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Selective hydrogenation of phenol to cyclohexanone is intriguing in chemical industry. Though a few catalysts with promising performances have been developed in recent years, the basic principle for catalyst design is still missing owing to the unclear catalytic mechanism. This work tries to unravel the mechanism of phenol hydrogenation and the reasons causing the selectivity discrepancy on noble metal catalysts under mild conditions. Results show that different reaction pathways always firstly converge to the formation of cyclohexanone under mild conditions. The selectivity discrepancy mainly depends on the activity for cyclohexanone sequential hydrogenation, in which two factors are found to be responsible, i.e. the hydrogenation energy barrier and the competitive chemisorption between phenol and cyclohexanone, if the specific co-catalyzing effect of H2O on Ru is not considered. Based on the above results, a quantitative descriptor, Eb(one/pl)/Ea, in which Ea can be further correlated to the d band center of the noble metal catalyst, is proposed by the first time to roughly evaluate and predict the selectivity to cyclohexanone for catalyst screening.

Nuclear magnetic resonance (NMR) is a non-destructive and atom-specific specific tool that has become a burgeoning analytic method for understanding the detailed molecular interactions in catalysis and energy storage materials. However, the observation of diverse chemical shifts arising from complex molecular interactions makes the interpretation of NMR spectroscopy increasingly challenging, in particular for a novel system without standards for comparison. Density functional theory-NMR (DFT-NMR) is an indispensable tool to mitigate these challenges and provide detailed 3D molecular structures that relate materials and reaction intermediate structures, and information about chemical interactions, dynamics, and reaction mechanisms. This review provides a fundamental background in DFT-NMR relating to theory development, critical parameters for calculating NMR properties, computational accuracy, and the current capabilities. A variety of practical examples from the fields of catalysis and energy storage, including CO2 capture, are summarized to illustrate the capabilities of DFT-NMR application to date. Last but not least, cautionary notes on the application of these strategies are presented for researchers modeling their own systems.

Metal-iodosylarene complexes have been recently viewed as a second oxidant alongside of the well-known high-valent metal-oxo species. Extensive efforts have been exerted to unveil the structure-function relationship of various metal-iodosylarene complexes. In the present manuscript, density functional theoretical calculations were employed to investigate such relationship of a specific manganese-iodosylbenzene complex [MnIII(TBDAP)(PhIO)(OH)]2+ (1). Our results fit the experimental observations and revealed new mechanistic findings. 1 acts as a stepwise 1e+1e oxidant in sulfoxidation reactions. Surprisingly, C-H bond activation of 9,10-dihydroanthracene (DHA) by 1 proceeds via a novel ionic hydride transfer/proton transfer (HT/PT) mechanism. As a comparison to 1, the electrophilicity of an iodosylbenzene monomer PhIO was investigated. PhIO performs concerted 2e-oxidations both in sulfoxidation and C-H activation. Hydroxylation of DHA by PhIO was found to proceed via a novel ionic and concerted proton-transfer/hydroxyl-rebound mechanism involving 2e-oxidation to form a transient carbonium species.

[Display omitted] • Temperature-dependent ethylene dissociative adsorption on ruthenium was computed quantitatively. • Revised PBE can best quantify the adsorption energy of ethylene, H 2 and CO. • Computed activation barriers of the dissociation of CH 2 CH 2 * and CH 3 C* agree quantitively with experiments. • CO co-adsorption stabilizes CH 3 C* by blocking surface sites and raising the dissociation barrier. • BEP relationship is found for the formation of CH 3 C* and HCC under the co-adsorbed CO and hydrogen. The dissociative adsorption of ethylene onto Ru(1 1 1) at different temperatures was computed systematically at the first time. At 105 K, ethylene dissociative adsorption has the co-adsorbed CH 2 C*+2H* and CH 3 C*+H* as the first and second stable surface intermediates. At over 330 K, CH 3 C*+H* is converted back into CH 2 C* accompanied by H 2 desorption and the subsequent dissociation of CH 2 C* into HCC*, HC*+C* and 2C*. The computed Arrhenius activation barriers of the dissociation of CH 2 CH 2 (0.18 vs. 0.22 ± 0.04 eV) and CH 3 C (0.54 vs. 0.52 ± 0.04 eV) agree perfectly with the available experimental values, and CH 3 C* represents the most stable surface species. Under CO co-adsorption, the most stable surface species are the co-adsorbed CH 3 C*+H*+3CO*. It is found that CO co-adsorption promotes H 2 desorption and stabilizes CH 3 C* by blocking the surface sites for dissociation and raises the dissociation barrier compared to the clean surface (0.78 vs 0.54 eV). Brønsted–Evans–Polanyi relationship between the activation Gibbs free energy barrier and reaction Gibbs free energy is found for CH 2 C*+2H*+ n CO* = CH 3 C*+H*+ n CO* and CH 2 C*+2H*+ n CO* = HCC*+3H*+ n CO* (n = 0–3). Ethylene adsorption has di-σ and π adsorption configurations in very close energy, and H 2 has adsorption energy of about 0.90 eV. [ABSTRACT FROM AUTHOR]

Abstract The surface energies and the morphologies of three iron oxides (α-Fe 2 O 3 , Fe 3 O 4 , and FeO) are systematically investigated by Density Functional Theory (DFT) employing PBE and PBE+U methods. The surface energies are computed under various O chemical potential which is directly related to atmosphere condition. Compared with available experimental observations, PBE provides reasonable prediction on surface stability of all three oxides while the results of PBE+U are not well consistent with experiments for Fe 2 O 3. Based on the Wulff construction and calculated surface energies, the micro-crystal morphologies of three iron oxides are predicted at various oxygen chemical potential. Subsequently, on basis of the data of surface energies, the effect of surface free energies on phase equilibrium of iron oxides nanoparticles are investigated. These results suggest that particle sizes of nanometer have a significant influence on the thermodynamic equilibrium shifting due to their large surfaces energies contributions. This principle can guide people control the phase transition of iron oxides by adjusting surface energies contributions by changing the sizes of particles. Graphical abstract Unlabelled Image Highlights • PBE provides more reasonable prediction on surface stability of three iron oxides (α-Fe 2 O 3 , Fe 3 O 4 , and FeO) than PBE+U. • O-terminations are generally more stable than the Fe-terminations over a wide range of Δμ O for three iron oxides. • The Wulff morphology of iron oxides is a function of O chemical potential. • Particle sizes of nanometer have a significant influence on the thermodynamic equilibrium shifting. [ABSTRACT FROM AUTHOR]

• Another available source of C 1 species is by HCO → CH + O, apart from CO → C + O. • Thermo stability of CH 2 species is a dominant factor in the CH 4 formation. • Different mechanisms of C 1 + C 1 couplings are found on the Fe surfaces. • Exposition of the Fe facets could tune CH 4 selectivity. To tune CH 4 selectivity of Fe-based Fischer-Tropsch synthesis (FTS) in the initial stage is of prime scientific and industrial importance to further improve the catalyst performance. Herein, distribution of CH 4 selectivity on the metallic Fe nanoparticle is predicted by DFT calculations and micro-kinetics analysis about the competition between C 1 hydrogenations and C 1 + C 1 couplings on abundant Fe surfaces including Fe(1 0 0), Fe(1 1 0), Fe(1 1 1), Fe(2 1 1), and Fe(3 1 0). The results show that HCO mechanism (HCO → CH + O) is an available source of C 1 species apart from CO direct dissociation. These Fe surfaces exhibit high effective barriers for CH 4 formation, which is linearly correlated to the thermal stability of CH 2 species. However, carbon chain prolongation on the more stable surfaces greatly depends on the coupling of C and CH species. On the less stable Fe(1 1 1) surface, the CO + C coupling is the main route for chain prolongation. Utilizing the effective barrier difference between the CH 4 formation and the most feasible C 1 + C 1 coupling as a descriptor of CH 4 selectivity, it is quantified that CH 4 selectivity decreases in sequence of Fe(1 0 0) > Fe(2 1 1) > Fe(1 1 0) > Fe(3 1 0) > Fe(1 1 1). It is revealed that thermal stability of the CH 2 species and exposition of the Fe facets could play essential roles in tuning CH 4 selectivity. Trying to expand the area of Fe(2 1 1), Fe(3 1 0) and especially Fe(1 1 1) surfaces would greatly suppress CH 4 selectivity without a decrease of activity. This work provides new insights and design principles for the Fe-based FTS catalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] • Real space evidence of p4g(2 × 2) Fe 2 C and Co 2 C surface carbides. • Tip-sample distance dependent STM imaging of Fe 2 C. • Fe 2 X (X = B, C, N, O) with increasing electrons the reconstruction becomes less favourable. Thin FCC (1 0 0) iron and cobalt carbide films were prepared on Cu(1 0 0) to study the connection between their structure, electronic properties and stability. We present the first detailed, real space experimental confirmation of the C-induced clock reconstruction on the FCC(1 0 0) surfaces of iron and cobalt. Both Fe and Co surface carbides show p4g (2 × 2) surface reconstruction with tetracoordinated square planar carbon and pure FCC (1 0 0) metal layers underneath. Combining tip-sample distance dependent STM imaging with theoretical calculations we present different imaging modes of Fe 2 C. Using a combination of angle-resolved x-ray photoelectron spectroscopy (AR-XPS), Auger electron spectroscopy (AES), low energy electron diffraction (LEED), scanning tunneling microscopy (STM), and theoretical calculations we provide detailed electronic and structural models for Fe 2 C and Co 2 C p4g (2 × 2) surface carbides and other 2D Fe 2 X interstitial compound systems. In various Fe 2 X (X = B, C, N, O) surface compounds moving to the right in the periodic table with increasing electrons the reconstruction becomes less favorable, while iron carbide shows the highest stability. [ABSTRACT FROM AUTHOR]

Periodic density functional theory (revised PBE; RPBE) and ab initio atomistic thermodynamics were used to assess the dissociative adsorption of H 2 O and CO 2 on a (5 × 5) Ru(0001) surface model. For H 2 O dissociation on clean Ru(0001) [H 2 O → OH + H → O + 2H], the first step has lower barrier than the second step (0.75 vs. 0.80 eV). On O pre-covered Ru(0001), H 2 O dissociation [H 2 O + O → 2OH] has lower barrier (0.62 eV) and is more exothermic (−0.29 vs. −0.15 eV). CO 2 dissociation on clean Ru(0001) [CO 2 → CO + O] needs low barrier (0.23 eV) and is highly exothermic by 1.47 eV. In turn, CO 2 formation from surface O removal by CO has barrier of 1.70 eV, in agreement with the experimentally detected 1.80 ± 0.15 eV. That the computed CO desorption energy (1.55 eV) is smaller than CO oxidation barrier is in agreement with the experimental finding. The computed desorption temperatures of H 2 O, CO and CO 2 under ultrahigh vacuum conditions agree perfectly with the experiments. In addition, high oxygen and OH pre-coverage do not significantly affect the energetics of the dissociation of H 2 O and CO 2 . The excellent agreement between theory and experiment confirms the applied models and methods, and in turn, gives the reliability and confidence about the further predicted results. [ABSTRACT FROM AUTHOR]

The mechanisms of CO hydrogenation with the formation of C 1 surface species on the clean and K 2 O-doped χ-Fe 5 C 2 (111) surfaces with carbon vacancies have been comparatively elucidated. On both surfaces, CO direct dissociation (CO → C + O) is not favored. On the clean surface, the preferred H-assisted pathway is CO → HCO → CH 2 O → CH 3 O → CH 3 OH. On the K 2 O-doped surface, the preferred paths are HCO → CHOH → CH + OH and HCO → CH 2 O → CH 2 OH → CH 2 + OH due to the barrier decrease of the C O bond cleavage of COH, CHOH and CH 2 OH by K 2 O promotion. These results might explain the K 2 O promoted carburization process and the formation of long-chain hydrocarbons. [ABSTRACT FROM AUTHOR]

The effect of Cu promoter on CH 4 formation from CO hydrogenation on Fe(100) has been investigated using spin-polarized density functional theory computations on periodic slab models. Two pathways of CH 4 formation are considered: (a) direct dissociation of CO followed by successive C hydrogenation and (b) successive hydrogenation of CO followed by deoxygenation of CH x O (x = 1–3). On the clean and Cu doped surfaces, direct dissociation of CO followed by successive C hydrogenation is more favorable kinetically and the overall CH 4 formation is endothermic. Compared with the clean surface, the Cu doped surface can suppress CH 4 formation by raising the barrier from the co-adsorbed CO + 4H. Methanol formation is unfavorable on both surfaces kinetically and thermodynamically. Reversely, methanol decomposition is favorable. It is also noted that Cu doping lowers the adsorption ability of the Fe(100) surface and therefore the adsorption energies of all species on the potential energy surfaces. [ABSTRACT FROM AUTHOR]

High coverage hydrogen adsorption on twenty two terminations of orthorhombic Mo2C has been systematically studied by using density functional theory and ab initio thermodynamics. Hydrogen stable coverage on the surfaces highly depends on temperatures and H2 partial pressure. The estimated hydrogen desorption temperatures under ultra-high vacuum condition on Mo2C are in reasonable agreement with the available temperature-programmed desorption data. Obviously, hydrogen adsorption can affect the surface stability and therefore modify the surface morphology of Mo2C. Upon increasing the chemical potential of hydrogen which can be achieved by increasing the H2 partial pressure and/or decreasing the temperature, the proportions of the (001), (010), (011) and (100) surfaces increase, while those of the (101), (110) and (111) surfaces decrease. Among these surfaces, the (100) surface is most sensitive upon hydrogen adsorption and the (111) surface is most exposed under a wide range of conditions. Our study clearly reveals the role of hydrogen on the morphology of orthorhombic Mo2C catalyst in conjugation with hydro-treating activity. Graphical abstractImage 1Highlights· Coverage dependent H2 adsorption on Mo2C surfaces is systematically calculated. · Hydrogen adsorption is essential in forming active Mo2C catalyst. · (111) is the most exposed Mo2C surface and (100) is the most sensitive to condition. · Hydrogen desorption temperatures on Mo2C can be reasonably predicted. [ABSTRACT FROM AUTHOR]

[Display omitted] • CO 2 Conversion to CH 4 and CH 3 OH on ZrO 2 support Ni catalysis was computed. • Metal-Metal and Metal-support Interaction was analysed. • Reaction Mechanisms, differently from metallic Ni, were identified. • Metal interaction determines structure of support Ni and reaction mechanisms. To better understand the metal-support interaction and structure–activity relationship, we computed the mechanisms of CO 2 hydrogenation to CH 4 and CH 3 OH on ZrO 2 supported Ni catalyst. On a supported irregular Ni 13 cluster, which exhibits a balanced metal–metal and metal-support interaction with surface Zr and O atoms covered, two preferred routes [CO 2 → CO → CHO → CH/CH 3 O → CH 3 → CH 4 /CH 3 OH] are found, and the rate-determining step is the CO 2 direct dissociation. Such mechanisms differ very strongly from those reported on flat metallic Ni(1 1 1) surface and Ni clusters supported on different metal oxides, demonstrating that different supports generate different metal-support interaction that simultaneously changes the metal structures and the reaction mechanisms. [ABSTRACT FROM AUTHOR]

In petrochemical industry, zeolites as solid acid catalysts play an important role and Y zeolites with high surface area and large pore openings are mainly used for catalytic cracking. Aiming at the problem that the specific positions of Al atoms in zeolites cannot be accurately distinguished experimentally and the acid strength can only be studied qualitatively, we used computational model and method to study the position of Al substitution and the resulted acid strength of Y zeolite at atomic and molecular level. The position of Al substitution with gradually decreasing Si/Al ratio (Si/Al = 47–2.4) and the corresponding Brønsted acid strength of the resulting multiple acid sites of HY zeolites are systematically investigated based on periodic DFT calculation including dispersion correction (GGA-PBE-D3). The thermodynamically more stable structures prefer Al distribution having the next-nearest neighbor of aluminum atom pairs (Al–O–Si–O–Al), and based on these stable configurations, the adsorption of ammonia (NH 3) and pyridine (C 5 H 5 N) has been computed to estimate the Brønsted acid strength. It is found that the adsorption of NH 3 and C 5 H 5 N prefers the formation of ammonium (NH 4 +) and pyridinium (C 5 H 5 NH+) ions at each acid sites and the adsorption enthalpy does not correlate with the Bader charge of the acid proton. Most importantly, the adsorption enthalpy decreases with the decrease of Si/Al ratio, indicating that the more the Al substitution the weaker the Brønsted acid strength. It is noted that the adsorption enthalpy of all individual acid sites at a given Si/Al ratio can differ strongly, despite the formation of NH 4 + and C 5 H 5 NH + ions, indicating their mutual interaction and local confinement effect. The calculated adsorption enthalpies agree fully with the experimentally measured results (Si/Al = 8.6–2.4). Hyroxyl nest, defect sites formed from dealumination, has much weaker acid strength than the Brønsted acid sites. Our results provide a rational basis for further studies on the enhanced catalytic activity of HY zeolites with different Si/Al ratios. [Display omitted] • Structure and stability of Y-Zeolite with multiple Al substitution were computed using DFT. • The stability of Al distribution prefers the next-nearest neighbor of aluminum atom pairs. • The acid strength was computed based on the adsorption enthalpy of ammonia (NH 4 +) and pyridine (C 5 H 5 NH+). • The adsorption enthalpy decreases with the decrease of Si/Al ratio. • The more the Al substitution the weaker the Brønsted acid strength. [ABSTRACT FROM AUTHOR]

Spin-polarized density functional theory computations have been performed to investigate n CO + m H 2 co-adsorption and mutual interaction on the Fe(1 1 0) and Fe(1 1 1) surfaces. It is found that CO pre-coverage affects hydrogen adsorption strongly, while H pre-coverage hardly affects CO adsorption. It is possible to have CO + H 2 co-adsorption on Fe(1 1 0), while very strong preference of CO pre-coverage on Fe(1 1 1) has been found. On Fe(1 1 1), it is also found that each CO molecule blocks on average 2H adsorption sites at all CO pre-coverage. All these findings are consistent with available experimental results. Compared with CO/H 2 ratios in gas phase, CO/H 2 surface ratios are very different and much more sensitive to temperature than pressure. Our results provide the basis for exploring the mechanisms of iron-catalyzed conversion of synthesis gas. [ABSTRACT FROM AUTHOR]

The structure and stability of seventeen facets of the Hägg carbide phase (χ-Fe 5 C 2 ) under the consideration of K 2 O promotion have been analyzed utilizing density functional theory approach and ab initio atomistic thermodynamics. On the basis of different interaction strengths of these facets with K 2 O promoter, the morphology of the χ-Fe 5 C 2 phase under the variation of K 2 O content has been predicated. At the surface Fe/K atomic ratio of 30, the morphology of the χ-Fe 5 C 2 phase can be modified apparently. Among the most exposed (1 1 1), (1 0 0), ( 1   1   1 ¯ ), (5 1 0) and ( 4 ¯   1   1 ) facets, the ( 1   1   1 ¯ ), (5 1 0) and ( 4 ¯   1   1 ) facets have more open surface structures as well as provide more surface Fe atoms and less carbon atoms. However, all these mostly exposed facets do not favor CO direct dissociation at low CO coverage. [ABSTRACT FROM AUTHOR]

• Coverage dependent hydrogen adsorption on Ir(111), Ir(100) and Ir(110) surfaces. • Change of adsorption site on Ir(100) from low to high coverage. • Surface dependent repulsive interaction on Ir(111). • Surface dependent attractive interaction on Ir(100) and Ir(110). • Regular line-shaped adsorption structures were found on Ir(100) and Ir(110). Hydrogen adsorption on the perfect Ir(111) as well as the metastable and unreconstructed Ir(100) and Ir(110) surfaces up to saturation coverage has been systematically computed using periodic density functional theory and ab initio atomistic thermodynamics for understanding the interaction mechanism of hydrogen on iridium surfaces. On the Ir(111) surface including van der Waals dispersion, hydrogen adsorption prefers the threefold hollow sites at low coverage and the top sites at high coverage; in agreement with the experiments (Phys. Rev. B 60 (1999) 14016). The computed adsorption energy and desorption temperature of hydrogen agree with the experiments [−0.57 (fcc-3H) and −0.53 (hcp-3H) vs. −0.55 eV; 180 and 325 K vs. 190 and 310 K, respectively]. On the Ir (100) surface, the bridge adsorption sites are preferred in the whole coverage range, in agreement with the LEED pattern (Phys. Rev. B 73 (2006) 75430), however, adsorption energy and desorption temperature are slightly overestimated by including van der Waals dispersion (−1.50 vs. −1.02 ± 0.15 eV; 470 vs. 425 – 389 K). On the Ir(110) surface, short-bridge sites are preferred at low coverage and the top sites become dominant at high coverage, and the calculated desorption temperatures are close to experiments by including van der Waals dispersion (210 and 365 K vs. 220 and 375 K). At low coverage, the different configurations of hydrogen adsorption on the Ir(111) have the similar energies, indicating their negligible repulsive interaction, while the Ir(100) and Ir(110) surfaces prefer regular line-shape adsorption configurations due to attractive interaction, and such adsorption configurations have not been observed experimentally. Our results show that differences in adsorption configurations and energies are associated with their differences in surface structures, and in turn explain the need of different methods in computing the adsorption properties on different surfaces. Such surface-dependent properties should also be possible on other metal surfaces. Image, graphical abstract [ABSTRACT FROM AUTHOR]