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Catalyst and microenvironment design for more efficient ethanol electrosynthesis 更有效的乙醇电合成催化剂和微环境设计
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1038/s44160-024-00663-w
Simultaneously achieving high energy and carbon efficiency in ethanol electrosynthesis is challenging. Now, an interfacial cation matrix (ICM) is developed that modifies the catalyst microenvironment to increase these performance metrics towards multicarbon products in the acidic CO2 reduction reaction. Furthermore, combining a tailored Cu–Ag catalyst with the ICM facilitates selective ethanol electrosynthesis.
同时实现乙醇电合成的高能量和碳效率是一项具有挑战性的工作。现在,一种界面阳离子基质(ICM)被开发出来,它可以改变催化剂的微环境,以提高酸性CO2还原反应中多碳产物的这些性能指标。此外,将定制的Cu-Ag催化剂与ICM结合可以促进选择性乙醇电合成。
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引用次数: 0
Metal/MXene composites via in situ reduction
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1038/s44160-024-00660-z
Qingxiao Zhang, Jia-ao Wang, Qinghua Yu, Qizhen Li, Runze Fan, Chong Li, Yiyi Fan, Cong Zhao, Weihua Cheng, Peiyi Ji, Jie Sheng, Chenhao Zhang, Songhai Xie, Graeme Henkelman, Hui Li
Metal/two-dimensional substrate composites offer a rich library of materials that can have application in catalysis, sensing, biotechnology and other fields. In situ reduction deposition provides a scalable method for fabricating metal/MXene composites, but the rational control of metal nanostructures growth on MXene remains difficult. Here a strategy for the in situ reduction deposition of various metals (Au, Pd, Ag, Pt, Rh, Ru and Cu) on Ti3C2Tx MXene is demonstrated. This study uncovers the guiding principles of the metal deposition process on MXene nanosheets, including the influence of redox potential, metal coordination and lattice mismatch. A series of metal/MXene composites with fine-tuned structures were constructed based on these guiding principles, such as Pd@Au-Edge/Ti3C2Tx, Pt@Au-Edge/Ti3C2Tx, Au@Ag@Au-Surface/Ti3C2Tx and Ag@Pd@Au-Edge/Ti3C2Tx. In addition, the in situ reduction strategy can be extended to other MXene materials, such as Mo2CTx, V2CTx, Ti3CNTx, Nb4C3Tx and Mo2TiC2Tx, which allows the creation of metal/MXene composites with versatile and customizable nanostructures for a wide range of applications. In situ reduction deposition is a scalable method for fabricating metal/MXene composites, but rational control remains difficult. Now an in situ reduction strategy for synthesizing metal/MXene composites with precise control over metal size, deposition site and nanostructure has been demonstrated.
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引用次数: 0
Carbon- and energy-efficient ethanol electrosynthesis via interfacial cation enrichment 界面阳离子富集的碳高效乙醇电合成
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1038/s44160-024-00662-x
Ali Shayesteh Zeraati, Feng Li, Tartela Alkayyali, Roham Dorakhan, Erfan Shirzadi, Fatemeh Arabyarmohammadi, Colin P. O’Brien, Christine M. Gabardo, Jonathan Kong, Adnan Ozden, Mohammad Zargartalebi, Yong Zhao, Lizhou Fan, Panagiotis Papangelakis, Dongha Kim, Sungjin Park, Rui Kai Miao, Jonathan P. Edwards, Daniel Young, Alexander H. Ip, Edward H. Sargent, David Sinton
The use of acidic electrolytes in CO2 reduction avoids costly carbonate loss. However, the energy efficiency of acid-fed electrolysers has been limited by high hydrogen production and operating potentials. We find that these stem from the lack of alkali cations at the catalyst surface, limiting CO2 and CO adsorption. In acid-fed membrane electrode assembly systems, the incorporation of these cations is challenging as there is no flowing catholyte. Here an interfacial cation matrix (ICM)–catalyst heterojunction is designed that directly attaches to the catalyst layer. The negatively charged nature of the ICM enriches the alkali cation concentration near the cathode surface, trapping generated hydroxide ions. This increases the local electric field and pH, increasing multi-carbon production. Integrating the ICM strategy with a tailored copper–silver catalyst enables selective ethanol production through a proton-spillover mechanism. We report a 45% CO2-to-ethanol Faradaic efficiency at 200 mA cm−2, carbon efficiency of 63%, full-cell ethanol energy efficiency of 15% (3-fold improvement over the best previous acidic CO2 reduction value) and energy cost of 260 GJ per tonne ethanol, the lowest among reported ethanol-producing CO2 electrolysers. Acidic CO2 electroreduction is carbon efficient but suffers from low energy efficiency and selectivity. Here an interfacial cation matrix is developed to enrich alkali cations and increase the local pH at a Cu–Ag catalyst surface, improving efficiency. A 45% CO2-to-ethanol Faradaic efficiency and 15% energy efficiency for ethanol production are achieved.
在二氧化碳还原中使用酸性电解质避免了代价高昂的碳酸盐损失。然而,酸供电解槽的能量效率受到高产氢率和操作电位的限制。我们发现这是由于催化剂表面缺乏碱阳离子,限制了CO2和CO的吸附。在酸供膜电极组装系统中,由于没有流动的阴极电解质,这些阳离子的结合是具有挑战性的。这里设计了一个界面阳离子矩阵(ICM) -催化剂异质结,它直接附着在催化剂层上。ICM的负电荷特性使阴极表面附近的碱阳离子浓度增加,从而捕获生成的氢氧化物离子。这增加了局部电场和pH值,增加了多碳产量。将ICM策略与定制的铜银催化剂相结合,可以通过质子溢出机制实现选择性乙醇生产。我们报告了在200毫安厘米−2下45%的二氧化碳到乙醇的法拉第效率,63%的碳效率,15%的全电池乙醇能量效率(比之前最好的酸性二氧化碳还原值提高了3倍)和每吨乙醇260吉焦的能量成本,这是报道的乙醇生产二氧化碳电解槽中最低的。酸性CO2电还原是一种碳效率高的方法,但存在能量效率低和选择性差的问题。在这里,开发了界面阳离子基质来富集碱阳离子并增加Cu-Ag催化剂表面的局部pH,从而提高效率。二氧化碳转化为乙醇的法拉第效率为45%,乙醇生产的能源效率为15%。
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引用次数: 0
Mechanical exfoliation of non-layered metal oxides into ultrathin flakes 将非层状金属氧化物机械剥离成超薄薄片
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-03 DOI: 10.1038/s44160-024-00657-8
Ruijie Li, Zhixin Yao, Zhenjiang Li, Lei Liao, Huacong Sun, Chaonan Cong, Xudan Huang, Kang Wu, Tingjun Wang, Huifeng Tian, PeiChi Liao, Shizhuo Liu, Yihan Wang, Lina Yang Zhang, U Sasaki, Ge Yin, Junjie Guo, Yu Ye, Xiaoding Wei, Xueyun Wang, Jiawang Hong, Jinhai Mao, Lihong Bao, Lifen Wang, Xuedong Bai, Peng Gao, Kaihui Liu, Lei Liao, Jun He, Shulin Bai, Yanfeng Zhang, Yanglong Hou, Ruqiang Zou, Hong-Jun Gao, Yue Zhang, Enge Wang, Lei Liu
The exfoliation of layered crystals can produce diverse two-dimensional (2D) materials and heterostructures. However, the micromechanical cleavage of non-stratified materials into 2D flakes remains challenging due to z-direction consecutive bonding. Here we report a mechanical exfoliation method for producing freestanding 2D metal oxide flakes. By synchronizing the thermal decomposition of metal salts and water-assisted forming, we synthesize large-aspect-ratio lamellae of amorphous and crystalline metal oxides as parent materials, which can exfoliate to ultrathin flakes. The freestanding, transferrable features allow the room temperature integration of high-k metal oxide flakes as top-gate dielectrics in 2D material transistors. We utilize the dual-function Cr-doped AlOx flake as the gating dielectric and component, sensing and storing the visible light by photon-programming floating gate effect, showing an in-sensor computing device. Our results provide a platform to investigate the fundamental properties of ultrathin metal oxides free of substrate clamping and pave the way to metal oxides-based functional devices. A mechanical exfoliation method for producing freestanding metal oxide ultrathin flakes is reported. The flakes can be transferred and integrated with 2D materials, providing a platform to investigate the fundamental properties of ultrathin metal oxides.
层状晶体的剥离可以产生多种二维材料和异质结构。然而,由于z方向连续键合,非分层材料的微机械切割成二维薄片仍然具有挑战性。在这里,我们报告了一种机械剥离方法,用于生产独立的二维金属氧化物薄片。通过同步金属盐的热分解和水助成型,合成了以非晶和结晶金属氧化物为母材的大宽高比片层,并可剥落成超薄薄片。独立的,可转移的特点允许室温集成高k金属氧化物片作为顶栅介电体在二维材料晶体管。我们利用双功能掺铬AlOx薄片作为门控介质和元件,利用光子编程浮栅效应对可见光进行传感和存储,展示了传感器内计算装置。我们的研究结果为研究无衬底夹紧的超薄金属氧化物的基本特性提供了一个平台,并为基于金属氧化物的功能器件铺平了道路。报道了一种机械剥离法制备独立金属氧化物超薄薄片的方法。薄片可以转移并与二维材料集成,为研究超薄金属氧化物的基本特性提供了一个平台。
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引用次数: 0
C–N coupling with cobalt 与钴的 C-N 耦合
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 DOI: 10.1038/s44160-024-00668-5
Thomas West
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引用次数: 0
Nitrogenated products from polyolefins 聚烯烃氮化产品
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 DOI: 10.1038/s44160-024-00667-6
Peter W. Seavill
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引用次数: 0
Selective coupling on molecular catalysts 分子催化剂上的选择性偶联
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-01 DOI: 10.1038/s44160-024-00670-x
Alexandra R. Groves
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引用次数: 0
Phase engineering of nitride thin films 氮化薄膜的相位工程
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-30 DOI: 10.1038/s44160-024-00666-7
Xing Ming, Xiaojun Kuang
Thermodynamically-stable layered cation-ordered 2D-like nitrides can be synthesized using kinetically-limited thin-film deposition methods.
利用动力学受限的薄膜沉积方法可以合成热稳定的层状阳离子有序二维类氮化物。
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引用次数: 0
Carbon isotopic labelling of carboxylic acids enabled by organic photoredox-catalysed cyanation 有机光氧化催化氰化作用下羧酸的碳同位素标记
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-27 DOI: 10.1038/s44160-024-00656-9
Zhengbo Zhu, Xuedan Wu, Gerald Thomas Bida, Huaifu Deng, Xinrui Ma, Siran Qian, Zhanhong Wu, Zibo Li, David A. Nicewicz
The application of molecular imaging has advanced personalized medicine and generated a profound impact on patient care. Positron emission tomography and magnetic resonance imaging are among the most widely used imaging modalities, often requiring the isotopic labelling of bioactive molecules to generate the desired imaging probes. Unfortunately, radiochemistry often limits the development of novel agents due to complicated syntheses and the incompatibility of complex molecules. Here, considering the prevalence of carboxylic acids in drug and bioactive molecules, we have developed a method to perform 11/13C labelling through carboxylic acid groups via organic photoredox reactions to generate radiolabelled nitriles. We applied this strategy to a range of aliphatic carboxylic acids, including complex and functionalized drug molecules, amino acids and short peptides. Notably, when benzylic and alkyl carboxylic acids were used as substrates, a copper co-catalyst was required to obtain the labelled nitriles, whereas when α-amino acids and peptides were used as substrates, a copper co-catalyst was not required to form labelled α-amino nitriles. The radiolabelled nitrile products could be easily converted back to radiolabelled carboxylic acids with high radiochemical yields and molar activities. Positron emission tomography and magnetic resonance imaging are two powerful imaging modalities that require the installation of isotopes in biologically relevant molecules. Now an organic photoredox-catalysed method for the conversion of a range of carboxylic acids to their 11C and 13C isotopomers via decarboxylative cyanation is reported.
分子成像的应用推动了个性化医疗的发展,并对患者护理产生了深远的影响。正电子发射断层扫描和磁共振成像是最广泛使用的成像方式,通常需要对生物活性分子进行同位素标记以产生所需的成像探针。不幸的是,由于复杂的合成和复杂分子的不相容性,放射化学常常限制了新药剂的发展。在这里,考虑到羧酸在药物和生物活性分子中的普遍存在,我们开发了一种通过有机光氧化还原反应通过羧酸基团进行11/13C标记的方法,以生成放射性标记的腈。我们将这一策略应用于一系列脂肪族羧酸,包括复合物和功能化药物分子,氨基酸和短肽。值得注意的是,当以苯基和烷基羧酸为底物时,需要铜助催化剂才能得到标记的腈,而当以α-氨基酸和肽为底物时,不需要铜助催化剂来形成标记的α-氨基腈。放射性标记的丁腈产物可以很容易地转化为放射性标记的羧酸,具有较高的放射化学产率和摩尔活性。正电子发射断层扫描和磁共振成像是两种强大的成像方式,需要在生物相关分子中安装同位素。现在报道了一种有机光氧化催化方法,通过脱羧氰化反应将一系列羧酸转化为11C和13C同位素体。
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引用次数: 0
Palladium-catalysed [2σ + 2π] cycloaddition reactions of bicyclo[1.1.0]butanes with aldehydes 钯催化双环[1.1.0]丁烷与醛的[2σ + 2π]环加成反应
0 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-09-27 DOI: 10.1038/s44160-024-00659-6
Tianzhu Qin, Mengyang He, Weiwei Zi
Cycloaddition reactions of bicyclo[1.1.0]butanes (BCBs) with 2π components are a powerful tool for preparing C(sp3)-rich arene bioisosteres. Despite enormous progress in this field, catalytic enantioselective cycloadditions of BCBs that produce enantioenriched three-dimensional bioisosteres are underdeveloped. Here we report a palladium-catalysed [3 + 2] cycloaddition reaction of vinyl-carbonyl-BCBs with carbonyl compounds, including formaldehyde, activated ketones, and aliphatic and aromatic aldehydes. This approach provides quick access to a wide variety of 2-oxabicyclo[2.1.1]hexanes. Density functional theory calculations indicate that the reaction occurs through a zwitterionic mechanism involving σ-bond cleavage, nucleophilic addition and allylic substitution. When (R,R)-ANDEN-phenyl Trost ligand is used, the stereoselectivity of the addition of palladium-zwitterionic enolates to carbonyl can be controlled to achieve enantioselective [3 + 2] cycloadditions. We further demonstrate the practicality of the method by carrying out several downstream transformations of cycloaddition products. Palladium catalysis enables the cycloaddition reaction between vinyl-carbonyl-bicyclo[1.1.0]butanes and aldehydes or ketones for the synthesis of 2-oxabicyclo[2.1.1]hexanes, an arene bioisotere. Enantiocontrol over the zwitterionic [2σ + 2π] cycloaddition process can be achieved using the commercially available (R,R)-ANDEN-phenyl Trost ligand.
含2π组分的双环[1.1.0]丁烷(BCBs)的环加成反应是制备富C(sp3)芳烃生物异构体的有力手段。尽管在这一领域取得了巨大的进展,但催化对映选择性环加成bcb产生富含对映体的三维生物同工异构体的研究尚不发达。本文报道了钯催化的乙烯基-羰基- bcbs与羰基化合物(包括甲醛、活化酮、脂肪和芳香醛)的[3 + 2]环加成反应。这种方法提供了快速获取各种2-氧杂环[2.1.1]己烷的途径。密度泛函理论计算表明,该反应是通过两性离子机制发生的,包括σ键裂解、亲核加成和烯丙基取代。当使用(R,R)-ANDEN-phenyl Trost配体时,可以控制钯两性离子烯醇酸酯对羰基加成的立体选择性,实现对映选择性[3 + 2]环加成。我们通过进行环加成产物的几个下游变换进一步证明了该方法的实用性。钯催化使乙烯基-羰基-双环[1.1.0]丁烷与醛或酮之间的环加成反应合成2-氧杂环[2.1.1]己烷,这是一种芳烃生物异质体。使用市售的(R,R)-ANDEN-phenyl Trost配体可以实现两性离子[2σ + 2π]环加成过程的对映体控制。
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引用次数: 0
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Nature synthesis
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