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Molecular tuning of CO2-to-ethylene conversion 期刊论文
NATURE, 2020, 577 (7791) : 509-+
作者:  Li, Fengwang;  39;Brien, Colin P.
收藏  |  浏览/下载:11/0  |  提交时间:2020/07/03

The electrocatalytic reduction of carbon dioxide, powered by renewable electricity, to produce valuable fuels and feedstocks provides a sustainable and carbon-neutral approach to the storage of energy produced by intermittent renewable sources(1). However, the highly selective generation of economically desirable products such as ethylene from the carbon dioxide reduction reaction (CO2RR) remains a challenge(2). Tuning the stabilities of intermediates to favour a desired reaction pathway can improve selectivity(3-5), and this has recently been explored for the reaction on copper by controlling morphology(6), grain boundaries(7), facets(8), oxidation state(9) and dopants(10). Unfortunately, the Faradaic efficiency for ethylene is still low in neutral media (60 per cent at a partial current density of 7 milliamperes per square centimetre in the best catalyst reported so far(9)), resulting in a low energy efficiency. Here we present a molecular tuning strategy-the functionalization of the surface of electrocatalysts with organic molecules-that stabilizes intermediates for more selective CO2RR to ethylene. Using electrochemical, operando/in situ spectroscopic and computational studies, we investigate the influence of a library of molecules, derived by electro-dimerization of arylpyridiniums(11), adsorbed on copper. We find that the adhered molecules improve the stabilization of an '  atop-bound'  CO intermediate (that is, an intermediate bound to a single copper atom), thereby favouring further reduction to ethylene. As a result of this strategy, we report the CO2RR to ethylene with a Faradaic efficiency of 72 per cent at a partial current density of 230 milliamperes per square centimetre in a liquid-electrolyte flow cell in a neutral medium. We report stable ethylene electrosynthesis for 190 hours in a system based on a membrane-electrode assembly that provides a full-cell energy efficiency of 20 per cent. We anticipate that this may be generalized to enable molecular strategies to complement heterogeneous catalysts by stabilizing intermediates through local molecular tuning.


Electrocatalytic reduction of CO2 over copper can be made highly selective by '  tuning'  the copper surface with adsorbed organic molecules to stabilize intermediates for carbon-based fuels such as ethylene


  
A droplet-based electricity generator with high instantaneous power density 期刊论文
NATURE, 2020, 578 (7795) : 392-+
作者:  Dabney, Will;  Kurth-Nelson, Zeb;  Uchida, Naoshige;  Starkweather, Clara Kwon;  Hassabis, Demis;  Munos, Remi;  Botvinick, Matthew
收藏  |  浏览/下载:173/0  |  提交时间:2020/07/03

Extensive efforts have been made to harvest energy from water in the form of raindrops(1-6), river and ocean waves(7,8), tides(9) and others(10-17). However, achieving a high density of electrical power generation is challenging. Traditional hydraulic power generation mainly uses electromagnetic generators that are heavy, bulky, and become inefficient with low water supply. An alternative, the water-droplet/solid-based triboelectric nanogenerator, has so far generated peak power densities of less than one watt per square metre, owing to the limitations imposed by interfacial effects-as seen in characterizations of the charge generation and transfer that occur at solid-liquid(1-4) or liquid-liquid(5,18) interfaces. Here we develop a device to harvest energy from impinging water droplets by using an architecture that comprises a polytetrafluoroethylene film on an indium tin oxide substrate plus an aluminium electrode. We show that spreading of an impinged water droplet on the device bridges the originally disconnected components into a closed-loop electrical system, transforming the conventional interfacial effect into a bulk effect, and so enhancing the instantaneous power density by several orders of magnitude over equivalent devices that are limited by interfacial effects.


A device involving a polytetrafluoroethylene film, an indium tin oxide substrate and an aluminium electrode allows improved electricity generation from water droplets, which bridge the previously disconnected circuit components.