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Register a new userTaking the Heat Off of Plasmonic Chemistry
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Authors
Prashant K. Jain
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Several chemical reactions catalyzed by plasmonic nanoparticles show enhanced rates under visible-light-excitation of the localized surface plasmon resonance of the nanoparticles. But it has been argued that there is an associated photothermal effect that can complicate the analysis and/or interpretation of the nature of the role played by plasmon excitation. This Viewpoint discusses this dilemma and provides some best practices for accounting for photothermal contributions in plasmon-excitation-driven chemistry. A classification of plasmonic chemistry into plasmonic photocatalysis and plasmonic photosynthesis is also proposed. It is argued that photosynthetic reactions, which require a Gibbs free energy input, constitute an ultimate test of the non-thermal, photochemical action of plasmon excitation.
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Here we highlight recent progress in the field of computational chemistry of nanoporous materials, focusing on methods and studies that address the extraordinary dynamic nature of these systems: the high flexibility of their frameworks, the large-scale structural changes upon external physical or chemical stimulation, and the presence of defects and disorder. The wide variety of behavior demonstrated in soft porous crystals, including the topical class of metal-organic frameworks, opens new challenges for computational chemistry methods at all scales.
Using infrared spectroscopy combined with ab initio methods we study reactions of H$_2$O and CO inside the confined spaces of Zn-MOF-74 channels. Our results show that, once the water dissociation reaction H$_2$O$;rightarrow;$OH+H takes place at the metal centers, the addition of 40 Torr of CO at 200 $^{circ}$C starts the production of formic acid via OH+H+CO$;rightarrow;$HCO$_2$H. Our detailed analysis shows that the overall reaction H$_2$O+CO$;rightarrow;$HCO$_2$H takes place in the confinement of MOF-74 without an external catalyst, unlike the same reaction on flat surfaces. This discovery has several important consequences: It opens the door to a new set of catalytic reactions inside the channels of the MOF-74 system, it suggests that a recovery of the MOFs adsorption capacity is possible after it has been exposed to water (which in turn stabilizes its crystal structure), and it produces the important industrial feedstock formic acid.
By generalizing the traditional concept of heat dQ and work dW to also include their time-dependent irreversible components d_{i}Q and d_{i}W allows us to express them in terms of the instantaneous internal temperature T(t) and pressure P(t), whereas the conventional form uses the constant values T_{0} and P_{0} of the medium. This results in an extremely useful formulation of non-equilibrium thermodynamics so that the first law turns into the Gibbs fundamental relation and the Clausius inequality becomes an equality ointdQ(t)/T(t)equiv0 in all cases, a quite remarkable but unexpected result. We determine the irreversible components d_{i}Qequivd_{i}W and discuss how they can be determined to obtain the generalized dW(t) and dQ(t).
Specific heat of dipolar glasses does not obey Debye law. It is of interest to know if the non-Debye specific heat can be accounted for in terms of Schottky-type specific heat arising from rotational tunneling states of the dipoles. This paper deals with rotational tunneling spectra of NH$_{4}^{+}$ ions and the non-Debye specific heat of mixed salts (e.g. (NH$_{4})_{x}$Rb$_{1-x}$Br) of ammonium and alkali halides which are known to exhibit dipolar glass phase. We have measured specific heat of above mixed salts at low temperatures (1.5 K $< T <$ 15 K). It is seen that while the specific heat of pure salts obeys Debye law, the specific heat of mixed salts does not obey Debye law. We have studied the effect of the NH$_{4}^{+}$ ion concentration, first neighbor environment of NH$_{4}^{+}$ ion and the lattice strain field on the non-Debye specific heat by carrying out measurements on suitably chosen mixed salts. Independent of above, we have measured the rotational tunneling spectra, $f(omega $), of the NH$_{4}^{+}$ ions in above salts using technique of neutron incoherent inelastic scattering. The above studies show that both the non-Debye specific heat and the tunneling spectra of the NH$_{4}^{+}$ ions depend on the NH$_{4}^{+}$ ion concentration, first neighbor environment of NH$_{4}^{+}$ ions and the lattice strain field. We have further shown that the temperature dependence of the measured specific heat can be explained for all the samples in terms of a model that takes account of contributions to the specific heat from the Debye phonons and the rotational tunneling states of the NH$_{4}^{+}$ ions. To the best of our knowledge, this is a first study where it is shown that measured specific heat of (NH$_{4})_{x}$Rb$_{1-x}$Br can be quantitatively explained in terms of an experimentally measured rotational tunneling spectra $f(omega $) of the NH$_{4}^{+}$ ions.
Using a materials genome approach on the basis of the density functional theory, we have formulated a new class of inorganic electrolytes for fast diffusion of Li+ ions, through fine-tuning of lattice chemistry of anti-perovskite structures. Systematic modelling has been carried out to elaborate the structural stability and ion transportation characteristics in Li3AX based cubic anti-perovskite, through alloying on the chalcogen lattice site (A) and alternative occupancy of the halogen site (X). In addition to identifying effective ways for reduction of diffusion barriers for Li+ ions in anti-perovskite phases via suitable designation of lattice occupancy, the current theoretical study leads to discovery and synthesis of a new phase with a double-anti-perovskite structure, Li6OSI2 (or Li3O0.5S0.5I). Such a new compound is of fairly low activation barrier for Li+ diffusion, together with a wide energy band gap to hinder conduction of electrons.
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