Browse
Submit Data
Databases
API
Help

Dataset Information

45 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Catalytic Potential of Post-Transition Metal Doped Graphene-Based Single-Atom Catalysts for the CO₂ Electroreduction Reaction.

ABSTRACT: Catalysts are required to ensure electrochemical reduction of CO₂ to fuels proceeds at industrially acceptable rates and yields. As such, highly active and selective catalysts must be developed. Herein, a density functional theory study of p-block element and noble metal doped graphene-based single-atom catalysts in two defect sites for the electrochemical reduction of CO₂ to CO and HCOOH is systematically undertaken. It is found that on all of the systems considered, the thermodynamic product is HCOOH. Pb/C₃ , Pb/N₄ and Sn/C₃ are identified as having the lowest overpotential for HCOOH production while Al/C₃ , Al/N₄ , Au/C₃ and Ga/C₃ are identified as having the potential to form higher order products due to the strength of binding of adsorbed HCOOH.

SUBMITTER: Lambie S

PROVIDER: S-EPMC9315035 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Catalytic Potential of Post-Transition Metal Doped Graphene-Based Single-Atom Catalysts for the CO2 Electroreduction Reaction.

Lambie Stephanie S Low Jian Liang JL Gaston Nicola N Paulus Beate B

Chemphyschem : a European journal of chemical physics and physical chemistry 20220323 8

Catalysts are required to ensure electrochemical reduction of CO2 to fuels proceeds at industrially acceptable rates and yields. As such, highly active and selective catalysts must be developed. Herein, a density functional theory study of p-block element and noble metal doped graphene-based single-atom catalysts in two defect sites for the electrochemical reduction of CO2 to CO and HCOOH is systematically undertaken. It is found that on all of the systems considered, the t ...[more]

PMID: 35224844

Similar Datasets

Transition Metal-Doped C20 Fullerene-Based Single-Atom Catalysts with High Catalytic Activity for Hydrogen Dissociation Reaction.

Project description:Hydrogen dissociation is a key step in almost all hydrogenation reactions; therefore, an efficient and cost-effective catalyst with a favorable band structure for this step is highly desirable. In the current work, transition metal-based C20 (M@C20) complexes are designed and evaluated as single-atom catalysts (SACs) for hydrogen dissociation reaction (HDR). Interaction energy (E int) analysis reveals that all the M@C20 complexes are thermodynamically stable, whereas the highest stability is observed for the Ni@C20 complex (E int = -6.14 eV). Moreover, the best catalytic performance for H2 dissociation reaction is computed for the Zn@C20 catalyst (E ads = 0.53 eV) followed by Ti@C20 (E ads = 0.65 eV) and Sc@C20 (E ads = 0.76 eV) among all considered catalysts. QTAIM analyses reveal covalent or shared shell interactions in H2* + M@C20 systems, which promote the process of H2 dissociation over M@C20 complexes. NBO and EDD analyses declare that transfer of charge from the metal atom to the antibonding orbital of H2 causes dissociation of the H-H bond. Overall outcomes of this study reveal that the Zn@C20 catalyst can act as a highly efficient, low-cost, abundant, and precious metal-free SAC to effectively catalyze HDR.

| S-EPMC10116631 | biostudies-literature

Understanding the catalytic performances of metal-doped Ta2O5 catalysts for acidic oxygen evolution reaction with computations.

Project description:The design of stable and active alternative catalysts to iridium oxide for the anodic oxygen evolution reaction (OER) has been a long pursuit in acidic water splitting. Tantalum pentoxide (Ta2O5) has the merit of great acidic stability but poor OER performance, yet strategies to improve its intrinsic OER activity are highly desirable. Herein, by using density functional theory (DFT) calculations combined with aqueous stability assessment from surface Pourbaix diagrams, we systematically evaluated the OER activity and acidic stability of 14 different metal-doped Ta2O5 catalysts. Apart from the experimentally reported Ir-doped Ta2O5, we computationally identified Ru- and Nb-doped Ta2O5 catalysts as another two candidates with reasonably high stability and activity in acidic OER. Our study also underscores the essence of considering stable surface states of catalysts under working conditions before a reasonable activity trend can be computationally achieved.

| S-EPMC11331345 | biostudies-literature

Rational Design of Novel Single-Atom Catalysts of Transition-Metal-Doped 2D AlN Monolayer as Highly Effective Electrocatalysts for Nitrogen Reduction Reaction.

Project description:The single-atom catalysts (SACs) for the electrocatalytic nitrogen reduction reaction (NRR) have garnered significant attention in recent years. The NRR is regarded as a milder and greener approach to ammonia synthesis. The pursuit of highly efficient and selective electrocatalysts for the NRR continues to garner substantial interest, yet it poses a significant challenge. In this study, we employed density functional theory calculations to investigate the stability and catalytic activity of 29 transition metal atoms loaded on the two-dimensional (2D) AlN monolayer with Al monovacancy (TM@AlN) for the conversion of N2 to NH3. After screening the activity and selectivity of NRR, it was found that Os@AlN exhibited the highest activity for NRR with a very low limiting potential of -0.46 V along the distal pathway. The analysis of the related electronic structure, Bader charge, electron localization function, and PDOS revealed the origin of NRR activity from the perspective of energy and electronic properties. The high activity and selectivity towards the NRR of SACs are closely associated with the Os-3N coordination. Our findings have expanded the scope of designing innovative high-efficiency SACs for NRR.

| S-EPMC11643860 | biostudies-literature

Remarkable Single Atom Catalyst of Transition Metal (Fe, Co & Ni) Doped on C2N Surface for Hydrogen Dissociation Reaction.

Project description:Currently, hydrogen is recognized as the best alternative for fossil fuels because of its sustainable nature and environmentally friendly processing. In this study, hydrogen dissociation reaction is studied theoretically on the transition metal doped carbon nitride (C2N) surface through single atom catalysis. Each TMs@C2N complex is evaluated to obtain the most stable spin state for catalytic reaction. In addition, electronic properties (natural bond orbital NBO & frontier molecular orbital FMO) of the most stable spin state complex are further explored. During dissociation, hydrogen is primarily adsorbed on metal doped C2N surface and then dissociated heterolytically between metal and nitrogen atom of C2N surface. Results revealed that theFe@C2N surface is the most suitable catalyst for H2 dissociation reaction with activation barrier of 0.36 eV compared with Ni@C2N (0.40 eV) and Co@C2N (0.45 eV) complexes. The activation barrier for H2 dissociation reaction is quite low in case of Fe@C2N surface, which is comparatively better than already reported noble metal catalysts.

| S-EPMC9823351 | biostudies-literature

Theoretical Evaluation of Electrochemical Nitrate Reduction Reaction on Graphdiyne-Supported Transition Metal Single-Atom Catalysts.

Project description:The electrochemical reaction can be applied as a powerful method to eliminate the pollution of nitrate (NO3 -) and as a feasible synthesis to enable the conversion of nitrate into ammonia (NH3) at room temperature. Herein, density functional theory calculations are applied to comprehensively analyze the electrochemical nitrate reduction reaction (NO3RR) on graphdiyne-supported transition metal single-atom catalysts (TM@GDY SACs) for the first time. It can be found that the vanadium-anchored graphdiyne (V@GDY) displays the lowest limiting potential of -0.63 V versus a reversible hydrogen electrode among the investigated systems in this work. Notably, the competing hydrogen evolution reaction is relatively restrained due to the comparatively weak adsorption of the H proton on the TM@GDY SACs. Moreover, higher energy intake is needed to overcome the energy barrier during the formation of byproducts (NO2, NO, N2O, and N2) on V@GDY without applying extra electrode potential, showing the selectivity of NH3 in the NO3RR process. The ab initio molecular dynamics simulation denotes that the V@GDY possesses excellent structure stability at the temperature of 600 K without much distortion, compared with the initial shape, indicating the promise for synthesis. This study not only offers a feasible NO3RR electrocatalyst but also paves the way for the development of the NO3RR process.

| S-EPMC9453955 | biostudies-literature

Can Metal-Nitrogen-Carbon Single-Atom Catalysts Boost the Electroreduction of Carbon Monoxide?

Project description:Metal-nitrogen-carbon single-atom catalysts (SACs) have exhibited substantial potential for CO2 electroreduction. Unfortunately, the SACs generally cannot generate chemicals other than CO, while deep reduction products are more appealing because of their higher market potential, and the origin of governing CO reduction (COR) remains elusive. Here, by using constant-potential/hybrid-solvent modeling and revisiting Cu catalysts, we show that the Langmuir-Hinshelwood mechanism is of importance for *CO hydrogenation, and the pristine SACs lack another site to place *H, thus preventing their COR. Then, we propose a regulation strategy to enable COR on the SACs: (I) the metal site has a moderate CO adsorption affinity; (II) the graphene skeleton is doped by a heteroatom to allow *H formation; and (III) the distance between the heteroatom and the metal atom is appropriate to facilitate *H migration. We discover a P-doped Fe-N-C SAC with promising COR reactivity and further extend this model to other SACs. This work provides mechanistic insight into the limiting factors of COR and highlights the rational design of the local structures of active centers in electrocatalysis.

| S-EPMC10052228 | biostudies-literature

Electrochemical Reduction of CO2 to CO over Transition Metal/N-Doped Carbon Catalysts: The Active Sites and Reaction Mechanism.

Project description:Electrochemical CO2 reduction to value-added chemicals/fuels provides a promising way to mitigate CO2 emission and alleviate energy shortage. CO2 -to-CO conversion involves only two-electron/proton transfer and thus is kinetically fast. Among the various developed CO2 -to-CO reduction electrocatalysts, transition metal/N-doped carbon (M-N-C) catalysts are attractive due to their low cost and high activity. In this work, recent progress on the development of M-N-C catalysts for electrochemical CO2 -to-CO conversion is reviewed in detail. The regulation of the active sites in M-N-C catalysts and their related adjustable electrocatalytic CO2 reduction performance is discussed. A visual performance comparison of M-N-C catalysts for CO2 reduction reaction (CO2 RR) reported over the recent years is given, which suggests that Ni and Fe-N-C catalysts are the most promising candidates for large-scale reduction of CO2 to produce CO. Finally, outlooks and challenges are proposed for future research of CO2 -to-CO conversion.

| S-EPMC8693035 | biostudies-literature

Comparative study of catalytic activities among transition metal-doped IrO2 nanoparticles.

Project description:Catalytic activities of transition metal-doped IrO2 nanoparticles (TM-IrO2 NPs; TM = Cr, Mn, Fe, Co, or Ni) are compared for various oxidation reactions such as electrochemical oxygen evolution reaction (OER), gas-phase photo-oxidation of thiol function group, and CO oxidative conversion. Here, we discovered a series of TM-IrO2 catalysts have a common activity trend for these oxidation reactions, and their activities are closely related with modified electronic states of IrO2, strongly affected by the types of the transition metal across the periodic table. For all oxidation reactions, Cr- and Mn-IrO2 achieved the highest oxidation catalytic activity, and sequentially decreased activities were obtained with Fe, Co, and Ni doped IrO2. For instance, the highest OER activity was achieved by Cr or Mn doping exhibiting the smallest overpotential η = 275~230 mV at 10 mA/cm2, while Ni-IrO2 showed rather larger overpotential (η = 347 mV) even compared with non-doped IrO2 (η = 314 mV). Scanning transmission X-ray microscopy and high-resolution photoemission spectra of TM-IrO2 indicated dopant metals modified the Ir-O interaction and thus increasing oxygen vacancy defects in IrO2. Strongly positive correlation was observed between the catalytic activities and vacancy states. The amount of defect related signals was observed the most for Cr- or Mn-IrO2, less so for Fe- or Co-IrO2, and unnoted for Ni-IrO2 compared with bare IrO2. Based on these catalytic activities and surface spectroscopic analysis results, vacancy defects induced by doping in TM-IrO2 NPs are proposed to contribute to enhance the oxidation activities.

| S-EPMC6233218 | biostudies-literature

Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements.

Project description:A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO2 reduction reaction over a competitive H2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential UL = -0.41 V) and Pt@dv-Gr (-0.27 V) for CH3OH production, and Os@dv-Gr (-0.52 V) and Ru@dv-Gr (-0.52 V) for CH4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH3OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals.

| S-EPMC5369399 | biostudies-literature

Electroreduction of CO2 and Quantification in New Transition-Metal-Based Deep Eutectic Solvents Using Single-Atom Ag Electrocatalyst.

Project description:Deep eutectic solvents (DESs) are efficient media for CO2 capture, and an electroreduction process using the deterministic surface of single-atom electrocatalysts is a facile way to screen gas absorption capacities of novel DESs. Using newly prepared transition-metal-based DESs indexed as TDESs, the interfacial mechanism, detection, quantification, and coordination modes of CO2 were determined for the first time. The CO2 has a minimum detection time of 300 s, whereas 500 s of continous ambient CO2 saturation provided ZnCl2/ethanolamine (EA) (1:4) and CoCl2/EA (1:4) TDESs with a maximum CO2 absorption capacity of 0.2259 and 0.1440 mmol/L, respectively. The results indicated that CO2 coordination modes of η1 (C) and η2 (O, O) with Zn in ZnCl2/EA (1:4) TDESs are conceivable. We found that the transition metals in TDESs form an interface at the compact layer of the electrocatalyst, while CO2 •-/CO2 reside in the diffuse layer. These findings are important because they provide reliable inferences about interfacial phenomena for facile screening of CO2 capture capacity of DESs or other green solvents.

| S-EPMC9089364 | biostudies-literature