Chemical transformations and transport phenomena at interfaces

Abstract

Interfaces, the boundary that separates two or more chemical compositions and/or phases of matter, alters basic chemical and physical properties including the thermodynamics of selectivity, transition states, and pathways of chemical reactions, nucleation events and phase growth, and kinetic barriers and mechanisms for mass transport and heat transport. While progress has been made in advancing more interface-sensitive experimental approaches, their interpretation requires new theoretical methods and models that in turn can further elaborate on the microscopic physics that make interfacial chemistry so unique compared to the bulk phase. In this review, we describe some of the most recent theoretical efforts in modeling interfaces, and what has been learned about the transport and chemical transformations that occur at the air-liquid and solid-liquid interfaces.

Integrated carbon capture and conversion: A review on C2+ product mechanisms and mechanism-guided strategies

“…Thus, the characterization techniques need to be specifically modified to enable a focus on the solid/liquid interface. Recent developments in characterization techniques like Fourier Transform Infrared spectroscopy (FTIR), Raman spectroscopy, and Ambient-Pressure X-Ray Spectroscopy (APXPS) have been able to overcome these challenges ( Tian & Ren, 2004 ; Zaera, 2014 ; Favaro et al, 2017b ; Salmeron, 2018 ; Lu et al, 2019 ; Han et al, 2021b ; Radjenovic et al, 2021 ; Ye & Liu, 2021 ; Hao et al, 2022 ). Using these characterization tools could enable a deeper understanding of the mechanisms involved in the activation process ( Favaro et al, 2017a ; Qian et al, 2019 ; Qian et al, 2020 ).…”

“…On the other hand, computational studies can play a key role in assessing the energy landscape involved in the conversion of CO 2 to specific products. These assessments can be accelerated by implementing larger scale density functional theory (DFT) calculations ( Kronik et al, 2006 ; Zhou et al, 2006 ; Xu et al, 2019 ; 2021 ; Motamarri et al, 2020 ; Dogan et al, 2022 ; Hao et al, 2022 ; Xu et al, 2022 ) along with a faster transition state search procedure ( Koistinen et al, 2017 ; Garrido Torres et al, 2019 ; Meyer et al, 2019 ). Eventually, a database common to both experimental and computational work, as outlined by the Materials Project ( Jain et al, 2013 ) can be constructed which can go a long way towards helping design high performance solutions.…”

Spiers Memorial Lecture: Water at interfaces

“…There are a number of experimental 109 and theoretical studies [110][111][112][113][114][115] of the eld strength at the air/water interface or within droplets, with a range of values reported, which are generally on the order of 10 MV cm −1 and above. As discussed recently by Hao et al, 116 theoretical determinations of this quantity can be quite challenging. Nevertheless, strong electric elds can alter reaction kinetics by lowering activation energies or redox potentials, repelling or attracting solutes, and/or altering solvation electrostatics.…”

Kinetic Monte Carlo Study on the Role of Heterogeneity in the Dissolution Kinetics of Glasses

“…Silicates and other oxide glasses, which consist of a non-equilibrium, disordered network of polyhedral units made of oxygen-coordinated ions, such as silicon or boron (network formers), depolymerized by cations such as calcium, sodium, or potassium (network modifiers), are intrinsically heterogeneous. , The weathering and dissolution of oxide glasses far from equilibrium are fundamentally regulated by the activation energy that the network-forming ions need to overcome to transition from the glass into solution . Such phenomena play an essential role in natural processes such as carbon sequestration, and its understanding is essential to advance technological applications such as the search for low-carbon alternatives to ordinary Portland cement .…”

“…1,2 The weathering and dissolution of oxide glasses far from equilibrium are fundamentally regulated by the activation energy that the network-forming ions need to overcome to transition from the glass into solution. 3 Such phenomena play an essential role in natural processes such as carbon sequestration, 4 and its understanding is essential to advance technological applications such as the search for low-carbon alternatives to ordinary Portland cement. 5 Compositional relationships and simple structural descriptors of the glass, such as the ratio of non-bridging to bridging oxygens, have been shown to correlate poorly, or not at all, with the dissolution rate of silicates.…”