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Aqueous Photoiniferter Polymerization of Acrylonitrile. 丙烯腈的水性光增塑聚合。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-11-19 DOI: 10.1021/acsmacrolett.4c00642
Evan K Stacy, Mac L McCormick, Kaden C Stevens, Penelope E Jankoski, Jeff Aguinaga, Derek L Patton, Brent S Sumerlin, Tristan D Clemons

Polyacrylonitrile (PAN) is a key industrial polymer for the production of carbon fiber for high-strength, lightweight composite material applications, with an estimated 90% of the carbon fiber market relying on PAN-based polymers. Traditionally, PAN synthesis is achieved by conventional radical polymerization, resulting in broad molecular weight distributions and the use of toxic organic solvents or surfactants during the synthesis. Additionally, attempts to improve polymer and processing properties by controlled radical polymerization methods suffer from low monomer conversions and struggle to achieve molecular weights suitable for producing high-performance carbon fiber. In this study, we present an aqueous photoiniferter (aqPI) polymerization of acrylonitrile, achieving high monomer conversion and high PAN molecular weights with significantly faster kinetics and dispersity control when compared to traditional methods. This approach allows for the unprecedented control of polymer properties that are integral for downstream processing for enhanced carbon fiber production.

聚丙烯腈(PAN)是生产高强度、轻质复合材料用碳纤维的主要工业聚合物,据估计,90% 的碳纤维市场依赖于 PAN 基聚合物。传统上,PAN 的合成是通过传统的自由基聚合法实现的,因此分子量分布较广,合成过程中需要使用有毒的有机溶剂或表面活性剂。此外,试图通过受控自由基聚合方法来改善聚合物和加工性能的尝试受到了单体转化率低的困扰,并且难以获得适合生产高性能碳纤维的分子量。在本研究中,我们介绍了一种丙烯腈的水性光增塑剂(aqPI)聚合方法,与传统方法相比,该方法实现了高单体转化率和高 PAN 分子量,且动力学和分散度控制明显更快。这种方法可对聚合物特性进行前所未有的控制,而聚合物特性是下游加工过程中不可或缺的一部分,可提高碳纤维的产量。
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引用次数: 0
Modeling of Chain Sequence Length and Distribution in Random Copolyesters 无规共聚物链序长度和分布建模
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-11-15 DOI: 10.1021/acsmacrolett.4c00598
Yisong Wang, Bingxue Jiang, Zhengqi Peng, Khak Ho Lim, Qingyue Wang, Shengbin Shi, Jieyuan Zheng, Deliang Wang, Xuan Yang, Pingwei Liu, Wen-Jun Wang
The performances and properties of random copolyesters, including biodegradability, mechanical and thermal properties, transparency, etc., are highly influenced by their chain structures. However, obtaining detailed chain sequence information remains a significant challenge. This study introduces a mathematical model based on a probabilistic approach to determine the sequence length and distribution in random copolyesters. Two types of copolyesters, A1A1BB-A2A2BB, representing poly(butylene adipate-co-terephthalate) (PBAT), and A1A1B1B1-A2B2, using poly(butylene succinate-co-glycolic acid) (PBT–PGA) as an example, are the focus. The predicted sequence lengths of various copolyesters derived from the model are in good agreement with the values reported in the literature. The chain sequence distribution obtained from the model provides better insights into the unique properties of the copolyesters. It is observed that the incorporation of hydroxyl acid units into copolyester chains effectively reduces the sequence length without altering the copolymer composition, offering a strategic approach for enhancing degradation performance while maintaining mechanical properties of random copolyesters. The influence of the number-average sequence length becomes particularly significant when the copolymer composition ranges between 0.7 and 0.9, with a higher copolymer composition required for copolyesters containing hydroxyl acid monomer units. This model represents a powerful tool for researchers, enabling a deeper understanding of the relationship between copolymer composition and its structural characteristics in random copolyesters and facilitating the development of high-performance random copolyesters.
无规共聚聚酯的性能和特性(包括生物降解性、机械和热特性、透明度等)受其链结构的影响很大。然而,获取详细的链序列信息仍是一项重大挑战。本研究介绍了一种基于概率方法的数学模型,用于确定无规共聚聚酯的序列长度和分布。研究重点是两类共聚物,即代表聚(己二酸丁二醇酯)(PBAT)的 A1A1BB-A2A2BB 和以聚(丁二酸丁二醇酯-聚乙二醇酸)(PBT-PGA)为例的 A1A1B1B1-A2B2。根据模型得出的各种共聚物的预测序列长度与文献报道的数值十分吻合。从模型中获得的链序分布可以更好地了解共聚物的独特性质。据观察,在共聚聚酯链中加入羟基酸单元可在不改变共聚物组成的情况下有效缩短链序长度,这为在保持无规共聚聚酯机械性能的同时提高降解性能提供了一种策略方法。当共聚物成分在 0.7 至 0.9 之间时,数均序列长度的影响尤为显著,含有羟基酸单体单元的共聚物需要更高的共聚物成分。该模型为研究人员提供了一个强有力的工具,使他们能够更深入地了解无规共聚聚酯中共聚物组成与其结构特征之间的关系,并促进高性能无规共聚聚酯的开发。
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引用次数: 0
Circular Cross-Linked Polyethylene Enabled by In-Chain Ketones. 链内酮促成环状交联聚乙烯。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-11-15 DOI: 10.1021/acsmacrolett.4c00660
Tobias O Morgen, Stefan Mecking

Cross-linked polyethylenes (PEs) are widely employed, but the permanent links between the chains impede recycling. We show that via imine formation with diamines keto-functionalized polyethylenes from both free-radical (keto-low-density PE, keto-LDPE) and catalytic (keto-high-density PE, keto-HDPE) nonalternating ethylene-CO copolymerization can be cross-linked efficiently in the melt, resulting in gel fractions of the formed cross-linked PEs of up to 85% and improved tensile properties. The imine-based cross-links in the material can be hydrolyzed at 140 °C to recycle up to 97% of the initial thermoplastic keto-polyethylene. Low keto contents of ≤1.5 mol % are found ideal to retain PE-like thermal properties, achieve sufficient cross-link density, and maintain circular recyclability.

交联聚乙烯(PE)被广泛使用,但其链之间的永久性连接阻碍了回收利用。我们的研究表明,通过与二胺形成亚胺,自由基(酮基低密度聚乙烯,keto-LDPE)和催化(酮基高密度聚乙烯,keto-HDPE)非交替乙烯-CO 共聚产生的酮基官能团聚乙烯可在熔体中高效交联,从而使形成的交联聚乙烯凝胶分数高达 85%,并改善了拉伸性能。材料中的亚胺基交联可在 140 °C 下水解,从而回收高达 97% 的初始热塑性酮基聚乙烯。低酮含量(≤1.5 mol %)是保持类似聚乙烯的热性能、达到足够的交联密度和保持循环可回收性的理想选择。
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引用次数: 0
Light-Driven Organocatalyzed Controlled Radical Copolymerization of (Perfluoroalkyl)ethylenes and Vinyl Esters/Amides 全氟烷基乙烯和乙烯基酯/酰胺的光驱动有机催化受控自由基共聚物
IF 5.8 Q1 POLYMER SCIENCE Pub Date : 2024-11-15 DOI: 10.1021/acsmacrolett.4c00737
Qianhao Ye, Kaixuan Chen, Chengda Zhou, Mengli Xu, Mao Chen
Fluoropolymers of well-defined structures exhibit significant potential in a broad range of high-tech applications. However, the controlled synthesis of fluoropolymers from easily available monomers remains difficult. In this work, we report the development of an organocatalyzed controlled radical copolymerization of (perfluoroalkyl)ethylenes (PFAEs) and unconjugated vinyl monomers (UCMs) under light irradiation, which has enabled on-demand access toward side-chain fluorinated polymers under metal-free conditions. This method furnishes a large variety of polymers with diverse fluoroalkyl and ester/amide as pendent groups, tunable molar masses, and low dispersities (ca. Đ = 1.1–1.3), and adjustable fractions of PFAE and UCM units. Obtained fluoropolymers exhibit good chain-end fidelity and activity, allowing chain-extension polymerizations to prepare block copolymers of complicated compositions. Furthermore, the PFAE copolymers exhibit outstanding light transmission and low refractive index.
结构明确的含氟聚合物在广泛的高科技应用领域具有巨大潜力。然而,利用容易获得的单体可控合成含氟聚合物仍然十分困难。在这项工作中,我们报告了在光照射下(全氟烷基)乙烯(PFAEs)和非共轭乙烯基单体(UCMs)的有机催化受控自由基共聚的发展情况,从而实现了在无金属条件下按需获得侧链含氟聚合物。这种方法可生产出多种聚合物,它们以不同的氟烷基和酯/酰胺作为悬垂基团,摩尔质量可调,分散度低(约 Đ = 1.1-1.3),PFAE 和 UCM 单元的比例可调。所获得的含氟聚合物具有良好的链端保真度和活性,可以通过链延伸聚合来制备成分复杂的嵌段共聚物。此外,PFAE 共聚物还具有出色的透光性和低折射率。
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引用次数: 0
Fast and generalizable micromagnetic simulation with deep neural nets 利用深度神经网络进行快速、通用的微磁模拟
IF 23.8 Q1 POLYMER SCIENCE Pub Date : 2024-11-14 DOI: 10.1038/s42256-024-00914-7
Yunqi Cai, Jiangnan Li, Dong Wang

Important progress has been made in micromagnetics, driven by its wide-ranging applications in magnetic storage design. Numerical simulation, a cornerstone of micromagnetics research, relies on first-principles rules to compute the dynamic evolution of micromagnetic systems using the renowned Landau–Lifshitz–Gilbert equation, named after Landau, Lifshitz and Gilbert. However, these simulations are often hindered by their slow speeds. Although fast Fourier transformation calculations reduce the computational complexity to O(Nlog(N)), it remains impractical for large-scale simulations. Here we introduce NeuralMAG, a deep learning approach to micromagnetic simulation. Our approach follows the Landau–Lifshitz–Gilbert iterative framework but accelerates computation of demagnetizing fields by employing a U-shaped neural network. This neural network architecture comprises an encoder that extracts aggregated spins at various scales and learns the local interaction at each scale, followed by a decoder that accumulates the local interactions at different scales to approximate the global convolution. This divide-and-accumulate scheme achieves a time complexity of O(N), notably enhancing the speed and feasibility of large-scale simulations. Unlike existing neural methods, NeuralMAG concentrates on the core computation—rather than an end-to-end approximation for a specific task—making it inherently generalizable. To validate the new approach, we trained a single model and evaluated it on two micromagnetics tasks with various sample sizes, shapes and material settings.

在磁存储设计的广泛应用推动下,微磁学取得了重要进展。数值模拟是微磁学研究的基石,它依赖于第一原理规则,利用以 Landau、Lifshitz 和 Gilbert 命名的著名的 Landau-Lifshitz-Gilbert 方程计算微磁系统的动态演化。然而,这些模拟往往因速度慢而受阻。虽然快速傅立叶变换计算能将计算复杂度降低到 O(Nlog(N)),但对于大规模仿真来说仍然不切实际。在此,我们介绍一种用于微磁模拟的深度学习方法--NeuralMAG。我们的方法遵循 Landau-Lifshitz-Gilbert 迭代框架,但通过采用 U 型神经网络来加速消磁场的计算。这种神经网络架构由一个编码器和一个解码器组成,编码器负责提取不同尺度的聚合自旋,并学习每个尺度的局部相互作用,解码器则负责累积不同尺度的局部相互作用,以近似全局卷积。这种 "分割-累积 "方案的时间复杂度为 O(N),显著提高了大规模模拟的速度和可行性。与现有的神经方法不同,NeuralMAG 专注于核心计算,而不是针对特定任务的端到端近似,因此具有内在的通用性。为了验证这种新方法,我们训练了一个单一模型,并在两个具有不同样本大小、形状和材料设置的微观磁学任务中对其进行了评估。
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引用次数: 0
Flexible Potassium-Ion Batteries Enabled by Encapsulating Hollow NiSe/SnSe Nanocubes within Freestanding N-doped Carbon Nanofibers 通过在独立的掺杂 N 的碳纳米纤维中封装中空镍硒/硒化纳米立方体实现柔性钾离子电池
IF 20.4 Q1 POLYMER SCIENCE Pub Date : 2024-11-14 DOI: 10.1016/j.ensm.2024.103908
Bo Yan, Yilong Yu, Hao Sun, Xueping Liu, Yahao Li, Lulu Zhang, Xuelin Yang, Shengkui Zhong, Renheng Wang
Self-supporting electrode materials are instrumental in accelerating the development of flexible potassium-ion batteries (PIBs). However, the challenge lies in designing self-supporting materials with sophisticated structures and compositions to overcome the sluggish kinetics and volume effect caused by the large size of potassium ions during K-storage. In this work, we present novel flexible anodes synthesized by confining hollow NiSe/SnSe nanocubes within nitrogen-doped carbon nanofibers (H-NiSe/SnSe@NC). Leveraging its unique organization and composition, the H-NiSe/SnSe@NC anode exhibits impressive initial Coulombic efficiency, excellent rate capability, and exceptional cyclability, even at high mass loadings, outperforming most reported PIBs anodes. Utilizing in-situ XRD and ex-situ TEM techniques, we elucidate the mechanism responsible for its high capacity and gain insights into the K-storage behavior and reaction kinetics through diverse electrochemical measurements. First-principles calculations further clarify the underlying mechanism by which the designed heterostructured anode enhances the adsorption/diffusion of K-ions. Additionally, we integrate this novel anode into full cells, achieving high energy density and extended cycling life. Remarkably, the pouch cell we fabricated delivers high reversible capacity and cyclability even under periodic bending conditions, highlighting its superiority for flexible devices. This research showcases the significance of designing and fabricating advanced self-supporting electrodes for flexible PIBs applications.
自支撑电极材料有助于加速柔性钾离子电池(PIB)的开发。然而,如何设计具有复杂结构和成分的自支撑材料,以克服钾离子储存过程中因钾离子尺寸过大而导致的动力学迟缓和体积效应,是一项挑战。在这项工作中,我们介绍了通过将空心镍硒/硒纳米立方体限制在掺氮碳纳米纤维(H-NiSe/SnSe@NC)内合成的新型柔性阳极。利用其独特的组织和成分,H-NiSe/SnSe@NC 阳极即使在高负载情况下也能表现出令人印象深刻的初始库仑效率、出色的速率能力和卓越的循环性,优于大多数已报道的 PIBs 阳极。利用原位 XRD 和原位 TEM 技术,我们阐明了造成其高容量的机理,并通过各种电化学测量深入了解了 K 存储行为和反应动力学。第一性原理计算进一步阐明了所设计的异质结构阳极增强 K 离子吸附/扩散的基本机制。此外,我们还将这种新型阳极集成到全电池中,实现了高能量密度并延长了循环寿命。值得注意的是,即使在周期性弯曲条件下,我们制造的袋式电池也能提供高可逆容量和循环能力,突出了其在柔性设备方面的优越性。这项研究展示了为柔性 PIB 应用设计和制造先进自支撑电极的重要意义。
{"title":"Flexible Potassium-Ion Batteries Enabled by Encapsulating Hollow NiSe/SnSe Nanocubes within Freestanding N-doped Carbon Nanofibers","authors":"Bo Yan, Yilong Yu, Hao Sun, Xueping Liu, Yahao Li, Lulu Zhang, Xuelin Yang, Shengkui Zhong, Renheng Wang","doi":"10.1016/j.ensm.2024.103908","DOIUrl":"https://doi.org/10.1016/j.ensm.2024.103908","url":null,"abstract":"Self-supporting electrode materials are instrumental in accelerating the development of flexible potassium-ion batteries (PIBs). However, the challenge lies in designing self-supporting materials with sophisticated structures and compositions to overcome the sluggish kinetics and volume effect caused by the large size of potassium ions during K-storage. In this work, we present novel flexible anodes synthesized by confining hollow NiSe/SnSe nanocubes within nitrogen-doped carbon nanofibers (H-NiSe/SnSe@NC). Leveraging its unique organization and composition, the H-NiSe/SnSe@NC anode exhibits impressive initial Coulombic efficiency, excellent rate capability, and exceptional cyclability, even at high mass loadings, outperforming most reported PIBs anodes. Utilizing in-situ XRD and ex-situ TEM techniques, we elucidate the mechanism responsible for its high capacity and gain insights into the K-storage behavior and reaction kinetics through diverse electrochemical measurements. First-principles calculations further clarify the underlying mechanism by which the designed heterostructured anode enhances the adsorption/diffusion of K-ions. Additionally, we integrate this novel anode into full cells, achieving high energy density and extended cycling life. Remarkably, the pouch cell we fabricated delivers high reversible capacity and cyclability even under periodic bending conditions, highlighting its superiority for flexible devices. This research showcases the significance of designing and fabricating advanced self-supporting electrodes for flexible PIBs applications.","PeriodicalId":18,"journal":{"name":"ACS Macro Letters","volume":"34 1","pages":""},"PeriodicalIF":20.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610448","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}
引用次数: 0
High-Resolution Total Internal Reflection-Based Structural Coloration by Electrohydrodynamic Jet Printing of Transparent Polyethylene Glycol Microdomes. 通过电流体动力喷射打印透明聚乙二醇微域实现基于全内反射的高分辨率结构着色。
IF 5.1 Q1 POLYMER SCIENCE Pub Date : 2024-11-14 DOI: 10.1021/acsmacrolett.4c00512
Dongho Lee, Doyoung Byun, Dae-Hyun Cho

Total internal reflection (TIR)-based structural coloration is a brilliant strategy to overcome the need for periodic nanostructures and complex fabrication processes. Light entering the microdome structure undergoes TIR, and owing to varying reflection paths, it exhibits a color that changes with the microdome size. Although solution-based printing techniques have been proposed to achieve this effect, they fall short of full-color realization owing to resolution limitations. Herein, we achieved 3628 dpi of full-color and high-resolution structural color images by printing transparent microdome structures with 1.2-9.9 μm diameter using electrohydrodynamic (EHD) jet printing. Additionally, high-resolution EHD jet-printed structural color images display complex encoded information, enhancing the anticounterfeiting effectiveness through their fabrication simplicity and precise control over the microdome size. Because of these advantages, this TIR-based structural coloration technique with EHD jet printing is highly suitable for anticounterfeiting applications.

基于全内反射(TIR)的结构着色是克服周期性纳米结构和复杂制造工艺需求的一个绝妙策略。进入微圆顶结构的光线经过全内反射后,由于反射路径不同,会呈现出随微圆顶尺寸变化的颜色。虽然已有人提出了基于溶液的打印技术来实现这一效果,但由于分辨率的限制,这些技术无法实现全彩打印。在此,我们利用电流体动力(EHD)喷射打印技术打印了直径为 1.2-9.9 μm 的透明微圆顶结构,实现了 3628 dpi 的全彩高分辨率结构彩色图像。此外,高分辨率的 EHD 喷射印刷结构彩色图像可显示复杂的编码信息,通过其制造简便性和对微圆顶尺寸的精确控制,提高了防伪效果。由于这些优点,这种基于 TIR 的结构着色技术与 EHD 喷射打印技术非常适合防伪应用。
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引用次数: 0
High-Entropy Strategy Flattening Lithium Ion Migration Energy Landscape to Enhance the Conductivity of Garnet-Type Solid-State Electrolytes 扁平化锂离子迁移能谱的高熵策略可增强石榴石型固态电解质的导电性
IF 19 Q1 POLYMER SCIENCE Pub Date : 2024-11-14 DOI: 10.1002/adfm.202416389
Shuhan Wang, Xiaojuan Wen, Zhenweican Huang, Haoyang Xu, Fengxia Fan, Xinxiang Wang, Guilei Tian, Sheng Liu, Pengfei Liu, Chuan Wang, Chenrui Zeng, Chaozhu Shu, Zhenxing Liang
Garnet-type solid-state electrolytes with exceptional stability are believed to promote the commercialization of all solid-state lithium metal batteries. However, the extensive application of garnet-type solid-state electrolytes is greatly impeded on account of their low ionic conductivity. Herein, a high-entropy fast lithium-ion conductor Li7(La,Nd,Sr)3(Zr,Ta)2O12 (LLNSZTO) with high lattice distortion is designed. It is found that the enhanced ionic conductivity of the high entropy garnet-type solid-state electrolyte LLNSZTO is achieved by introducing disorder in the lattice, which creates fast ion penetration paths with flattened energy landscapes within the pristine ordered lattice. Thus, the prepared high-entropy garnet-type solid electrolyte LLNSZTO exhibits low activation energy for Li+ migration (0.34 eV) and elevated ionic conductivity (6.26 × 10−4 S cm−1). Full cells assembled with LLNSZTO electrolyte, lithium metal anode, and LiFePO4 (LFP) cathode exhibit excellent capacity retention of 86.81% after 200 cycles at room temperature. Moreover, the superior ionic conductivity of LLNSZTO enables all solid-state battery with high-loading LFP cathode (>12 mg cm−2), achieving stable cycling exceeding 120 cycles. The large area pouch cell (5.5 cm × 8 cm) exhibits stable long-term cycling performance, showing a capacity retention of 96.50% after 50 cycles.
石榴石型固态电解质具有优异的稳定性,被认为可以促进所有固态锂金属电池的商业化。然而,由于石榴石型固态电解质的离子电导率较低,其广泛应用受到很大阻碍。本文设计了一种具有高晶格畸变的高熵快速锂离子导体 Li7(La,Nd,Sr)3(Zr,Ta)2O12(LLNSZTO)。研究发现,高熵石榴石型固态电解质 LLNSZTO 离子电导率的增强是通过在晶格中引入无序性来实现的,无序性在原始有序晶格中形成了能量景观扁平化的快速离子穿透路径。因此,制备的高熵石榴石型固态电解质 LLNSZTO 具有较低的 Li+ 迁移活化能(0.34 eV)和较高的离子电导率(6.26 × 10-4 S cm-1)。使用 LLNSZTO 电解质、锂金属阳极和磷酸铁锂(LFP)阴极组装的全电池在室温下循环 200 次后,容量保持率高达 86.81%。此外,LLNSZTO 优越的离子导电性使所有固态电池都能使用高负载 LFP 正极(12 mg cm-2),实现超过 120 次的稳定循环。大面积袋式电池(5.5 厘米 × 8 厘米)表现出稳定的长期循环性能,50 次循环后容量保持率达到 96.50%。
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引用次数: 0
Fibrous Pb(II)-Based Coordination Polymer Operable as a Photocatalyst and Electrocatalyst for High-Rate, Selective CO2-to-Formate Conversion 可用作光催化剂和电催化剂的纤维状铅(II)基配位聚合物,可实现二氧化碳到甲酸盐的高速度、选择性转化
IF 19 Q1 POLYMER SCIENCE Pub Date : 2024-11-13 DOI: 10.1002/adfm.202417223
Chomponoot Suppaso, Ryosuke Nakazato, Shoko Nakahata, Yoshinobu Kamakura, Fumitaka Ishiwari, Akinori Saeki, Daisuke Tanaka, Kazuhide Kamiya, Kazuhiko Maeda
A nonporous [Pb(tadt)]n (tadt = 1,3,4-thiadiazole-2,5-dithiolate) coordination polymer, KGF-9, with a 2D infinite (−Pb−S−)n structure has been previously reported as a precious-metal-free photocatalyst for selective CO2-to-formate conversion under visible light. In the present work, a microwave (MW)-assisted solvothermal reaction is used to synthesize KGF-9 with improved physicochemical properties and catalytic activity. Compared with KGF-9 prepared by the previously reported methods, that prepared by the new synthesis route exhibited a greater specific surface area, greater crystallinity, and greater photoconductivity. These improved properties led to a drastic increase of the apparent quantum yield (AQY) for selective formate production, from 2.6 to 25% at 400 nm; this AQY represents a record-high value among reported heterogeneous photocatalysts for CO2-to-formate conversion. Interestingly, the AQY for formate production is unchanged irrespective of the light intensity (0.04–14 mW cm−2), indicating little contribution of charge accumulation in the bulk during the reaction (i.e., indicating efficient charge transport to surface reactants). When composited with Ketjen Black, KGF-9 enabled the electrochemical conversion of CO2 to formate in aqueous solution while maintaining a high selectivity. A high-rate reduction of CO2 to formate with a total absolute current density of 200–300 mA cm−2 is achieved, with a Faradaic efficiency (FE) of >90%.
一种具有二维无限 (-Pb-S-)n 结构的无孔 [Pb(tadt)]n(tadt = 1,3,4-噻二唑-2,5-二硫酸盐)配位聚合物 KGF-9 已被报道为一种无贵金属光催化剂,可在可见光下将二氧化碳选择性地转化为甲酸盐。本研究利用微波(MW)辅助溶热反应合成了具有更好理化性质和催化活性的 KGF-9。与之前报道的方法制备的 KGF-9 相比,新合成路线制备的 KGF-9 比表面积更大、结晶度更高、光导率更高。这些改进的特性使得选择性生产甲酸盐的表观量子产率(AQY)在 400 纳米波长下从 2.6% 大幅提高到 25%;在已报道的将二氧化碳转化为甲酸盐的异质光催化剂中,这一 AQY 值创下了历史新高。有趣的是,无论光照强度(0.04-14 mW cm-2)如何,甲酸生产的 AQY 都保持不变,这表明在反应过程中,电荷在体积中的累积作用很小(即表明电荷向表面反应物的高效传输)。KGF-9 与 Ketjen Black 复配后,可在水溶液中实现二氧化碳到甲酸盐的电化学转化,同时保持较高的选择性。在总绝对电流密度为 200-300 mA cm-2 的条件下,可实现二氧化碳到甲酸盐的高速率还原,法拉第效率(FE)为 90%。
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引用次数: 0
High-Throughput Screening of Dual-Atom Catalysts for Methane Combustion: A Combined Density Functional Theory and Machine-Learning Study 高通量筛选用于甲烷燃烧的双原子催化剂:密度泛函理论与机器学习的结合研究
IF 19 Q1 POLYMER SCIENCE Pub Date : 2024-11-13 DOI: 10.1002/adfm.202414145
Jiaqi Ding, Haonan Gu, Yao Shi, Yi He, Yaqiong Su, Mi Yan, Pengfei Xie
Ceria-supported precious metal catalysts have undergone extensive investigation for the catalytic methane combustion. However, it remains a significant challenge to achieve both highly synergistic oxidation activity and efficient atom utilization remains a challenge for commonly used supported nanoparticles and single-atom catalysts. Dual-atom catalysts (DACs) emerges as a frontier of advanced catalysts, presenting unique catalytic properties that benefit from the synergy of neighboring metal sites. In this study, 361 ceria-supported DACs (M1M2/CeO2) encompassing combinations of 19 transition metals are systematically explored. Using high-throughput density functional theory calculations, the structures, stability as well as activity of M1M2/CeO2 are assessed. Notably, Au1Ga1/CeO2 is identified as a promising DAC exhibiting high activity for methane total oxidation, substantiated by comprehensive DFT-calculated reaction pathways. Furthermore, employing six machine-learning algorithms, the structure-properties relationship is explored within ceria-based DACs and highlight the importance of oxidation states and atomic radii of doped metals as the descriptors. The trained model by computational dataset exhibits high accuracy and predict a more active Mn1Au1/CeO2 than those screened using only DFT datasets. The high-throughput strategy demonstrated in this work not only provides insights into the rational design of methane oxidation catalysts, but also paves the way for exploring DACs for diverse applications.
在催化甲烷燃烧方面,对铈支撑贵金属催化剂进行了广泛的研究。然而,对于常用的支撑纳米颗粒和单原子催化剂来说,如何同时实现高度协同氧化活性和高效原子利用仍然是一项重大挑战。双原子催化剂(DACs)作为先进催化剂的前沿技术出现了,其独特的催化特性得益于相邻金属位点的协同作用。本研究系统地探讨了 361 种铈支撑的双原子催化剂(M1M2/CeO2),包括 19 种过渡金属的组合。通过高通量密度泛函理论计算,对 M1M2/CeO2 的结构、稳定性和活性进行了评估。值得注意的是,Au1Ga1/CeO2 被确定为一种有前途的 DAC,在甲烷全氧化方面表现出很高的活性,这一点通过全面的 DFT 计算反应路径得到了证实。此外,利用六种机器学习算法探索了铈基 DAC 的结构-性质关系,并突出了氧化态和掺杂金属原子半径作为描述因子的重要性。与仅使用 DFT 数据集筛选出的模型相比,通过计算数据集训练出的模型具有很高的准确性,并能预测出活性更强的 Mn1Au1/CeO2。这项工作中展示的高通量策略不仅为甲烷氧化催化剂的合理设计提供了启示,还为探索 DACs 的多样化应用铺平了道路。
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引用次数: 0
期刊
ACS Macro Letters
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