Abstract
Populist political movements claim to be democratic in expressing what the people want, against the political establishment. These claims are misconceived to begin with in presupposing a ...definitive unitary people. Nonetheless, constitutional democracies face a special challenge to resist these claims in principle because they are unmistakably democratic sounding claims; they purport to empower popular will so that the people can rule themselves. Populist movements can be successful at the ballot box and push political culture in antidemocratic directions through democratic means, all the while claiming democratic legitimacy. The very processes of democracy are under threat. Traditionally, political winners are not motivated to change the system that saw them elected; populists are different in this regard. The populist challenge prompts a revisit of the debate about the democratic legitimacy of judges being empowered to displace the decisions of elected legislative assemblies (the constitutional review debate). An underdeveloped aspect of the constitutional review debate was the scope for courts to intervene specifically in political processes to correct them when they have gone awry and to help prevent them going awry in the first place. Judicial intervention is costly in democratic terms, and yet democracy has to be protected. This Article analyzes the search for a balance between popular will shaping democratic processes and judicially managed constitutional limitations on popular will shaping those processes. The recommended judicial role is styled as courts protecting—not perfecting—democracy, and it is a John Hart Ely-inspired modification of a separation of powers defense of constitutional review. In addressing the populist challenge, courts can, in principle, try to be a step ahead in anticipating and, where they can, slowing degradation of democracy and thereby helping to prevent it.
Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox ...is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li
Ni
Co
Mn
O
, these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.
The molecular structure of the electrical double layer determines the chemistry in all electrochemical processes. Using x-ray absorption spectroscopy (XAS), we probed the structure of water near gold ...electrodes and its bias dependence. Electron yield XAS detected at the gold electrode revealed that the interfacial water molecules have a different structure from those in the bulk. First principles calculations revealed that ∼50% of the molecules lie flat on the surface with saturated hydrogen bonds and another substantial fraction with broken hydrogen bonds that do not contribute to the XAS spectrum because their core-excited states are delocalized by coupling with the gold substrate. At negative bias, the population of flat-lying molecules with broken hydrogen bonds increases, producing a spectrum similar to that of bulk water.
The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of greenhouse gases in the atmosphere. If implemented, the cost of electricity generated by a ...fossil fuel-burning power plant would rise substantially, owing to the expense of removing CO2 from the effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended metal-organic frameworks can behave as 'phase-change' adsorbents, with unusual step-shaped CO2 adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which, above a metal-dependent threshold pressure, CO2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO2 separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient adsorbents for removing CO2 from various gas mixtures, and yield insights into the conservation of Mg(2+) within the ribulose-1,5-bisphosphate carboxylase/oxygenase family of enzymes.
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