;Qin Wu* and Weihong Tan*,&nbsp;","doi":"10.1021/acsnano.4c0796910.1021/acsnano.4c07969","DOIUrl":"https://doi.org/10.1021/acsnano.4c07969https://doi.org/10.1021/acsnano.4c07969","url":null,"abstract":"<p >The era of molecular medicine arose as we began to diagnose and treat diseases based on understanding how genes, proteins, and cells work, providing optimal therapeutic care through molecular profiling. Central to molecular medicine is molecular recognition, which is underpinned by techniques involving omics analysis, gene editing, and targeted agents. Recent advancements in these tools not only expand our understanding of biological processes but also aid in the development of diagnostic and treatment modalities at the molecular level, thus bridging the gap between medical research and clinical applications. This perspective traces the development of molecular tools, highlighting, along the way, their pivotal role in advancing molecular medicine for the global health of people.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"30911–30918 30911–30918"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In Situ Self-Inflating-Modeled Giant-Vesicle-Like Quantum Dot Assembly for Biomimetic Artificial Photosynthesis","authors":"Jing Liu,&nbsp;Zi-Hao Liao,&nbsp;Ting Zhu,&nbsp;Jin Wu and Feng Wang*,&nbsp;","doi":"10.1021/acsnano.4c1272810.1021/acsnano.4c12728","DOIUrl":"https://doi.org/10.1021/acsnano.4c12728https://doi.org/10.1021/acsnano.4c12728","url":null,"abstract":"<p >The study of biomimetic self-assembly is crucial for scientists aiming to understand the origin of life and construct biomimetic functional structures. In our endeavor to create a biomimetic photosynthetic assembly, we discover a self-inflation behavior that drives the components, MPA-CdSe quantum dots (QDs) and a solid cationic polyelectrolyte, <b>CPPA</b>, to form a giant-vesicle-like (GVL) architecture, termed <b>GVL-QDs@CPPA</b>. The <i>in situ</i> generation of osmotic pressure during the self-assembly of QDs onto swollen <b>CPPA</b> in water was found to cause this self-inflation process. The resulting vesicle-like structure exhibits spatial characteristics similar to those of natural photosynthetic cells, with QDs acting as pigments uniformly distributed on the <b>CPPA</b> membranes, which have embedded cobalt catalytic centers. This architecture ensures optimal absorption of visible light and facilitates efficient electron transfer between the QDs and catalytic centers. As a result, <b>GVL-QDs@CPPA</b> assemblies efficiently harness photogenerated electrons and holes to convert protons and isopropanol into hydrogen (H₂) and acetone, respectively, achieving a nearly 1:1 ratio of the reduction product (H₂) to the oxidation product (acetone).</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31537–31546 31537–31546"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"MOF-Derived Nitrogen-Rich Hollow Nanocages as a Sulfur Carrier for High-Voltage Aluminum Sulfur Batteries","authors":"Tianming Liu,&nbsp;Guocheng Lv*,&nbsp;Meng Liu,&nbsp;Xiaoya Cui,&nbsp;Hao Liu,&nbsp;Haodong Li,&nbsp;Changchun Zhao,&nbsp;Longfei Wang,&nbsp;Juchen Guo and Libing Liao,&nbsp;","doi":"10.1021/acsnano.4c1309210.1021/acsnano.4c13092","DOIUrl":"https://doi.org/10.1021/acsnano.4c13092https://doi.org/10.1021/acsnano.4c13092","url":null,"abstract":"<p >Aluminum–sulfur batteries (ASBs) are emerging as promising energy storage systems due to their safety, low cost, and high theoretical capacity. However, it remains a challenge to overcome voltage hysteresis and short cycle life in the sulfur/Al₂S₃ conversion reaction, which hinders the development of ASBs. Here, we studied a high-voltage ASB system based on sulfur oxidation in an AlCl₃/urea electrolyte. Nitrogen-doped hollow nanocages (HNCs) synthesized from MOF precursors were rationally designed as sulfur/carbon composite electrodes (S@HNC), and the impact of the nitrogen species on the electrochemical performance of sulfur electrodes was systematically investigated. The S@HNC-900 achieved efficient conversion at 1.9 V, delivering a stable capacity of 197.3 mA h g^–1 and a Coulombic efficiency of 93.28% after 100 cycles. Furthermore, the S@HNC-900 electrode exhibited exceptional rate capacity and 800th long-term cycling stability, retaining a capacity of 87.1 mA h g^–1 at 500 mA g^–1. Ex situ XPS and XRD characterizations elucidated the redox mechanism, revealing a four-electron transfer process (S/AlSCl₇) at the S@HNC-900 electrode. Density functional theory calculations demonstrated that pyridinic nitrogen-enriched HNC-900 significantly enhanced the sulfur conversion reaction and facilitated the adsorption of sulfur intermediates (SCl₃⁺) on the carbon interface. This work provides critical insights into the high-voltage sulfur redox mechanism and establishes a foundation for the rational design of carbon-based electrocatalysts for the enhancement of ASB performance.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"18 45","pages":"31559–31568 31559–31568"},"PeriodicalIF":15.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Elucidating Details of the Transformation of Birnessite into a Tunnel Structure in the Presence of Tl(I)","authors":"Rodrigo J. Martínez,&nbsp;Teresa Pi-Puig and Mario Villalobos*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0022710.1021/acsearthspacechem.4c00227","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00227https://doi.org/10.1021/acsearthspacechem.4c00227","url":null,"abstract":"<p >The affinity between highly toxic Tl⁺ and birnessite has been a matter of active research because the sorption mechanism involved seems to depend upon the doses of applied Tl⁺ per Mn present, which also affects how birnessite is transformed. Aqueous Tl⁺ is very mobile; therefore, its transformation and strong immobilization by Mn oxides is of high interest for environmental research. Birnessites are laminar Mn oxides that show a complex sorption behavior, which involves binding to internal sites of the structure and external surface groups and a high oxidation potential. In the present short investigation, we report some important issues not resolved over the mechanism involved when small Tl⁺/Mn interacts, in which the laminar structure changes to a tunneled structure. Specifically, because very little Tl⁺ is oxidized (as opposed to when higher ratios are involved), water was experimentally confirmed as the reducing agent and the probable mechanism involved was theoretically worked out. Also, the irreversible nature of Tl(I) sorption inside the transformed tunneled structure was tested, which confirmed the extremely high affinity of the Mn oxide tunnels for dehydrated Tl(I).</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 11","pages":"2117–2122 2117–2122"},"PeriodicalIF":2.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00227","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142691614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}