Highly stable Mo-doped Fe2P and Fe3P monolayers as low-onset-potential electrocatalysts for nitrogen fixation
02 Mar 2021-Catalysis Science & Technology (The Royal Society of Chemistry)-Vol. 11, Iss: 4, pp 1419-1429
TL;DR: In this paper, the authors investigated nitrogen reduction reaction (NRR) pathways occurring on iron-based phosphide monolayers and found that Mo-doped Fe2P and Fe3P can efficiently promote the NRR with onset potentials of − 0.30 V and −0.17 V, respectively.
About: This article is published in Catalysis Science & Technology.The article was published on 2021-03-02. It has received 26 citations till now.
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TL;DR: In this article, a conductor-like screening model was proposed to screen out eligible NRR electrocatalysts from 29 atomic transition metals embedded on the defective boron phosphide (BP) monolayer with B-monovacancy (M/BP single-atom catalysts, SAC, M = Sc-Zn, Y-Cd, and Hf-Hg).
Abstract: Conversion of dinitrogen (N2) molecules into ammonia through electrochemical methods is a promising alternative to the traditional Haber-Bosch process. However, searching for an eligible electrocatalyst with high stability, low-onset potential, and superior selectivity is still one of the most challenging and attractive topics for the electrochemical N2 reduction reaction (NRR). Here, by means of first-principles calculations and the conductor-like screening model, four comprehensive criteria were proposed to screen out eligible NRR electrocatalysts from 29 atomic transition metals embedded on the defective boron phosphide (BP) monolayer with B-monovacancy (M/BP single-atom catalysts, SAC, M = Sc-Zn, Y-Cd, and Hf-Hg). Consequently, the Nb/BP and W/BP SACs are identified as the promising candidates, on which the N2 molecule can only be activated through the enzymatic pathway with the onset potentials of -0.25 and -0.19 V, and selectivities of 90.5 and 100%, respectively. It is worth noting that the W/BP SAC has the lowest overpotential among the 29 systems investigated. The electronic properties were also calculated in detail to analyze the activity origin. Importantly, the Nb/BP and W/BP SACs possess high thermal stabilities due to that their structures can be retained very well up to 1000 and 700 K, respectively. This work not only provides an efficient and reliable method to screen eligible NRR electrocatalysts but also paves a new way for advancing sustainable ammonia synthesis.
55 citations
TL;DR: In this paper, a series of transition-metal-doped hexagonal boron phosphide (h-BP) monolayers were comprehensively evaluated using density functional theory, and it was shown that the Vdoped h-BP monolayer stands near the top of the volcano plot with the limiting potential of -0.22 V versus a reversible hydrogen electrode, exhibiting the lowest overpotential among the investigated systems.
Abstract: Electrocatalytic conversion of nitrate (NO3-) into ammonia can not only eliminate harmful pollutant but also provide a green method for a low-temperature ammonia synthesis. The electrochemical NO3- reduction reactions (NO3RRs) of a series of transition-metal-doped hexagonal boron phosphide (h-BP) monolayers were comprehensively evaluated using density functional theory. The V-doped h-BP monolayer was found to stand near the top of the volcano plot with the limiting potential of -0.22 V versus a reversible hydrogen electrode, exhibiting the lowest overpotential among the investigated systems in this work. Besides, the competing hydrogen evolution reaction is significantly suppressed due to the weak adsorption of the H atom. Importantly, the structure of the V-doped h-BP monolayer can be retained very well until 900 K, illustrating the initial indication of high thermal stability and great promise for synthesis. This study not only offers an eligible NO3RR electrocatalyst but also provides an atomic understanding of the behind mechanisms of the NO3RR process.
44 citations
21 citations
TL;DR: In this paper , a review of the recent progress and contributions of computational studies in understanding the reaction mechanism and rational catalyst design for electrochemical nitrogen reduction reaction (eNRR) under mild reaction conditions is presented.
Abstract: Large-scale ammonia synthesis via the electrochemical nitrogen reduction reaction (eNRR) under mild reaction conditions represents a green prospect for agriculture, industry, and energy. This bioinspired and carbon-free reaction has been proposed as an ideal alternative to the Haber–Bosch process. However, the yield and selectivity of the current eNRR have not met the requirements for industrialization. Mechanistic understanding and catalysts’ design are still long-term pursuits in this field, where theoretical simulations will have significant contributions. In this Review, we will start with the natural N2 fixation enzymes, the nitrogenases, followed by a summary of the key experimental eNRR performances on hundreds of recently reported catalysts, and we analyze the general trend and challenges before eNRR can significantly impact the ammonia industry. Then, we will systematically review the recent progress and contributions of computational studies in understanding the reaction mechanism and rational catalyst design for eNRR. The fundamental principles, reaction mechanisms, crucial theoretical criteria, modeling methods, and computationally predicted catalysts for eNRR are systematically summarized and discussed. Finally, we outline the current challenges and future opportunities for experimental and computational studies of electrochemical N2 reduction.
16 citations
TL;DR: In this article, a nitrogen reduction reaction (NRR) which converts nitrogen (N2) to ammonia (NH3) normally requires harsh conditions to break the bound nitrogen bond.
Abstract: A nitrogen reduction reaction (NRR) which converts nitrogen (N2) to ammonia (NH3) normally requires harsh conditions to break the bound nitrogen bond. Herein, via first-principles calculation it is revealed that a superior NRR catalytic activity could be obtained by anchoring an atomic catalyst above the phosphorene-like puckered surface of germanium selenide (GeSe). By examining the single- and double-atoms (B, Fe, Mo Ru and W) decorated on GeSe, it is found that its rippled structure allows an intimate contact between the deposited species and the GeSe which significantly promotes the states hybridization. Out of all the various atomic catalysts, it is found that the Ru dimer decorated GeSe monolayer (Ru2@GeSe) has superior catalytic activity for the N2 fixation and reduction. By examining the three NRR pathways (distal, alternating and enzymatic), it was found that the distal and enzymatic pathways are both thermodynamically favorable with the maximum Gibbs free energy change (ΔGMAX) of 0.25 and 0.26 eV, respectively. Such a superior activity could be attributed to the Ru dimer filtering the states of GeSe which leads to the effective activation of the adsorbed N2 bond. As an efficient near-infrared absorber of GeSe, the Ru mediated hybridization of the GeSe–Ru–N2 complex enables an in-gap state which further broadens the absorption window, rendering for a broadband solar absorption and possible photocatalysis.
14 citations
References
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TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.
Abstract: Generalized gradient approximations (GGA’s) for the exchange-correlation energy improve upon the local spin density (LSD) description of atoms, molecules, and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental constants. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential. [S0031-9007(96)01479-2] PACS numbers: 71.15.Mb, 71.45.Gm Kohn-Sham density functional theory [1,2] is widely used for self-consistent-field electronic structure calculations of the ground-state properties of atoms, molecules, and solids. In this theory, only the exchange-correlation energy EXC › EX 1 EC as a functional of the electron spin densities n"srd and n#srd must be approximated. The most popular functionals have a form appropriate for slowly varying densities: the local spin density (LSD) approximation Z d 3 rn e unif
146,533 citations
TL;DR: A new density functional of the generalized gradient approximation (GGA) type for general chemistry applications termed B97‐D is proposed, based on Becke's power‐series ansatz from 1997, and is explicitly parameterized by including damped atom‐pairwise dispersion corrections of the form C6 · R−6.
Abstract: A new density functional (DF) of the generalized gradient approximation (GGA) type for general chemistry applications termed B97-D is proposed. It is based on Becke's power-series ansatz from 1997 and is explicitly parameterized by including damped atom-pairwise dispersion corrections of the form C(6) x R(-6). A general computational scheme for the parameters used in this correction has been established and parameters for elements up to xenon and a scaling factor for the dispersion part for several common density functionals (BLYP, PBE, TPSS, B3LYP) are reported. The new functional is tested in comparison with other GGAs and the B3LYP hybrid functional on standard thermochemical benchmark sets, for 40 noncovalently bound complexes, including large stacked aromatic molecules and group II element clusters, and for the computation of molecular geometries. Further cross-validation tests were performed for organometallic reactions and other difficult problems for standard functionals. In summary, it is found that B97-D belongs to one of the most accurate general purpose GGAs, reaching, for example for the G97/2 set of heat of formations, a mean absolute deviation of only 3.8 kcal mol(-1). The performance for noncovalently bound systems including many pure van der Waals complexes is exceptionally good, reaching on the average CCSD(T) accuracy. The basic strategy in the development to restrict the density functional description to shorter electron correlation lengths scales and to describe situations with medium to large interatomic distances by damped C(6) x R(-6) terms seems to be very successful, as demonstrated for some notoriously difficult reactions. As an example, for the isomerization of larger branched to linear alkanes, B97-D is the only DF available that yields the right sign for the energy difference. From a practical point of view, the new functional seems to be quite robust and it is thus suggested as an efficient and accurate quantum chemical method for large systems where dispersion forces are of general importance.
23,058 citations
TL;DR: In this paper, the DMol3 local orbital density functional method for band structure calculations of insulating and metallic solids is described and the method for calculating semilocal pseudopotential matrix elements and basis functions are detailed together with other unpublished parts of the methodology pertaining to gradient functionals and local orbital basis sets.
Abstract: Recent extensions of the DMol3 local orbital density functional method for band structure calculations of insulating and metallic solids are described. Furthermore the method for calculating semilocal pseudopotential matrix elements and basis functions are detailed together with other unpublished parts of the methodology pertaining to gradient functionals and local orbital basis sets. The method is applied to calculations of the enthalpy of formation of a set of molecules and solids. We find that the present numerical localized basis sets yield improved results as compared to previous results for the same functionals. Enthalpies for the formation of H, N, O, F, Cl, and C, Si, S atoms from the thermodynamic reference states are calculated at the same level of theory. It is found that the performance in predicting molecular enthalpies of formation is markedly improved for the Perdew–Burke–Ernzerhof [Phys. Rev. Lett. 77, 3865 (1996)] functional.
8,496 citations
TL;DR: In this paper, an algorithm for the accurate calculation of dielectric screening effects in solvents is presented, which leads to rather simple expressions for the screening energy and its analytic gradient with respect to the solute coordinates.
Abstract: Starting from the screening in conductors, an algorithm for the accurate calculation of dielectric screening effects in solvents is presented, which leads to rather simple explicit expressions for the screening energy and its analytic gradient with respect to the solute coordinates. Thus geometry optimization of a solute within a realistic dielectric continuum model becomes practicable for the first time. The algorithm is suited for molecular mechanics as well as for any molecular orbital algorithm. The implementation into MOPAC and some example applications are reported.
7,865 citations
TL;DR: In this paper, the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations was analyzed and a detailed description of the free energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias was presented.
Abstract: We present a method for calculating the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations. We used that method in combination with detailed density functional calculations to develop a detailed description of the free-energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias. This allowed us to identify the origin of the overpotential found for this reaction. Adsorbed oxygen and hydroxyl are found to be very stable intermediates at potentials close to equilibrium, and the calculated rate constant for the activated proton/electron transfer to adsorbed oxygen or hydroxyl can account quantitatively for the observed kinetics. On the basis of a database of calculated oxygen and hydroxyl adsorption energies, the trends in the oxygen reduction rate for a large number of different transition and noble metals can be accounted for. Alternative reaction mechanisms involving proton/electron transfer to ...
7,711 citations