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Electrospinning of LaB6/PEDOT:PSS/PEO Fiber Composites of Unique Morphologies. 独特形态的 LaB6/PEDOT:PSS/PEO 纤维复合材料的电纺丝。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-15 DOI: 10.1021/acs.langmuir.4c03538
C Ingram Vargas-Consuelos, Victor R Vasquez, Olivia A Graeve

We present a direct electrospinning fabrication technique for the manufacture of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/poly(ethylene oxide) (PEDOT:PSS/PEO) polymer fibers containing embedded cubic lanthanum hexaboride (LaB6) particles. We focus on the impact of relative humidity on the formation of uniform polymer fibers and show that a relative humidity of 5% is optimal, resulting in an average fiber thickness of 266 ± 88 nm. As the relative humidity is increased, the fibers contain beads as a consequence of Rayleigh instabilities. The addition of lanthanum hexaboride cubic particles to the polymer solution before electrospinning results in the encapsulation of the LaB6 particles inside the fibers. We investigate the effect of LaB6 particle size on morphology and observe that particles of ∼500 nm yield a fiber-cube-fiber morphology, while 2 μm particles result in fewer embedded cubes along the length of the polymer fibers. This phenomenon likely arises from electrodynamic interactions between the LaB6 particles in the polymer solution and the electric field lines generated during electrospinning between the spinneret and the collector. Our results display the versatility of the electrospinning technique in the fabrication of unique polymer/hexaboride composite fibers.

我们介绍了一种直接电纺丝制造聚(3,4-亚乙二氧基噻吩):聚(苯乙烯磺酸)/聚(环氧乙烷)(PEDOT:PSS/PEO)聚合物纤维的技术,这种纤维含有嵌入式立方六硼化镧(LaB6)颗粒。我们重点研究了相对湿度对形成均匀聚合物纤维的影响,结果表明,5% 的相对湿度是最佳湿度,可形成平均厚度为 266 ± 88 nm 的纤维。随着相对湿度的增加,由于瑞利不稳定性的影响,纤维中会出现微珠。在电纺丝前向聚合物溶液中添加立方六硼化镧颗粒可将 LaB6 颗粒包裹在纤维内部。我们研究了 LaB6 粒子大小对形态的影响,观察到 500 纳米以下的粒子会产生纤维立方体形态,而 2 微米的粒子会导致聚合物纤维长度上嵌入的立方体数量减少。这种现象可能是由于聚合物溶液中的 LaB6 粒子与电纺丝过程中在喷丝板和收集器之间产生的电场线之间的电动相互作用造成的。我们的研究结果展示了电纺丝技术在制造独特的聚合物/六硼化物复合纤维方面的多功能性。
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引用次数: 0
Engineering ZnIn2S4 Nanosheets with Zinc Vacancies: Unleashing Enhanced Photocatalytic Degradation of Tetracycline. 含有锌空位的 ZnIn2S4 纳米片工程:增强四环素的光催化降解。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-15 DOI: 10.1021/acs.langmuir.4c03707
Quanhua Xie, Jiani Qin, Ting Gao, Fei Li, Nianbing Zhong, Bao Pan

Defect engineering is a highly effective strategy for accelerating charge transfer and enhancing the performance of photocatalysts. In this study, ZnIn2S4 nanosheets were designed and prepared with controlled Zn vacancies to optimize the electronic band structure and localized charge density of ZnIn2S4. EPR results confirmed the formation of Zn vacancies. This modification enabled efficient capture of photoexcited charges in defect centers, thereby prolonging the carrier's lifetime. Theoretical calculations demonstrated that these vacancies induced the formation of new defect states and highly efficient surface reaction sites. As anticipated, under visible light irradiation, the photocatalytic tetracycline removal rate of the ZnIn2S4 nanosheets with Zn vacancies reached 82.8% within 60 min, significantly higher than that observed for the pristine ZnIn2S4 sample. These findings offer valuable insights into the deliberate construction of metal-vacancy-containing photocatalytic nanomaterials for the enhanced degradation of micropollutants.

缺陷工程是加速电荷转移和提高光催化剂性能的一种非常有效的策略。本研究设计并制备了具有可控锌空位的 ZnIn2S4 纳米片,以优化 ZnIn2S4 的电子能带结构和局部电荷密度。EPR 结果证实了锌空位的形成。这种改性使得光激发电荷能被有效地捕获到缺陷中心,从而延长了载流子的寿命。理论计算表明,这些空位诱导形成了新的缺陷态和高效的表面反应位点。正如预期的那样,在可见光照射下,带有 Zn 空位的 ZnIn2S4 纳米片的光催化四环素去除率在 60 分钟内达到 82.8%,明显高于原始 ZnIn2S4 样品。这些发现为有意构建含金属空位的光催化纳米材料以提高微污染物的降解能力提供了宝贵的启示。
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引用次数: 0
Fine-Tuning Microporosity of Crystalline Vanadomolybdate Frameworks for Selective Adsorptive Separation of Kr from Xe. 微调结晶钒钼酸盐框架的微孔,从 Xe 中选择性吸附分离 Kr。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1021/acs.langmuir.4c02910
Suchona Akter, Yong Li, Min-Bum Kim, Md Omar Faruque, Zhonghua Peng, Praveen K Thallapally, Mohammad R Momeni

Selective adsorptive capture and separation of chemically inert krypton (Kr) and xenon (Xe) noble gases with very low ppmv concentrations in air and industrial off-gases constitute an important technological challenge. Here, using a synergistic combination of experiment and theory, the microporous crystalline vanadomolybdates (MoVOx) as highly selective Kr sorbents are studied in detail. By varying the Mo/V ratios, we show for the first time that their one-dimensional (1D) pores can be fine-tuned for the size-selective adsorption of Kr over the larger Xe with selectivities reaching >100. Using extensive electronic structure calculations and grand canonical Monte Carlo simulations, the competition between Kr uptake with CO2 and N2 was also investigated. As most materials reported so far are selective toward the larger, more polarizable Xe than Kr, this work constitutes an important step toward robust Kr-selective sorbent materials. This work highlights the potential use of porous crystalline transition metal oxides as energy-efficient and selective noble gas capture sorbents for industrial applications.

选择性吸附捕获和分离空气和工业废气中化学惰性气体浓度极低的氪(Kr)和氙(Xe)惰性气体是一项重要的技术挑战。在此,通过实验与理论的协同结合,详细研究了作为高选择性 Kr 吸附剂的微孔结晶钒钼酸盐(MoVOx)。通过改变 Mo/V 比率,我们首次发现其一维(1D)孔隙可以微调,以实现对较大 Xe 上 Kr 的尺寸选择性吸附,选择性可达 >100。通过大量的电子结构计算和大规范蒙特卡洛模拟,还研究了 Kr 与 CO2 和 N2 之间的吸附竞争。由于迄今为止报道的大多数材料都是选择性大于 Kr 的、极化性更强的 Xe,因此这项研究工作是向强 Kr 选择性吸附材料迈出的重要一步。这项研究强调了多孔结晶过渡金属氧化物作为高能效、高选择性惰性气体捕集吸附剂在工业应用中的潜在用途。
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引用次数: 0
Capsaicin-Loaded Melanin Nanoparticles for Long-Lasting Nociceptive-Selective Nerve Blockade. 用于长效痛觉选择性神经阻滞的涂有辣椒素的黑色素纳米颗粒
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1021/acs.langmuir.4c01725
Xiaosi Li, Qi Li, Xinyu Xia, Edward Deng, Yue Zhao, Yi He, Chao Zhao

Clinically used amino-ester and amino-amide local anesthetics, such as bupivacaine and lidocaine, face two primary challenges: inadequate duration of action and nonselective action on both sensory and motor neurons, resulting in motor function loss alongside pain relief. In this work, we developed capsaicin-loaded melanin nanoparticles (Cap-MNPs) to address these two challenges. Capsaicin selectively acts on sensory neurons without affecting motor neurons, thereby achieving nociceptive-selective nerve blockade. Melanin is known for its exceptional biocompatibility, biodegradability, and abundance in pigmented human tissue. Melanin's inherent chemical structure and hydrophobic nature enable the encapsulation and sustained release of amino-ester and amino-amide local anesthetics with aromatic rings through π-π interactions and hydrophobic interactions. The drug loading efficiency of Cap-MNPs was 82.99 ± 1.55%, the drug loading capacity was 67.47 ± 4.24%, and capsaicin was continuously released for more than 360 h. In rats, a single injection of Cap-MNPs containing 8.04 mg of capsaicin produced a sciatic sensory nerve block lasting for 6 h without causing any local toxicity and capsaicin-related systemic toxicity. Cap-MNPs show promise as clinically useful therapeutics for pain management.

临床使用的氨基酯和氨基酰胺局麻药(如布比卡因和利多卡因)面临两个主要挑战:作用时间不足以及对感觉和运动神经元的作用不具有选择性,从而导致在止痛的同时丧失运动功能。在这项工作中,我们开发了载入辣椒素的黑色素纳米颗粒(Cap-MNPs)来解决这两个难题。辣椒素选择性地作用于感觉神经元,而不影响运动神经元,从而实现痛觉选择性神经阻断。黑色素以其优异的生物相容性、生物可降解性和人体色素组织的丰富性而闻名。黑色素固有的化学结构和疏水性使其能够通过π-π相互作用和疏水作用封装和持续释放带有芳香环的氨基酯和氨基酰胺局麻药。Cap-MNPs 的载药效率为 82.99 ± 1.55%,载药量为 67.47 ± 4.24%,辣椒素的持续释放时间超过 360 小时。在大鼠体内单次注射含有 8.04 毫克辣椒素的 Cap-MNPs 可产生持续 6 小时的坐骨神经感觉阻滞,且不会引起任何局部毒性和辣椒素相关的全身毒性。Cap-MNPs有望成为临床上治疗疼痛的有效药物。
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引用次数: 0
Antimicrobial GL13K Peptide-Decorated ZnO Nanoparticles To Treat Bacterial Infections 治疗细菌感染的抗菌 GL13K 肽装饰氧化锌纳米粒子
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1021/acs.langmuir.4c03206
Xu Zhang, Yinghao Liu, Xue’e Zhang, Mengzhen Tang, Weihong Xi, Junchao Wei
As a broad-spectrum antimicrobial material, ZnO nanoparticles (NPs) offer a novel approach to infected wounds in the clinic; however, it is very necessary to improve the antimicrobial performance of ZnO to satisfy the clinic requirements. In this work, a new antimicrobial hybrid ZnO@PDA/GL13K was prepared by attaching the antimicrobial GL13K peptide on the surface of ZnO NPs via polydopamine (PDA) as a covalent bonding agent, which can enhance the reactive oxygen species (ROS) production and damage the cell wall, showing superior antimicrobial efficacy. Besides, the ZnO@PDA/GL13K hybrid can promote the healing of bacterial infected wounds, with the wound area only remaining 1.8% on day 9, about 2 times smaller than that of the ZnO group. Moreover, ZnO@PDA/GL13K also showed good biocompatibility, and no side effect on normal tissue and organs was found, implying that the antimicrobial hybrid may possess prospective application in biomedical fields.
作为一种广谱抗菌材料,氧化锌纳米粒子(NPs)为临床治疗感染性伤口提供了一种新方法;然而,如何提高氧化锌的抗菌性能以满足临床需求是非常必要的。本研究通过聚多巴胺(PDA)作为共价键合剂,将抗菌肽 GL13K 附着在 ZnO NPs 表面,制备了一种新型的抗菌杂化 ZnO@PDA/GL13K,这种杂化 ZnO@PDA/GL13K 可增强活性氧(ROS)的产生并破坏细胞壁,显示出卓越的抗菌功效。此外,ZnO@PDA/GL13K 杂化物还能促进细菌感染伤口的愈合,伤口面积在第 9 天仅剩余 1.8%,比 ZnO 组小约 2 倍。此外,ZnO@PDA/GL13K 还表现出良好的生物相容性,对正常组织和器官没有副作用,这意味着该抗菌杂化物在生物医学领域具有广阔的应用前景。
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引用次数: 0
Simple Models of Directly Measured Energy Landscapes for Different Shaped Particles in Nonuniform AC Electric Fields 非均匀交流电场中不同形状粒子直接测量能量分布的简单模型
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1021/acs.langmuir.4c03101
Lechuan Zhang, Alec J. Pellicciotti, Rachel S. Hendley, Xiao Wang, Michael A. Bevan
We report direct measurements of potential energy landscapes for different shaped colloidal particles interacting with nonuniform AC electric fields. Epoxy particle shapes investigated include disks, ellipses, squares, rectangles, and rhombuses, which are all part of the superelliptical prism shape class and are chosen to systematically vary particle anisotropy and corner features. The measurement configuration consists of noninteracting single particles sedimented onto microscope slides within electric fields between parallel coplanar electrodes. Thermally sampled positions and orientations of single particles in nonuniform fields are tracked in an optical microscope, and measured potential energy landscapes are obtained via Boltzmann inversions. We develop a new analytically simple model that captures all measured energy landscapes for superelliptical prism shaped colloidal particles with electrostatic double layers. The model recovers known validated potentials for spherical and ellipsoidal particles, and therefore captures energy landscapes for a variety of different colloidal particle sizes, shapes, and materials reported in prior studies.
我们报告了对与非均匀交流电场相互作用的不同形状胶体粒子的势能景观的直接测量结果。研究的环氧颗粒形状包括圆盘、椭圆、正方形、长方形和菱形,它们都属于超椭圆棱柱形状类别,选择这些形状是为了系统地改变颗粒的各向异性和边角特征。测量配置包括在平行共面电极之间的电场中,沉积在显微载玻片上的非相互作用单颗粒。在光学显微镜中跟踪非均匀场中单个粒子的热采样位置和方向,并通过玻尔兹曼反演获得测量的势能景观。我们建立了一个新的简单分析模型,该模型能捕捉到具有静电双层的超椭圆棱柱形胶体粒子的所有测量能谱。该模型恢复了已知的球形和椭圆形颗粒的验证电势,因此能捕捉到先前研究中报告的各种不同胶体颗粒尺寸、形状和材料的能量景观。
{"title":"Simple Models of Directly Measured Energy Landscapes for Different Shaped Particles in Nonuniform AC Electric Fields","authors":"Lechuan Zhang, Alec J. Pellicciotti, Rachel S. Hendley, Xiao Wang, Michael A. Bevan","doi":"10.1021/acs.langmuir.4c03101","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03101","url":null,"abstract":"We report direct measurements of potential energy landscapes for different shaped colloidal particles interacting with nonuniform AC electric fields. Epoxy particle shapes investigated include disks, ellipses, squares, rectangles, and rhombuses, which are all part of the superelliptical prism shape class and are chosen to systematically vary particle anisotropy and corner features. The measurement configuration consists of noninteracting single particles sedimented onto microscope slides within electric fields between parallel coplanar electrodes. Thermally sampled positions and orientations of single particles in nonuniform fields are tracked in an optical microscope, and measured potential energy landscapes are obtained via Boltzmann inversions. We develop a new analytically simple model that captures all measured energy landscapes for superelliptical prism shaped colloidal particles with electrostatic double layers. The model recovers known validated potentials for spherical and ellipsoidal particles, and therefore captures energy landscapes for a variety of different colloidal particle sizes, shapes, and materials reported in prior studies.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"42 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis, Performance Evaluation, and Adsorption-Dispersion Mechanism of Sulfonic Acid-Terminated Long Side Chain Polycarboxylate Superplasticizers. 磺酸封端长侧链聚羧酸盐超塑化剂的合成、性能评估和吸附分散机理。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1021/acs.langmuir.4c03026
Haotian Duan, Tianfeng Zhou, Beibei Li, Yuxia Pang, Hongming Lou, Dongjie Yang, Xueqing Qiu

Polycarboxylate superplasticizers (PCEs) achieve dispersion mainly via steric hindrance from poly(ether) side chains. However, long side chains may cause structural collapse. This study mitigates this issue by introducing sulfonic acid terminations to the long side chains, synthesizing sulfonic-terminated polycarboxylates (PCEPS). Electrostatic repulsion between sulfonic and carboxyl groups on the main chain reduces the level of collapse, enhancing PCE dispersion in cement. PCEPS-4000 showed the strongest dispersion compared with conventional PCEs (PCEC). PCEPS-4000 formed an adsorption layer thickness (ALT) of 11.65 nm, showing a significant improvement over the 7.93 nm observed in the carboxyl-terminated long side chain polycarboxylate (PCETA). Stronger negative charge and lower complexation of sulfonic acid groups enhance the side chain extension. PCEPS also shows good clay tolerance and slump retention, proving its versatility as a concrete admixture.

聚羧酸盐超塑化剂(PCE)主要通过聚(醚)侧链的立体阻碍实现分散。然而,长侧链可能会导致结构坍塌。本研究通过在长侧链上引入磺酸端接,合成磺酸端接聚羧酸盐(PCEPS),从而缓解了这一问题。主链上的磺酸基和羧基之间的静电斥力降低了塌陷程度,增强了 PCE 在水泥中的分散性。与传统 PCE(PCEC)相比,PCEPS-4000 的分散性最强。PCEPS-4000 形成的吸附层厚度(ALT)为 11.65 nm,与羧基封端长侧链聚羧酸盐(PCETA)的 7.93 nm 相比有了显著改善。较强的负电荷和较低的磺酸基复合性增强了侧链的延伸。PCEPS 还具有良好的粘土耐受性和坍落度保持性,证明了其作为混凝土外加剂的多功能性。
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引用次数: 0
Investigation of Erosion and Deposition Due to Flows with Particles 带颗粒的水流造成的侵蚀和沉积调查
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1021/acs.langmuir.4c03418
Sol Johanne Mehammer, Martin M. Greve, Pawel Kosinski, Anna Kosinska
In this work, we employed experimental technique to study the issue of particle erosion and deposition in multiphase flows involving both particles of micro/meso- and nanoscale (sand particles and iron oxide particles). Especially, liquids with immersed nanoparticles gained a lot of interest in the recent years due to their enhanced thermal properties. At the same time, this type of fluids is still not widely used in practical and engineering applications, and one of the reasons is a risk of leading to erosion and deposition on, for instance, pipe walls. In our experiments, an aluminum plate was subjected to a flow with particles by immersing it in a beaker with a rotating fluid for 530 h. After this, the plate was investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM), followed by energy dispersive X-ray (EDX) analysis. According to our observations, the erosion was mainly caused by the largest particles (sand particles), while the nanoparticles did not lead to clear erosion but resulted in significant deposition due to strong adhesion, as well as corrosion, resulting in aluminum oxide formation. This issue was also confirmed through theoretical analysis by comparing the momentum response time and the characteristic time of the flow, as well as computational fluid dynamics (CFD) simulations.
在这项工作中,我们采用实验技术研究了微米级和纳米级粒子(沙粒和氧化铁粒子)在多相流中的侵蚀和沉积问题。近年来,浸入纳米颗粒的液体因其更强的热性能而备受关注。与此同时,这类液体在实际和工程应用中仍未得到广泛使用,原因之一是有可能导致侵蚀和沉积在管壁等处。在我们的实验中,我们将一块铝板浸入装有旋转流体的烧杯中 530 小时,使其受到颗粒流的影响。根据我们的观察,侵蚀主要是由最大的颗粒(沙粒)引起的,而纳米颗粒并没有导致明显的侵蚀,但由于附着力强而导致大量沉积,以及腐蚀,形成氧化铝。通过比较流动的动量响应时间和特征时间以及计算流体动力学(CFD)模拟,理论分析也证实了这一问题。
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引用次数: 0
Transition Metals Doped into g-C3N4 via N,O Coordination as Efficient Electrocatalysts for the Carbon Dioxide Reduction Reaction 通过 N、O 配位掺入 g-C3N4 的过渡金属作为二氧化碳还原反应的高效电催化剂
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1021/acs.langmuir.4c03938
Haoyang Qiu, Huohai Yang, Peng Wang, Manxi Leng, Xingbo Ge, Xu Yang, Xin Chen
The electrochemical carbon dioxide reduction reaction (CO2RR) is a potential and efficient method that can directly convert CO2 into high-value-added chemicals under mild conditions. Owing to the exceptionally high activation barriers of CO2, catalysts play a pivotal role in CO2RR. In this study, the transition metal (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) is doped into g-C3N4 with a unique N,O-coordination environment, namely, TM–N1O2/g-C3N4. Herein, the catalytic performance and reaction mechanism for the CO2RR on TM–N1O2/g-C3N4 are systematically investigated by density functional theory methods. Especially, through the calculation of ΔG*H and ΔG*COOHG*OCHO, the catalysts with preference for the CO2RR over the hydrogen evolution reaction (HER) are selected for further study. Furthermore, Gibbs free energy computation results of each elementary step for the CO2RR on these catalysts indicate that Ti–N1O2/g-C3N4 has significant catalytic activity and selectivity for reducing CO2 to methanol (CH3OH) with the limiting potential (UL) of −0.55 V. Finally, through frontier molecular orbital theory and charge transfer analyses, the introduction of the O atoms illustrates that it is instrumental in regulating the electron distribution of the catalytic active site, thereby improving the catalytic performance. This work provides insight into the design of single-atom catalysts with unique coordination structures for the CO2RR.
电化学二氧化碳还原反应(CO2RR)是一种潜在的高效方法,可在温和条件下直接将二氧化碳转化为高附加值化学品。由于 CO2 的活化势垒极高,催化剂在 CO2RR 中起着举足轻重的作用。本研究将过渡金属(TM = Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu 和 Zn)掺杂到具有独特 N、O 配位环境的 g-C3N4 中,即 TM-N1O2/g-C3N4。本文采用密度泛函理论方法系统地研究了 TM-N1O2/g-C3N4 上 CO2RR 的催化性能和反应机理。特别是通过计算ΔG*H 和 ΔG*COOH/ΔG*OCHO,筛选出 CO2RR 比氢气进化反应(HER)更优先的催化剂,以作进一步研究。此外,这些催化剂上 CO2RR 各基本步骤的吉布斯自由能计算结果表明,Ti-N1O2/g-C3N4 在将 CO2 还原为甲醇(CH3OH)时具有显著的催化活性和选择性,极限电位(UL)为 -0.55 V。最后,通过前沿分子轨道理论和电荷转移分析,O 原子的引入说明它有助于调节催化活性位点的电子分布,从而改善催化性能。这项研究为设计具有独特配位结构的 CO2RR 单原子催化剂提供了启示。
{"title":"Transition Metals Doped into g-C3N4 via N,O Coordination as Efficient Electrocatalysts for the Carbon Dioxide Reduction Reaction","authors":"Haoyang Qiu, Huohai Yang, Peng Wang, Manxi Leng, Xingbo Ge, Xu Yang, Xin Chen","doi":"10.1021/acs.langmuir.4c03938","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03938","url":null,"abstract":"The electrochemical carbon dioxide reduction reaction (CO<sub>2</sub>RR) is a potential and efficient method that can directly convert CO<sub>2</sub> into high-value-added chemicals under mild conditions. Owing to the exceptionally high activation barriers of CO<sub>2</sub>, catalysts play a pivotal role in CO<sub>2</sub>RR. In this study, the transition metal (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) is doped into g-C<sub>3</sub>N<sub>4</sub> with a unique N,O-coordination environment, namely, TM–N<sub>1</sub>O<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub>. Herein, the catalytic performance and reaction mechanism for the CO<sub>2</sub>RR on TM–N<sub>1</sub>O<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> are systematically investigated by density functional theory methods. Especially, through the calculation of Δ<i>G</i><sub>*H</sub> and Δ<i>G</i><sub>*COOH</sub>/Δ<i>G</i><sub>*OCHO</sub>, the catalysts with preference for the CO<sub>2</sub>RR over the hydrogen evolution reaction (HER) are selected for further study. Furthermore, Gibbs free energy computation results of each elementary step for the CO<sub>2</sub>RR on these catalysts indicate that Ti–N<sub>1</sub>O<sub>2</sub>/g-C<sub>3</sub>N<sub>4</sub> has significant catalytic activity and selectivity for reducing CO<sub>2</sub> to methanol (CH<sub>3</sub>OH) with the limiting potential (<i>U</i><sub>L</sub>) of −0.55 V. Finally, through frontier molecular orbital theory and charge transfer analyses, the introduction of the O atoms illustrates that it is instrumental in regulating the electron distribution of the catalytic active site, thereby improving the catalytic performance. This work provides insight into the design of single-atom catalysts with unique coordination structures for the CO<sub>2</sub>RR.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"98 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Two-Step Chemical Vapor Deposition for Fabrication of FAPbI3 Single-Crystal Microsheets with High Exciton Binding Energy 两步化学气相沉积法制造具有高激子结合能的 FAPbI3 单晶微片
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-14 DOI: 10.1021/acs.langmuir.4c02782
Qianpeng Zhang, Fang Li, Pei Zuo
Hybrid perovskites exhibit highly efficient optoelectronic properties and find widespread applications in areas such as solar cells, light-emitting diodes, photodetectors, and lasers. Here, we report the innovative synthesis of formamidinium lead iodide (FAPbI3) single-crystal microsheets via a two-step chemical vapor deposition (CVD) method. The microsheets exhibit hexagonal and trapezoidal shapes, with hexagonal FAPbI3 growing parallel to the substrate and trapezoidal FAPbI3 growing perpendicular to the substrate. The dominant role of single-exciton recombination in the photoluminescence (PL) of these microsheets is observed, especially pronounced at low temperatures, attributed to the relatively large exciton binding energies of the samples. Calculations reveal exciton binding energies as high as 110.8 meV for hexagonal and 133.3 meV for trapezoidal FAPbI3 single-crystal microsheets, attributed to reduced rotational freedom of the formamidinium (FA) ions. Further investigation into low-temperature phase transitions indicates lower transition temperatures (around 100 K) for these microsheets, suggesting reduced FA ion rotational freedom and consequently higher exciton binding energies.
混合包晶石具有高效的光电特性,在太阳能电池、发光二极管、光电探测器和激光器等领域有着广泛的应用。在此,我们报告了通过两步化学气相沉积(CVD)法创新合成甲脒碘化铅(FAPbI3)单晶微片的过程。微片呈现六边形和梯形,六边形 FAPbI3 与基底平行生长,梯形 FAPbI3 与基底垂直生长。观察到单激子重组在这些微片的光致发光(PL)中起主导作用,在低温下尤为明显,这归因于样品相对较大的激子结合能。计算显示,六边形 FAPbI3 单晶微片和梯形 FAPbI3 单晶微片的激子结合能分别高达 110.8 meV 和 133.3 meV,这归因于甲脒离子(FA)的旋转自由度降低。对低温相变的进一步研究表明,这些微片的相变温度较低(约 100 K),这表明 FA 离子的旋转自由度降低,因此激子结合能较高。
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引用次数: 0
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