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Without that crystalline touch 没有那晶莹剔透的触感
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01222-4
Xiaofei Guan
Traditional heterogeneous catalytic processes primarily hinge on the reactivity of solids. Now, a liquid metal catalyst based on a Cu–Ga binary system with dynamic structure and intriguing properties opens up an alternative for the conventional Haber–Bosch process for ammonia synthesis.
传统的异相催化工艺主要取决于固体的反应性。现在,一种基于铜-镓二元体系的液态金属催化剂具有动态结构和有趣的特性,为传统的哈伯-博什合成氨工艺开辟了另一种选择。
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引用次数: 0
Solid electrolyte reactor for nitrate-to-ammonia 硝酸制氨固体电解质反应器
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01223-3
Yuting Wang, Bin Zhang
Electrochemical nitrate reduction to ammonia is a promising approach for waste conversion, yet the use of a concentrated supporting electrolyte creates a product separation issue. Now, a porous solid electrolyte reactor with a cation shielding effect is reported for nitrate wastewater treatment and the production of pure ammonia.
电化学硝酸盐还原成氨是一种很有前景的废物转化方法,但使用浓缩的支撑电解质会产生产品分离问题。现在,一种具有阳离子屏蔽效应的多孔固体电解质反应器被报道用于硝酸盐废水处理和纯氨的生产。
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引用次数: 0
Deciphering electrochemical methanol production 解密电化学甲醇生产
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01224-2
Stefan Ringe
Methanol selectivity is uncommon among CO2 reduction electrocatalysts. A notable exception is the cobalt phthalocyanine catalyst supported on carbon nanotubes, yet the mechanism is still poorly understood. Now, two studies use a variety of analytical approaches to investigate the mechanism of the process including the role of alkali cations.
在二氧化碳还原电催化剂中,甲醇选择性并不常见。碳纳米管支撑的酞菁钴催化剂是一个显著的例外,但人们对其机理仍然知之甚少。现在,有两项研究采用多种分析方法研究了这一过程的机理,包括碱阳离子的作用。
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引用次数: 0
Metallaphotoredox catalysis for sp3 C–H functionalizations through single-electron transfer 通过单电子转移实现 sp3 C-H 功能化的金属光氧催化
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01215-3
Jingchang Zhang, Magnus Rueping
Metallaphotoredox catalysis merging photocatalysis and transition metal catalysis is now the most efficient platform for sp3 C–H functionalizations due to its very efficient activation and transformation capability. In such a process, photocatalysis is usually in charge of C–H bond activation to generate an sp3-hybridized carbon-centred radical, whereas transition metal catalysis is in charge of the subsequent transformation of this radical. Here we review advances in sp3 C–H functionalizations under matallaphotoredox catalysis via photocatalytic single-electron transfer mechanisms as opposed to hydrogen atom transfer processes. The delineation of these advancements is initially organized according to distinct sp3 C–H bonds and subsequently categorized by various transition metal catalytic systems. We encompass a thorough exploration of diverse metallaphotoredox catalysis strategies, along with their synthetic applications and mechanisms. Similarities and differences between these strategies are described to inspire new reaction designs, thus promoting further development of this field. The merger of photocatalysis and transition metal catalysis has broadened the scope of chemical reactivity in organic synthesis. This Review provides an overview of the use of metallaphotoredox catalysis for sp3 C–H functionalizations that occur via single-electron, rather than hydrogen atom transfer.
光催化与过渡金属催化相结合的金属光氧催化因其高效的活化和转化能力而成为目前最有效的 sp3 C-H 功能化平台。在这一过程中,光催化通常负责 C-H 键的活化,以生成 sp3 杂化的碳中心自由基,而过渡金属催化则负责该自由基的后续转化。在此,我们回顾了通过光催化单电子转移机制(而非氢原子转移过程)在母萘氧化催化下进行 sp3 C-H 功能化的进展。我们首先根据不同的 sp3 C-H 键对这些研究进展进行了划分,然后按照各种过渡金属催化系统进行了分类。我们深入探讨了各种金属萘氧化催化策略及其合成应用和机制。我们描述了这些策略之间的异同,以启发新的反应设计,从而促进这一领域的进一步发展。
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引用次数: 0
Unlocking C–C cleavage in the electrochemical toolbox 打开电化学工具箱中的 C-C 裂解功能
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01217-1
Nikolay Kornienko
Electrifying the fragmentation of hydrocarbons is an emerging challenge in the context of decarbonizing the chemical industry. To this end, competing electrocatalytic C–C cleavage and oxidation pathways of butane were investigated.
在化工行业去碳化的背景下,碳氢化合物的电催化裂解是一个新出现的挑战。为此,我们研究了丁烷的竞争电催化 C-C 裂解和氧化途径。
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引用次数: 0
Carbon conversion on biophotonic leaf 生物光子叶片上的碳转化
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-24 DOI: 10.1038/s41929-024-01216-2
Jinhyeong Jang, Elena A. Rozhkova
A photodiode can trigger bias-free redox reactions but is often hindered by thermodynamic barriers. Now, a bacteria-conjugated silicon biophotochemical diode allows simultaneous conversion of various carbon molecules with high efficacy.
光电二极管可以触发无偏压氧化还原反应,但往往受到热力学障碍的阻碍。现在,一种细菌共轭硅生物光化学二极管可以同时高效转化各种碳分子。
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引用次数: 0
Cation effect on the elementary steps of the electrochemical CO reduction reaction on Cu 阳离子对 Cu 上电化学 CO 还原反应基本步骤的影响
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-23 DOI: 10.1038/s41929-024-01227-z
Yifei Xu, Zhaoming Xia, Wenqiang Gao, Hai Xiao, Bingjun Xu
The nature of the cations in an electrolyte has a substantial impact on the performance of the electrochemical CO2 and CO reduction reaction (CO(2)RR), however, its mechanism at the molecular level remains the subject of debate. Major gaps in our understanding include how cations affect key physicochemical variables at electrochemical interfaces and the elementary steps of the CO(2)RR. In this work, we have quantitatively determined the impact of cations on the enthalpy and entropy of CO adsorption on Cu under electrochemical conditions. CO adsorption becomes increasingly unfavourable in the sequence Li+ > Na+ > K+ > Cs+ with a substantial enthalpy–entropy compensation effect. Importantly, cations affect the stability of the initial and transition states of the CORR in opposite directions. Our results provide insights into the effect of cations on individual elementary steps in the CORR and demonstrate that the ability to stabilize the transition state in the conversion of adsorbed CO is a decisive factor. The mechanism of electrocatalytic CO/CO2 reduction on Cu surfaces is complex and its various mechanisms remain under debate, including the important role of cations in the electrolyte. Here the authors quantitatively determine the impact of alkali cations on the thermodynamics of CO adsorption under electrochemical conditions and the activation parameters of the rate-determining step.
电解质中阳离子的性质对二氧化碳和一氧化碳电化学还原反应(CO(2)RR)的性能有重大影响,但其分子水平上的机理仍存在争议。我们对阳离子如何影响电化学界面上的关键物理化学变量以及 CO(2)RR 的基本步骤的理解还存在很大差距。在这项工作中,我们定量测定了阳离子对电化学条件下 CO 在铜上吸附的焓和熵的影响。在 Li+ > Na+ > K+ > Cs+ 的序列中,CO 的吸附变得越来越不利,并产生了很大的焓熵补偿效应。重要的是,阳离子以相反的方向影响 CORR 初始状态和过渡状态的稳定性。我们的研究结果让我们深入了解了阳离子对 CORR 中各个基本步骤的影响,并证明了在吸附 CO 的转化过程中稳定过渡态的能力是一个决定性因素。
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引用次数: 0
Ammonia synthesis via an engineered nitrogenase assembly pathway in Escherichia coli 大肠杆菌通过改造的氮酶组装途径合成氨
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-19 DOI: 10.1038/s41929-024-01229-x
Joseph B. Solomon, Chi Chung Lee, Yiling A. Liu, Calder Duffin, Markus W. Ribbe, Yilin Hu
Heterologous expression of nitrogenase has been actively pursued because of the far-reaching impact of this enzyme on agriculture, energy and the environment. However, isolation of an active two-component, metallocentre-containing nitrogenase from a non-diazotrophic host has yet to be accomplished. Here we report the heterologous synthesis of an active molybdenum-nitrogenase by combining genes from Azotobacter vinelandii and Methanosarcina acetivorans in Escherichia coli. Metal, activity and electron paramagnetic resonance analyses demonstrate the integrity of the metallocentres in the purified nitrogenase enzyme; whereas growth, nanoscale secondary ion mass spectrometry and nuclear magnetic resonance experiments illustrate diazotrophic growth and 15N enrichment by the E. coli expression strain, and accumulation of extracellular ammonia upon deletion of the ammonia transporter that permits incorporation of thus-generated nitrogen into the cellular mass of a non-diazotrophic E. coli strain. As such, this study provides a crucial prototype system that could be optimized/modified to enable future transgenic expression and biotechnological adaptations of nitrogenase. Heterologous expression of an active, metallocentre-containing nitrogenase in a non-diazotrophic host is challenging. Now, the heterologous biosynthetic pathway of Mo-nitrogenase is pieced together in Escherichia coli using genes from Azotobacter vinelandii and Methanosarcina acetivorans.
由于氮酶对农业、能源和环境的深远影响,人们一直在积极寻求氮酶的异源表达。然而,从非氮养宿主中分离出活性双组分、含金属中心的氮酶的工作尚未完成。在此,我们报告了通过在大肠杆菌中结合来自乙烯氮芽胞杆菌(Azotobacter vinelandii)和乙酰甲烷菌(Methanosarcina acetivorans)的基因异源合成活性钼氮酶的情况。金属、活性和电子顺磁共振分析表明了纯化的氮酶中金属中心的完整性;而生长、纳米级二次离子质谱分析和核磁共振实验表明了大肠杆菌表达菌株的重氮生长和 15N 富集,以及氨转运体缺失后细胞外氨的积累,氨转运体允许将由此产生的氮并入非重氮大肠杆菌菌株的细胞质中。因此,这项研究提供了一个重要的原型系统,可以对其进行优化/改造,使氮酶将来能够进行转基因表达和生物技术改造。
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引用次数: 0
Unveiling metal mobility in a liquid Cu–Ga catalyst for ammonia synthesis 揭示用于合成氨的液态铜-镓催化剂中的金属迁移率
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-19 DOI: 10.1038/s41929-024-01219-z
Karma Zuraiqi, Yichao Jin, Caiden J. Parker, Jaydon Meilak, Nastaran Meftahi, Andrew J. Christofferson, Salvy P. Russo, Michelle J. S. Spencer, Huai Yong Zhu, Lizhuo Wang, Jun Huang, Rosalie K. Hocking, Ken Chiang, Sarina Sarina, Torben Daeneke
The outlook for sustainable economic and ecological growth projects an ammonia economy as a key enabler to the energy transition landscape. The predominance of the Haber–Bosch process, however, as the current industrial process for producing ammonia subdues the sustainability of establishing an energy route predicated on ammonia. Here we capitalize on the inherent atomic structure of liquid metal alloys and the ability to modulate the electronic and geometric structures of liquid metal catalysts to drive the thermocatalytic synthesis of ammonia. By exploiting the mobility of the metal atoms in the liquid metal configuration and purposefully designing disordered metal catalysts, we provide insights into designing future transition metal-based catalysts that produce ammonia from gaseous nitrogen and hydrogen under mild operating conditions. The use of a molten Cu–Ga catalyst offers a dynamic metal complex with synergistic advantages that lift the activity of its constituent elements, exceeding the activity of a control Ru-based catalyst. The traditional Haber–Bosch process as well as recent alternative approaches based on photo- or electrocatalysis all rely on solid catalysts to convert nitrogen into ammonia. Here the authors disclose an effective method for the synthesis of this crucial commodity based on a Cu–Ga liquid metal catalyst instead.
可持续经济和生态增长的前景预测,氨经济将成为能源转型的关键因素。然而,哈伯-博施工艺作为当前生产氨的主要工业工艺,削弱了建立以氨为基础的能源路线的可持续性。在此,我们利用液态金属合金固有的原子结构以及调节液态金属催化剂电子和几何结构的能力来推动氨的热催化合成。通过利用液态金属构型中金属原子的流动性和有目的地设计无序金属催化剂,我们为设计未来的过渡金属基催化剂提供了启示,这种催化剂可在温和的操作条件下从气态氮和氢中生产氨。熔融铜-镓催化剂提供了一种具有协同优势的动态金属复合物,可提高其组成元素的活性,超过基于 Ru 的对照催化剂的活性。
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引用次数: 0
Eliminating redox-mediated electron transfer mechanisms on a supported molecular catalyst enables CO2 conversion to ethanol 消除支撑分子催化剂上氧化还原介导的电子传递机制,实现二氧化碳到乙醇的转化
IF 42.8 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2024-09-13 DOI: 10.1038/s41929-024-01225-1
Maryam Abdinejad, Amirhossein Farzi, Robin Möller-Gulland, Fokko Mulder, Chengyu Liu, Junming Shao, Jasper Biemolt, Marc Robert, Ali Seifitokaldani, Thomas Burdyny
Molecular catalysts play a significant role in chemical transformations, utilizing changes in redox states to facilitate reactions. To date molecular electrocatalysts have efficiently produced single-carbon products from CO2 but have struggled to achieve a carbon–carbon coupling step. Conversely, copper catalysts can enable carbon–carbon coupling, but lead to broad C2+ product spectra. Here we subvert the traditional redox-mediated reaction mechanisms of organometallic compounds through a heterogeneous nickel-supported iron tetraphenylporphyrin electrocatalyst, facilitating electrochemical carbon–carbon coupling to produce ethanol. This represents a marked behavioural shift compared with carbon-supported metalloporphyrins. Extending the approach to a three-dimensional porous nickel support with adsorbed iron tetraphenylporphyrin, we attain ethanol Faradaic efficiencies of 68% ± 3.2% at −0.3 V versus a reversible hydrogen electrode (pH 7.7) with partial ethanol current densities of −21 mA cm−2. Separately we demonstrate maintained ethanol production over 60 h of operation. Further consideration of the wide parameter space of molecular catalyst and metal electrodes shows promise for additional chemistries and achievable metrics. The electrochemical reduction of CO2 on organometallic catalysts is commonly limited to two-electron products. Now, an iron tetraphenylporphyrin catalyst immobilized onto a nickel electrode is shown to achieve a Faradaic efficiency for ethanol of 68% due to the strong electronic coupling between the catalyst and the support.
分子催化剂利用氧化还原状态的变化促进反应,在化学转化中发挥着重要作用。迄今为止,分子电催化剂能有效地从二氧化碳中产生单碳产物,但却难以实现碳-碳偶联步骤。相反,铜催化剂可以实现碳-碳偶联,但会导致宽泛的 C2+ 产物光谱。在这里,我们通过一种异质镍支撑的四苯基卟啉铁电催化剂,颠覆了有机金属化合物传统的氧化还原介导反应机制,促进了电化学碳-碳偶联生成乙醇。与碳支撑金属卟啉相比,这是一种明显的行为转变。将这种方法扩展到吸附了四苯基卟啉铁的三维多孔镍载体上,我们在-0.3 V电压下与可逆氢电极(pH 值为 7.7)相比,乙醇法拉第效率达到 68% ± 3.2%,乙醇部分电流密度为 -21 mA cm-2。另外,我们还展示了运行 60 小时后乙醇的持续生产情况。对分子催化剂和金属电极的宽广参数空间的进一步研究表明,我们有望获得更多的化学成分和可实现的指标。
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Nature Catalysis
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