Carbon dioxide (CO) electroreduction could provide a useful source of ethylene, but low conversion efficiency, low production rates, and low catalyst stability limit current systems. Here we report that a copper electrocatalyst at an abrupt reaction interface in an alkaline electrolyte reduces CO to ethylene with 70% faradaic efficiency at a potential of -0.55 volts versus a reversible hydrogen electrode (RHE). Hydroxide ions on or near the copper surface lower the CO reduction and carbon monoxide (CO)-CO coupling activation energy barriers; as a result, onset of ethylene evolution at -0.165 volts versus an RHE in 10 molar potassium hydroxide occurs almost simultaneously with CO production. Operational stability was enhanced via the introduction of a polymer-based gas diffusion layer that sandwiches the reaction interface between separate hydrophobic and conductive supports, providing constant ethylene selectivity for an initial 150 operating hours.
Low-dimensional perovskites have-in view of their high radiative recombination rates-shown great promise in achieving high luminescence brightness and colour saturation. Here we investigate the effect of electron-phonon interactions on the luminescence of single crystals of two-dimensional perovskites, showing that reducing these interactions can lead to bright blue emission in two-dimensional perovskites. Resonance Raman spectra and deformation potential analysis show that strong electron-phonon interactions result in fast non-radiative decay, and that this lowers the photoluminescence quantum yield (PLQY). Neutron scattering, solid-state NMR measurements of spin-lattice relaxation, density functional theory simulations and experimental atomic displacement measurements reveal that molecular motion is slowest, and rigidity greatest, in the brightest emitter. By varying the molecular configuration of the ligands, we show that a PLQY up to 79% and linewidth of 20 nm can be reached by controlling crystal rigidity and electron-phonon interactions. Designing crystal structures with electron-phonon interactions in mind offers a previously underexplored avenue to improve optoelectronic materials' performance.
As energy demand continues to increase, so too do anthropogenic carbon emissions and global temperatures. Renewable energy sources such as solar, wind and hydroelectricity displace fossil fuel carbon emissions and continue to progress to wider deployment. However, long-term (seasonal) energy storage remains a challenge that must be addressed for renewables to meet a major fraction of global energy demand 1 . Carbon dioxide electroreduction to renewable fuels and feedstocks provides an energy storage solution to the seasonal variability of renewable energy sources 2 . When coupled with carbon capture technology, the carbon dioxide reduction reaction (CO 2 RR) offers a means to close the carbon cycle.CO 2 RR electrocatalysts lower energetic barriers to CO 2 reduction by stabilizing intermediates and transition states in the multistep electrochemical reduction process 3 . Copper reduces CO 2 to a wide range of hydrocarbon products such as methane, ethylene, ethanol and propanol 4 . Unfortunately, bulk copper is not selective among various carbon products, and it also suffers Faradaic efficiency (FE) losses to the competing hydrogen evolution reaction.Among possible products, C2+ hydrocarbons are highly sought in view of their commercial value. Ethylene, for example, is a precursor to the production of polyethylene, a major plastic. Selectively producing ethylene over methane circumvents costly paraffin-olefin separation 5 . Developing catalysts that work at ambient conditions to produce C2 selectively over C1 gaseous products will increase the relevance of renewable feedstocks in the chemical sector.Oxide-derived copper is one class of catalyst that has shown enhanced CO 2 RR activity and increased selectivity towards multi-carbon products [6][7][8] . The selectivity of these catalysts is dependent on structural morphology and copper oxidation state 9-17 . Electrochemical reduction of copper oxide catalyst films can lead to grain boundaries, undercoordinated sites and roughened surfaces that are hypothesized to be catalytically active sites 8,18 . Residual oxides, proposed to play a key role in catalysis, may exist after electrochemical reduction 7 . A recent report of oxygen plasma-activated oxide-derived copper catalysts achieved an ethylene FE of 60% at − 0.9 V versus reversible hydrogen electrode (RHE) 9 , with activity attributed to the presence of Cu + species. In situ hard X-ray absorption spectroscopy (hXAS) experiments have suggested stable Cu + species exist at highly negative CO 2 RR potentials of ~− 1.0 versus RHE 9 . However, the presence of Cu + species during CO 2 RR is still the subject of debate; 7,19 and in situ tracking of the copper oxidation state with time resolution during CO 2 RR has remained elusive.Morphological effects of copper nanostructures have a significant effect on the selectivity of CO 2 RR to multi-carbon products [20][21][22][23][24] . Copper catalysts with different morphologies have been synthesized through annealing, chemical treatments on thin films, colloidal synthesis and ...
As our understanding and control of intra- and intermolecular interactions evolve, ever more complex molecular systems are synthesized and assembled that are capable of performing work or completing sophisticated tasks at the molecular scale. Commonly referred to as molecular machines, these dynamic systems comprise an astonishingly diverse class of motifs and are designed to respond to a plethora of actuation stimuli. In this Review, we outline the conditions that distinguish simple switches and rotors from machines and draw from a variety of fields to highlight some of the most exciting recent examples of opportunities for driven molecular mechanics. Emphasis is placed on the need for controllable and hierarchical assembly of these molecular components to display measurable effects at the micro-, meso-, and macroscales. As in Nature, this strategy will lead to dramatic amplification of the work performed via the collective action of many machines organized in linear chains, on functionalized surfaces, or in three-dimensional assemblies.
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