Concepts, models, and methods in computational heterogeneous catalysis illustrated through CO2 conversion

Theoretical investigations and computational studies have notoriously contributed to the development of our understanding of heterogeneous catalysis during the last decades, when powerful computers have become generally available and efficient codes have been written that can make use of the new highly parallel architectures. The outcomes of these studies have shown not only a predictive character of theory but also provide inputs to experimentalists to rationalize their experimental observations and even to design new and improved catalysts. In this review, we critically describe the advances in computational heterogeneous catalysis from different viewpoints. We firstly focus on modeling because it constitutes the first key step in heterogenous catalysis where the systems involved are tremendously complex. A realistic description of the active sites needs to be accurately achieved to produce trustable results. Secondly, we review the techniques used to explore the potential energy landscape and how the information thus obtained can be used to bridge the gap between atomistic insight and macroscale experimental observations. This leads to the description of methods that can describe the kinetic aspects of catalysis, which essentially encompass microkinetic modeling and kinetic Monte Carlo simulations. The puissance of computer simulations in heterogeneous catalysis is further illustrated by choosing CO2 conversion catalyzed by different materials for most of which a comparison between computational information and experimental data is available. Finally, remaining challenges and a near future outlook of computational heterogeneous catalysis are provided.publishe

MXenes atomic layer stacking phase transitions and their chemical activity consequences

Two-dimensional (2D) transition-metal nitrides and carbides (MXenes), containing a few atomic layers only, are novel materials which have become a hub of research in many applied technological fields, ranging from catalysis, to environmental scrubber materials, up to batteries. MXenes are obtained by removing the A element from precursor MAX phases, and it is for this reason that it is often assumed that the resulting 2D material displays the MAX atomic layer stacking—an ABC sequence with trigonal (D3d) symmetry. By means of density functional theory calculations, including dispersion, this work thoroughly explores the stability of alternative ABA stacking, with D3h hexagonal symmetry, for a total of 54 MXene materials with M2X, M3X2, and M4X3 stoichiometries (M=Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W; and X=C or N), revealing that for clean MXenes, the ABA stacking is fostered (i) by the number of d electrons in M, (ii) when X=N rather than X=C, and (iii) when the surface is terminated by oxygen adatoms. The results suggest that stacking phase transitions are likely to take place under working operando conditions, surmounting affordable layer sliding energy barriers, in accordance with the experimentally observed layer distortions in Mo2N. Finally, we tackled the adsorptive and catalytic capabilities implications of such layer phase transition by considering N2 adsorption, dissociation, and hydrogenation on selected ABC and ABA stacked MXenes. Results highlight changes in adsorption energies of up to ∼1 eV, and in N2 dissociation energy barriers of up to ∼0.3 eV, which can critically change the reaction step rate constant by three to four orders of magnitude for working temperatures in the 400–700 K range. Consequently, it is mandatory to carefully determine the atomic structure of MXenes and to use models with the most stable stacking when inspecting their chemical or physical properties.publishe

Facile heterogeneously catalyzed nitrogen fixation by MXenes

The rate-limiting step for ammonia (NH3) production via the Haber–Bosch process is the dissociation of molecular nitrogen (N2), which requires quite harsh working conditions, even when using appropriate heterogeneous catalysts. Here, motivated by the demonstrated enhanced chemical activity of MXenes— a class of two-dimensional inorganic materials— toward the adsorption of quite stable molecules such as CO2 and H2O, we use density functional theory including dispersion, to investigate the suitability of such MXene materials to catalyze N2 dissociation. Results show that MXenes exothermically adsorb N2, with rather large adsorption energies ranging from −1.11 to −3.45 eV and elongation of the N2 bond length by ∼20%, greatly facilitating their dissociation with energy barriers below 1 eV, reaching 0.28 eV in the most favorable studied case of W2N. Microkinetic simulations indicate that the first hydrogenation of adsorbed atomic nitrogen is feasible at low pressures and moderate temperatures, and that the production of NH3 may occur above 800 K on most studied MXenes, in particular, in W2N. These results reinforce the promising capabilities of MXenes to dissociate nitrogen and suggest combining them co-catalytically with Ru nanoparticles to further improve the efficiency of ammonia synthesis.publishe

Carbon capture and usage by MXenes

Two-dimensional pristine M2X MXenes are proposed as highly active catalytic materials for carbon dioxide (CO2) greenhouse gas conversion into carbon monoxide (CO) on the basis of a multiscale modeling approach, coupling calculations carried out in the framework of density functional theory and newly developed kinetic phase diagrams. The extremely facile CO2 conversion into CO leaves the MXene surfaces partially covered by atomic oxygen, recovering its pristine nature by a posterior catalyst regeneration by hydrogen (H2) treatment at high temperatures, with MXenes effectively working as two-step catalysts for the reverse water–gas shift reaction.publishe

Selectivity for CO2 over CH4 on a functionalized periodic mesoporous phenylene-silica explained by transition state theory

Efficient separation of CO2/CH4 is critical in biogas upgrading, requiring highly selective adsorbents. Based on the adsorption energies of 0.30 and 0.14 eV, previously calculated by dispersion corrected density functional theory for adsorption/desorption of CO2 and CH4 on the functionalized periodic mesoporous phenylene-silica material APTMS@Ph-PMO, respectively, transition state theory rates were derived and used to simulate the adsorption/desorption rates of these two gases on APTMS@Ph-PMO. The latter yielded an estimation of initial CO2/CH4 selectivity at various temperatures. At T= 298 K, selectivity of 32.2 agrees to an experimental value of 26.1, which validates the method used for evaluating CO2/CH4 adsorption selectivities. 2017 Elsevier B.V. All rights reserved

First-principles calculations on the adsorption behavior of amino acids on a titanium carbide MXene

Due to their vast range of promising biomedical and electronic applications, there is a growing interest in bioinorganic lamellar nanomaterials. MXenes are one such class of materials, which stand out by virtue of their demonstrated biocompatibility, pharmacological applicability, energy storage performance, and feasibility as single-molecule sensors. Here, we report on first-principles predictions, based on density functional theory, of the binding energies and ground-state configurations of six selected amino acids (AAs) adsorbed on O-terminated two-dimensional titanium carbide, Ti2CO2. We find that most AAs (aspartic acid, cysteine, glycine, and phenylalanine) prefer to adsorb via their nitrogen atom, which forms a weak bond with a surface Ti atom, with bond lengths of around 2.35 Å. In contrast, histidine and serine tend to adsorb parallel to the MXene surface, with their α carbon about 3 Å away from it. In both adsorption configurations, the adsorption energies are on the order of the tenths of an electronvolt. In addition, we find a positive, nearly linear correlation between the binding energy of each studied AA and its van der Waals volume, which suggests an adsorption dominated by van der Waals forces. This relationship allowed us to predict the adsorption energies for all of the proteinogenic AAs on the same Ti2CO2 MXene. Our analysis additionally shows that in the parallel adsorption mode there is a negligible transfer of charge density from the AA to the surface but noticeable in the N-bonded adsorption mode. In the latter, the isosurfaces of charge density differences show accumulation of shared electrons in the region between N and Ti, confirming the predicted N–Ti bond. The moderate adsorption energy values calculated, as well as the preservation of the integrity of both the AAs and the surface upon adsorption, reinforce the capability of Ti2CO2 as a promising reusable biosensor for amino acids.publishe

Effect of the exchange-correlation potential on the transferability of Bronsted-Evans-Polanyi relationships in heterogeneous catalysis

As more and more accurate density functional methods emerge, the transferability of Bronsted-Evans-Polanyi (BEP) relationships obtained with previous models is an open question. In this work, BEP relationships derived from different density functional theory based calculations are analyzed to answer this question. In particular, BEP relationships linking the activation energy of O-H bond breaking reactions taking place on metallic surfaces with the adsorption energy of the reaction products are chosen as a case study. These relationships are obtained with the widely used Perdew-Wang (PW91) generalized gradient approximation (GGA) exchange-correlation functional and with the more accurate meta-GGA Tao-Perdew Staroverov-Scuseria (TPSS) one. We provide compelling evidence that BEP relationships derived from PW91 and TPSS functionals are essentially coincidental. This finding validates previously published BEP relationships and indicates that the reaction activation energy barrier can be obtained by the determination of the energy reaction descriptor value at the less computationally demanding GGA level; an important aspect to consider in future studies aimed at the computational design of catalysts :with improved characteristics

MXenes as promising catalysts for water dissociation

Two-dimensional few-layered transition-metal nitrides and carbides, called MXenes, have attracted a great interest given their large surface areas and their unique physicochemical properties. Motivated by the known reactivity of surfaces of bulk transition metal carbides on the mechanism behind the water-gas shift (WGS) reaction, density functional theory (DFT) calculations were employed to investigate the bonding of water and its dissociation on a set of eighteen M2X MXene (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W, while X = C or N) surfaces. Here it is shown that all the studied MXenes exothermically adsorb water, with adsorption energies ranging from -1.43 to -2.94 eV, and greatly facilitate its dissociation, with energy barriers below 0.44 eV. These results reinforce the role of MXenes in promoting water dissociation, effectively suggesting their potential as catalysts for industrially relevant processes such as the WGS reaction.publishe

Learning Objects, Learning Objectives and Learning Design.

Educational research and development into e-learning mainly focuses on the inclusion of new technological features without taking into account psycho-pedagogical concerns that are likely to improve a learner's cognitive process in this new educational category. This paper presents an instructional model that combines objectivist and constructivist learning theories. The model is based on the concept of a learning objective which is composed of a set of learning objects. A software tool, called the Instruction Aid System (IAS), has been developed to guide instructors through the development of learning objectives and the execution of the analysis and design phases of the proposed instructional model. Additionally, a blended approach to the learning process in Web-based distance education is also presented. This approach combines various event-based activities: self-paced learning, live e-learning and the use of face-to-face contact in classrooms

Rowing against the wind: how do times of austerity shape academic entrepreneurship in unfriendly environments?

[EN] Academic spin-offs (ASOs) help universities transfer knowledge or technology through business projects developed by academic staff. This investigation aims at analyzing the critical factors for spin-off creation at universities operating in crisis-raven, entrepreneurship-unfriendly environments. Such factors revolve around four types of resources: environmental, institutional, organizational, and personal. Focusing on a Southern European context, as an example of an unfriendly environment affected by economic crisis, an entrepreneurial university (the Technical University of Valencia in Spain, UPV) is our research setting. Through a case study approach, we examine the potential of UPV as a springboard for ASOs. Our results show an adverse local environment, a rather favorable influence of institutional and organizational drivers, and a mixed role of personal factors. Our findings illustrate that UPV consistently supports spin-off creation due to a greater (rather positive) reflexivity from its institutional, organizational and personal resources than the (negative) imprinting of the unfriendly environment. This helps counter-balance the structural unfriendliness for academic entrepreneurship, and trigger a crisis-led risk-taking attitude by academic staff. Hence, UPV should continue with its current strategy of supporting academic entrepreneurship, and might transfer best practices to other universities also affected by unfavorable environmental conditions. Generally speaking, we would advise universities facing adverse circumstances to develop rules and mechanisms for academic entrepreneurship, carefully revise and improve malfunctions, and become involved throughout the whole process of spin-off development. All in all, our study advances understanding of how the different drivers for ASO creation can be revamped by universities located in unfriendly environments, having in mind the key role that universities play in fostering social and economic development through academic entrepreneurship in such environments.The authors would like to thank the Universitat Politecnica de Valencia (grant PAID-06-12-0916), and the Spanish Ministry of Economy and Competitiveness (grant ECO2011-29863), for their financial support for this research.Seguí-Mas, E.; Oltra, V.; Tormo-Carbó, G.; Sarrión Viñes, F. (2017). Rowing against the wind: how do times of austerity shape academic entrepreneurship in unfriendly environments?. International Entrepreneurship and Management Journal. 1-42. doi:10.1007/s11365-017-0478-zS142Acs, Z. J., Audretsch, D. B., & Lehmann, E. E. (2013). The knowledge spillover theory of entrepreneurship. Small Business Economics, 41, 757–774.Alemany, L. (2011). 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