Autonomous execution of highly reactive chemical transformations in the Schlenkputer DOI Creative Commons
Nicola L. Bell, Florian Boser, Andrius Bubliauskas

et al.

Nature Chemical Engineering, Journal Year: 2024, Volume and Issue: 1(2), P. 180 - 189

Published: Feb. 8, 2024

Abstract We design a modular programmable inert-atmosphere Schlenkputer (Schlenk-line computer) for the synthesis and manipulation of highly reactive compounds, including those that are air moisture sensitive or pyrophoric. Here, to do this, we constructed Schlenk line using Chemputer architecture inertization glassware can achieve vacuum pressure 1.5 × 10 −3 mbar, integrated range automated handling, storage isolation compounds at sub-ppm levels O 2 H O. This has enabled automation common organometallic reaction types four compounds: [Cp Ti III (MeCN) ] + , Ce {N(SiMe 3 ) } B(C 6 F 5 { Dipp NacNacMg I which variously temperature, pressure, water oxygen. Automated crystallization, filtration sublimation demonstrated, along with analysis inline nuclear magnetic resonance sampling ultraviolet–visible spectroscopy. Finally, demonstrate low-temperature reactivity down −90 °C as well safe handling quenching alkali metal reagents dynamic feedback from an in situ temperature probe.

Language: Английский

Conductive Two-Dimensional Magnesium Metal–Organic Frameworks for High-Efficiency O2 Electroreduction to H2O2 DOI
Kai Dong, Jie Liang, Yuanyuan Wang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(10), P. 6092 - 6099

Published: May 6, 2022

Direct electrosynthesis of H2O2 via a two-electron oxygen reduction reaction (2e– ORR) under ambient conditions is emerging as promising solution toward on-site applications for the replacement energy-consuming, waste-intensive, and indirect anthraquinone process. To date, state-of-the-art 2e– ORR catalysis mostly performed with transition-metal-based materials, while main-group element-based catalysts are much less established, which there an urgent need proper understanding. Herein, we report conductive two-dimensionally layered Mg3(hexaiminotriphenylene)2 electrocatalyst selective hydrogenation O2 to synthesize (selectivity >90%) robust high catalytic efficiency. In situ spectroscopic monitoring reactions kinetic studies not only illustrate mechanisms on but confirm that Mg2+ center serving real active site responsible critical intermediate OOH* forming event. Additionally, in-depth density functional theory calculations further discuss excellent activity selectivity production.

Language: Английский

Citations

147
Boosting Nitrogen Activation via Bimetallic Organic Frameworks for Photocatalytic Ammonia Synthesis DOI
Zhanfeng Zhao, Hanjie Ren, Dong Yang

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(15), P. 9986 - 9995

Published: July 27, 2021

Photocatalytic ammonia synthesis from N2 is a carbon-neutral strategy, although its efficiency impeded by the activation of inert N≡N triple bonds. In activation, electron acceptance process often strongly coupled with donation process, leading to high potential energy barrier and low photocatalytic activity. Herein, we proposed strategy decouple these two processes bimetallic organic frameworks (BMOFs) for boosting activation. The rationally designed BMOFs are composed functional metal nodes, in which hard acid node ionization (In) accepts soft donates N2. Owing bimetal synergistic effect, reduced, as confirmed situ Fourier transform infrared (FTIR) spectra density theory (DFT) calculations. Via testing six kinds combinations, it found that, difference (ΔIn) between metals ≥6 eV proportion reaches ∼20%, effect becomes dominant. all as-prepared BMOFs, optimal BMOF(Sr)–0.2Fe photocatalyst exhibits an NH3 evolution rate up 780 μmol g–1 h–1. This work may unveil corner hidden mechanism chemical bond broad range catalytic processes.

Language: Английский

Citations

116
Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis DOI
Xianbiao Fu, Valerie A. Niemann, Yuanyuan Zhou

et al.

Nature Materials, Journal Year: 2023, Volume and Issue: 23(1), P. 101 - 107

Published: Oct. 26, 2023

Language: Английский

Citations

89
Double-atom catalysts for energy-related electrocatalysis applications: a theoretical perspective DOI
Donghai Wu, Bingling He, Yuanyuan Wang

et al.

Journal of Physics D Applied Physics, Journal Year: 2022, Volume and Issue: 55(20), P. 203001 - 203001

Published: Jan. 13, 2022

Abstract Due to the excellent activity, selectivity, and stability, atomically dispersed metal catalysts with well-defined structures have attracted intensive research attention. As extension of single-atom catalyst, double-atom catalyst (DAC) featuring dimer anchored on a suitable substrate has recently emerged as focus for energy-related electrocatalysis reactions. flexible dual-metal sites synergetic effect between two atoms in DACs, there are more possibilities adjust their geometrical configurations electronic structures. The wide tunability active could offer opportunities optimize binding strength reaction intermediates thus catalytic activity and/or selectivity chemical Moreover, neighboring provide platform perform complex involving bond coupling. This review aims summarize recent advance theoretical DACs diverse electrocatalytic It starts brief introduction DACs. Then an overview main experimental synthesis strategies is provided. Emphatically, performance together underlying mechanism different reactions, including nitrogen reduction reaction, carbon dioxide oxygen hydrogen evolution highlighted by discussing how outstanding attributes mentioned above affect pathway, product selectivity. Finally, challenges development prospected shed fresh light rational design efficient at atomic scale future.

Language: Английский

Citations

79
Catalytic active centers beyond transition metals: atomically dispersed alkaline-earth metals for the electroreduction of nitrate to ammonia DOI
Donghai Wu, Peng Lv,

Jiarui Wu

et al.

Journal of Materials Chemistry A, Journal Year: 2022, Volume and Issue: 11(4), P. 1817 - 1828

Published: Dec. 19, 2022

Taking an alkaline-earth (AE) metal single-atom catalyst supported on graphene as the representative, feasibility of AE metals active centers for electrocatalytic nitrate reduction reaction to produce NH 3 has been theoretically explored.

Language: Английский

Citations

74
An Illustrated Guide to Schlenk Line Techniques DOI Open Access
Andryj M. Borys

Organometallics, Journal Year: 2023, Volume and Issue: 42(3), P. 182 - 196

Published: Jan. 29, 2023

Schlenk lines are versatile pieces of laboratory equipment that enable the safe and convenient manipulation air- moisture-sensitive compounds. First pioneered in 1913 by Wilhelm Schlenk, apparatus techniques used today have evolved considerably, allowing more challenging sensitive synthetic chemistry to be carried out on a routine basis. This tutorial, which is based The Line Survival Guide, aims showcase explain key technical aspects line through series illustrated guides. It hoped this practical guide provides useful introductory resource teaching tool for beginner users, as well go-to aid chemists all proficiency.

Language: Английский

Citations

51
Low oxidation state and hydrido group 2 complexes: synthesis and applications in the activation of gaseous substrates DOI
Matthew J. Evans, Cameron Jones

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 5054 - 5082

Published: Jan. 1, 2024

This review summarises advances in the chemistry of low-oxidation state and hydrido group 2 metal complexes, focussing on their use for reductive activation feed-stock gaseous small molecules, subsequent transformation into value added products.

Language: Английский

Citations

20
Four-electron reduction of benzene by a samarium(ii)-alkyl without the addition of external reducing agents DOI
Georgia M. Richardson,

Thayalan Rajeshkumar,

Finlay M. Burke

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: 17(1), P. 20 - 28

Published: Jan. 1, 2025

Language: Английский

Citations

3
Catalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers DOI Creative Commons
Yue Pang, Markus Leutzsch,

Nils Nöthling

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(32), P. 12487 - 12493

Published: Aug. 6, 2021

Herein, we report a hydrodefluorination reaction of polyfluoroarenes catalyzed by bismuthinidenes, Phebox-Bi(I) and OMe-Phebox-Bi(I). Mechanistic studies on the elementary steps support Bi(I)/Bi(III) redox cycle that comprises C(sp2)–F oxidative addition, F/H ligand metathesis, C(sp2)–H reductive elimination. Isolation characterization cationic Phebox-Bi(III)(4-tetrafluoropyridyl) triflate manifests feasible addition into bond. Spectroscopic evidence was provided for formation transient hydride during catalysis, which decomposes at low temperature to afford corresponding bond while regenerating propagating Phebox-Bi(I). This protocol represents distinct catalytic example where main-group center performs three organometallic in low-valent manifold.

Language: Английский

Citations

81
Electrochemical Nitrate Production via Nitrogen Oxidation with Atomically Dispersed Fe on N-Doped Carbon Nanosheets DOI
Ying Guo, Shaoce Zhang, Rong Zhang

et al.

ACS Nano, Journal Year: 2021, Volume and Issue: 16(1), P. 655 - 663

Published: Dec. 22, 2021

Electrocatalytic N2 oxidation (NOR) into nitrate is a potential alternative to the emerging electrochemical reduction (NRR) ammonia achieve higher efficiency and selectivity of artificial fixation, as O2 from competing oxygen evolution reaction (OER) potentially favors oxygenation NOR, which different parasitic hydrogen (HER) for NRR. Here, we develop an atomically dispersed Fe-based catalyst on N-doped carbon nanosheets (AD-Fe NS) exhibits exceptional catalytic NOR capability with record-high yield 6.12 μ mol mg-1 h-1 (2.45 cm-2 h-1) Faraday 35.63%, outperforming all reported catalysts most well-developed NRR catalysts. The isotopic labeling test validates N source resultant electro-oxidation catalyzed by AD-Fe NS. Experimental theoretical investigations identify Fe atoms in NS active centers can effectively capture molecules elongate N≡N bond hybridization between 3d orbitals 2p orbitals. This activates triggers subsequent NOR. In addition, NOR-related pathway has been proposed that reveals positive effect derived OER NO3- formation.

Language: Английский

Citations

77