Single-Atom Molybdenum-N3 Sites for Selective Hydrogenation of CO2 to CO.

The design of efficient non-noble metal catalysts for CO2 hydrogenation to fuels and chemicals is desired yet remains a challenge. Herein, we report that single Mo atoms with a MoN3 (pyrrolic) moiety enable remarkable CO2 adsorption and hydrogenation to CO, as predicted by density functional theory studies and evidenced by a high and stable conversion of CO2 reaching about 30.4 % with a CO selectivity of almost 100 % at 500 °C and very low H2 partial pressure. Atomically dispersed MoN3 is calculated to facilitate CO2 activation and reduces CO2 to CO* via the direct dissociation path. Furthermore, the highest transition state energy in CO formation is 0.82 eV, which is substantially lower than that of CH4 formation (2.16 eV) and accounts for the dominant yield of CO. The enhanced catalytic performances of Mo/NC originate from facile CO desorption with the help of dispersed Mo on nitrogen-doped carbon (Mo/NC), and in the absence of Mo nanoparticles. The resulting catalyst preserves good stability without degradation of CO2 conversion rate even after 68 hours of continuous reaction. This finding provides a promising route for the construction of highly active, selective, and robust single-atom non-precious metal catalysts for reverse water-gas shift reaction.

Autobifunctional Mechanism of Jagged Pt Nanowires for Hydrogen Evolution Kinetics via End-to-End Simulation.

The extraordinary mass activity of jagged Pt nanowires can substantially improve the economics of the hydrogen evolution reaction (HER). However, it is a great challenge to fully unveil the HER kinetics driven by the jagged Pt nanowires with their multiscale morphology. Herein we present an end-to-end framework that combines experiment, machine learning, and multiscale advances of the past decade to elucidate the HER kinetics catalyzed by jagged Pt nanowires under alkaline conditions. The bifunctional catalysis conventionally refers to the synergistic increase in activity by the combination of two different catalysts. We report that monometals, such as jagged Pt nanowires, can exhibit bifunctional characteristics owing to its complex surface morphology, where one site prefers electrochemical proton adsorption and another is responsible for activation, resulting in a 4-fold increase in the activity. We find that the conventional design guideline that the sites with a 0 eV Gibbs free energy of adsorption are optimal for HER does not hold under alkaline conditions, and rather, an energy between -0.2 and 0.0 eV is shown to be optimal. At the reaction temperatures, the high activity arises from low-coordination-number (≤7) Pt atoms exposed by the jagged surface. Our current demonstration raises an emerging prospect to understand highly complex kinetic phenomena on the nanoscale in full by implementing end-to-end multiscale strategies.

Ti(N5)4 as a Potential Nitrogen-Rich Stable High-Energy Density Material.

We have studied molecular structures and kinetic stabilities of M(N5)3 (M = Sc, Y) and M(N5)4 (M = Ti, Zr, Hf) complexes theoretically. All of these compounds are found to be stable with more than a 13 kcal/mol of kinetic barrier. In particular, Ti(N5)4 showed the largest dissociation energy of 173.0 kcal/mol and thermodynamic stability. This complex had a high nitrogen content (85% by weight), and a significantly high nitrogen to metal ratio (20:1) among the neutral M(N5)n species studied here and in the literature. Ti(N5)4 is thus forecasted to be a good candidate for a nitrogen-rich high-energy density material (HEDM). We reveal in further detail using ab initio molecular dynamics simulations that the dissociation pathways of M(N5)n involve the rearrangements of the bonding configurations before dissociation.

Atomic-Scale Homogeneous RuCu Alloy Nanoparticles for Highly Efficient Electrocatalytic Nitrogen Reduction.

Ruthenium (Ru) is the most widely used metal as an electrocatalyst for nitrogen (N2 ) reduction reaction (NRR) because of the relatively high N2 adsorption strength for successive reaction. Recently, it has been well reported that the homogeneous Ru-based metal alloys such as RuRh, RuPt, and RuCo significantly enhance the selectivity and formation rate of ammonia (NH3 ). However, the metal combinations for NRR have been limited to several miscible combinations of metals with Ru, although various immiscible combinations have immense potential to show high NRR performance. In this study, an immiscible combination of Ru and copper (Cu) is first utilized, and homogeneous alloy nanoparticles (RuCu NPs) are fabricated by the carbothermal shock method. The RuCu homogeneous NP alloys on cellulose/carbon nanotube sponge exhibit the highest selectivity and NH3 formation rate of ≈31% and -73 µmol h-1 cm-2 , respectively. These are the highest values of the selectivity and NH3 formation rates among existing Ru-based alloy metal combinations.

Engineering vacancy and hydrophobicity of two-dimensional TaTe2 for efficient and stable electrocatalytic N2 reduction.

Demand for ammonia continues to increase to sustain the growing global population. The direct electrochemical N2 reduction reaction (NRR) powered by renewable electricity offers a promising carbon-neutral and sustainable strategy for manufacturing NH3, yet achieving this remains a grand challenge. Here, we report a synergistic strategy to promote ambient NRR for ammonia production by tuning the Te vacancies (VTe) and surface hydrophobicity of two-dimensional TaTe2 nanosheets. Remarkable NH3 faradic efficiency of up to 32.2% is attained at a mild overpotential, which is largely maintained even after 100 h of consecutive electrolysis. Isotopic labeling validates that the N atoms of formed NH4 + originate from N2. In situ X-ray diffraction indicates preservation of the crystalline structure of TaTe2 during NRR. Further density functional theory calculations reveal that the potential-determining step (PDS) is ∗NH2 + (H+ + e-) → NH3 on VTe-TaTe2 compared with that of ∗ + N2 + (H+ + e-) → ∗N-NH on TaTe2. We identify that the edge plane of TaTe2 and VTe serve as the main active sites for NRR. The free energy change at PDS on VTe-TaTe2 is comparable with the values at the top of the NRR volcano plots on various transition metal surfaces.

Shifting the scaling relations of single-atom catalysts for facile methane activation by tuning the coordination number.

We investigate oxidative methane activation on a wide range of single transition metal atom catalysts embedded on N-doped graphene derivatives using density functional theory calculations. An inverse scaling relationship between *O formation and its hydrogen affinity is observed, consistent with a previous report. However, we find that the latter scaling line can be shifted towards a more reactive region by tuning the coordination number (CN) of the active metal sites. Specifically, we find that lowering the CN plays an important role in increasing the reactivity for methane activation via a radical-like transition state by moving the scaling lines. Thus, in the new design strategy suggested here, different from the conventional efforts focusing mainly on breaking the scaling relations, one maintains the scaling relations but moves them towards more reactive regions by controlling the coordination number of the active sites. With this design principle, we suggest several single atom catalysts with lower C-H activation barriers than some of the most active methane activation catalysts in the literature such as Cu-based zeolites.

Understanding potential-dependent competition between electrocatalytic dinitrogen and proton reduction reactions.

A key challenge to realizing practical electrochemical N2 reduction reaction (NRR) is the decrease in the NRR activity before reaching the mass-transfer limit as overpotential increases. While the hydrogen evolution reaction (HER) has been suggested to be responsible for this phenomenon, the mechanistic origin has not been clearly explained. Herein, we investigate the potential-dependent competition between NRR and HER using the constant electrode potential model and microkinetic modeling. We find that the H coverage and N2 coverage crossover leads to the premature decrease of NRR activity. The coverage crossover originates from the larger charge transfer in H+ adsorption than N2 adsorption. The larger charge transfer in H+ adsorption, which potentially leads to the coverage crossover, is a general phenomenon seen in various heterogeneous catalysts, posing a fundamental challenge to realize practical electrochemical NRR. We suggest several strategies to overcome the challenge based on the present understandings.

Progress in Computational and Machine-Learning Methods for Heterogeneous Small-Molecule Activation.

The chemical conversion of small molecules such as H2 , H2 O, O2 , N2 , CO2 , and CH4 to energy and chemicals is critical for a sustainable energy future. However, the high chemical stability of these molecules poses grand challenges to the practical implementation of these processes. In this regard, computational approaches such as density functional theory, microkinetic modeling, data science, and machine learning have guided the rational design of catalysts by elucidating mechanistic insights, identifying active sites, and predicting catalytic activity. Here, the theory and methodologies for heterogeneous catalysis and their applications for small-molecule activation are reviewed. An overview of fundamental theory and key computational methods for designing catalysts, including the emerging data science techniques in particular, is given. Applications of these methods for finding efficient heterogeneous catalysts for the activation of the aforementioned small molecules are then surveyed. Finally, promising directions of the computational catalysis field for further outlooks are discussed, focusing on the challenges and opportunities for new methods.

Single yttrium sites on carbon-coated TiO2 for efficient electrocatalytic N2 reduction.

We report single yttrium sites anchored on carbon-coated TiO2 for efficient and stable electrocatalytic N2 fixation, delivering an NH3 faradaic efficiency exceeding 11.0% and an NH3 yield rate as high as 6.3 µgNH3 h-1 mgcat.-1 at low overpotentials, thus surpassing many reported metal electrocatalysts.

Interaction Mediator Assisted Synthesis of Mesoporous Molybdenum Carbide: Mo-Valence State Adjustment for Optimizing Hydrogen Evolution.

To overcome inherent limitations of molybdenum carbide (MoxC) for hydrogen evolution reaction (HER), i.e., low density of active site and nonideal hydrogen binding strength, we report the synthesis of valence-controlled mesoporous MoxC as a highly efficient HER electrocatalyst. The synthesis procedure uses an interaction mediator (IM), which significantly increases the density of active site by mediating interaction between PEO-b-PS template and Mo source. The valence state of Mo is tuned by systematic control of the environment around Mo by controlled heat treatment under air before thermal treatment at 1100 °C. Theoretical calculations reveal that the hydrogen binding is strongly influenced by Mo valence. Consequently, MoxC achieves a significant increase in HER activity (exceeding that of Pt/C at high current density ∼35 mA/cm2 in alkaline solution). In addition, a volcano-type correlation between HER activity and Mo valence is identified with various experimental indicators. The present strategies can be applied to various carbide and Mo-based catalysts, and the established Mo valence and HER relations can guide development of highly active HER electrocatalysts.

High-yield production of few-layer boron nanosheets for efficient electrocatalytic N2 reduction.

We report ambient electrochemical N2 fixation at low overpotentials by using two-dimensional (2D) ß-boron. The metal-free catalyst afforded both an excellent NH3 yield rate and faradaic efficiency, approximately two times higher than those of bulk boron. We found that several binding sites, especially those involving icosahedral boron in the 2D material, can indeed catalyze N2 reduction efficiently with strong N2 adsorption, thus benefiting initial activation.

Efficient visible-light driven N2 fixation over two-dimensional Sb/TiO2 composites.

Photochemical ammonia production under ambient conditions remains a grand challenge. Here we demonstrate efficient visible-light fixation of N2 to NH3 in water using novel two-dimensional (2D) Sb/TiO2 nanocomposites. Such hybrids afford a remarkable NH3 formation rate of about 20.8 µmol h-1 gcat.-1, showing promise as photochemical materials for sustainable NH3 production.

Carbon-supported Ni nanoparticles for efficient CO2 electroreduction.

The development of highly selective, low cost, and energy-efficient electrocatalysts is crucial for CO2 electrocatalysis to mitigate energy shortages and to lower the global carbon footprint. Herein, we first report that carbon-coated Ni nanoparticles supported on N-doped carbon enable efficient electroreduction of CO2 to CO. In contrast to most previously reported Ni metal catalysts that resulted in severe hydrogen evolution during CO2 conversion, the Ni particle catalyst here presents an unprecedented CO faradaic efficiency of approximately 94% at an overpotential of 0.59 V, even comparable to that of the best single Ni sites. The catalyst also affords a high CO partial current density and a large CO turnover frequency, reaching 22.7 mA cm-2 and 697 h-1 at -1.1 V (versus the reversible hydrogen electrode), respectively. Experiments combined with density functional theory calculations showed that the carbon layer coated on Ni and N-dopants in carbon material both play important roles in improving catalytic activity for electrochemical CO2 reduction to CO by stabilizing *COOH without affecting the easy *CO desorption ability of the catalyst.

Studies on Catalytic Activity of Hydrogen Peroxide Generation according to Au Shell Thickness of Pd/Au Nanocubes.

The catalytic properties of materials are determined by their electronic structures, which are based on the arrangement of atoms. Using precise calculations, synthesis, analysis, and catalytic activity studies, we demonstrate that changing the lattice constant of a material can modify its electronic structure and therefore its catalytic activity. Pd/Au core/shell nanocubes with a thin Au shell thickness of 1 nm exhibit high H2O2 production rates due to their improved oxygen binding energy (Δ EO) and hydrogen binding energy (Δ EH), as well as their reduced activation barriers for key reactions.