A US perspective on closing the carbon cycle to defossilize difficult-to-electrify segments of our economy.

Electrification to reduce or eliminate greenhouse gas emissions is essential to mitigate climate change. However, a substantial portion of our manufacturing and transportation infrastructure will be difficult to electrify and/or will continue to use carbon as a key component, including areas in aviation, heavy-duty and marine transportation, and the chemical industry. In this Roadmap, we explore how multidisciplinary approaches will enable us to close the carbon cycle and create a circular economy by defossilizing these difficult-to-electrify areas and those that will continue to need carbon. We discuss two approaches for this: developing carbon alternatives and improving our ability to reuse carbon, enabled by separations. Furthermore, we posit that co-design and use-driven fundamental science are essential to reach aggressive greenhouse gas reduction targets.

Neutron Scattering Investigations of Hydride Species in Heterogeneous Catalysis.

In heterogeneous catalysis, hydrides on the surface or in the bulk play a critical role as either active components or reaction intermediates in many hydrogen-involving reactions, but characterization of the nature and structure of these hydride species remains challenging. Neutron scattering, which is extremely sensitive to light elements, such as hydrogen, has shown great potential in meeting this challenge. In this Minireview, recent advances in neutron studies of hydride species, mainly over the two most typical classes of catalysts-metals and oxides-are surveyed. Findings on catalysts outside these categories are raised if they are considered to be relevant for contextualization in the present Minireview. The adsorption, dissociation, spillover, and reactivity of hydrogen, especially hydride species over supported metal and oxide catalysts, have been successfully investigated, mostly by means of neutron vibrational spectroscopy. Insights from these neutron studies, which are otherwise not possible with other techniques, shed light on the interaction mechanism of hydrogen with solid surfaces and reaction mechanisms in which hydrogen is involved. Future research challenges on neutron scattering studies of hydrides, as well as catalysis in general, are also highlighted, and more operando-type neutron studies need be conducted to advance the field.

Kinetic analysis of the pyrolysis of phenethyl phenyl ether: computational prediction of alpha/beta-selectivities.

We calculated an overall alpha/beta-selectivity for the pyrolysis of phenethyl phenyl ether as a composite of the alpha/beta-selectivities in the hydrogen abstraction reactions by the phenoxyl and by the benzyl radical that is in excellent agreement with experiment. The difference between the individual selectivities for these radicals is explained by analyzing the electronic structure of the transition states. Spin delocalization of the single electron favors the alpha-pathways. An opposing effect occurs for polarized transition states, such as the transition states for the hydrogen abstraction by the electrophilic phenoxyl radical, where the adjacent ether oxygen in phenethyl phenyl ether stabilizes the beta-transition states. These results indicate that theory will be able to provide excellent predictions of alpha/beta-product selectivities for more complicated lignin model compounds bearing multiple substituents. We have developed a scheme to predict alpha/beta-product selectivities in the pyrolysis of model compounds for the beta-ether linkage in lignin. The approach is based on computation of the relative rate constant, which profits from error cancellation in the individual rate constants. The Arrhenius prefactors depend strongly on the description of the low-frequency modes for which anharmonic contributions are important. We use density functional theory in combination with transition-state theory in this analysis. Diagonal anharmonic effects for individual low-frequency modes are included by employing a second-order Wigner-Kirkwood expansion in a semiclassical expression for the vibrational partition function. The composite alpha/beta-product selectivity is obtained by applying quasi-steady-state kinetic analysis for the intermediate radicals.

Confinement effects on product selectivity in the pyrolysis of phenethyl phenyl ether in mesoporous silica.

Pyrolysis of phenethyl phenyl ether confined in mesoporous silicas by covalent grafting results in significantly increased product selectivity compared with fluid phases.

Pyrolysis of mesoporous silica-immobilized 1,3-diphenylpropane. Impact of pore confinement and size.

Mesoporous silicas such as SBA-15 and MCM-41 are being actively investigated for potential applications in catalysis, separations, and synthesis of nanostructured materials. A new method for functionalizing these mesoporous silicas with aromatic phenols is described. The resulting novel hybrid materials possess silyl aryl ether linkages to the silica surface that are thermally stable to ca. 550 degrees C, but can be easily cleaved at room temperature with aqueous base for quantitative recovery of the organic moieties. The materials have been characterized by nitrogen physisorption, FTIR, NMR, and quantitative analysis of surface coverages. The maximum densities of 1,3-diphenylpropane (DPP) molecules that could be grafted to the surface were less than those measured on a nonporous, fumed silica (Cabosil) and were also found to decrease as a function of decreasing pore size (5.6-1.7 nm). This is a consequence of steric congestion in the pores that is magnified at the smaller pore sizes, consistent with parallel studies conducted using a conventional silylating reagent, 1,1,3,3-tetramethyldisilazane. Pyrolysis of the silica-immobilized DPP revealed that pore confinement leads to enhanced rates and altered product selectivity for this free-radical reaction compared with the nonporous silica, and the rates and selectivities also depended on pore size. The influence of confinement is discussed in terms of enhanced encounter frequencies for bimolecular reaction steps and pore surface curvature that alters the accessibility and resultant selectivity for hydrogen transfer steps.

Pore size effects in the pyrolysis of 1,3-diphenylpropane confined in mesoporous silicas.

A new method for derivatizing mesoporous silicas, SBA-15 and MCM-41, with a substituted phenol is described, and pore confinement and surface curvature are shown to impact the reaction rate and product selectivity for the pyrolysis of surface-immobilized 1,3-diphenylpropane.

Free-radical reactions under diffusional constraints: orientation does matter in hydrogen transfer.

Pyrolysis of silica-immobilized 1,3-diphenylpropane at 375 degrees C has been examined in the presence of a series of isomeric (by point of attachment) co-attached hydroaromatic spacer molecules. Under the diffusional constraints, the pyrolysis rate is sensitive to the orientation of the spacer molecule, which must transfer hydrogen to intermediate benzylic radicals on the surface. Spacer molecules possessing a meta-orientation of the benzylic hydrogens with respect to the surface linkage are able to attain a better geometry for the hydrogen transfer on the surface resulting in faster reaction rates.