Dissociative Oxygen Reduction Reaction Mechanism on the Neighboring Active Sites of a Boron-Doped Pyrolyzed Fe–N–C Catalyst

Saputro, Adhitya Gandaryus; Fajrial, Apresio Kefin; Fathurrahman, Fadjar; Agusta, Mohammad Kemal; Akbar, Fiki T.; Dipojono, Hermawan Kresno

doi:10.1021/acs.jpcc.0c00632

Cited by 37 publications

(38 citation statements)

References 35 publications

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“…One promising solution that has been successfully applied is co-doping boron and nitrogen into the TM-N-C . Our group previously reported that the existence of boron and nitrogen substitutional defect adjacent to an FeN 4 active site provides a controlled additional active site to facilitate a more preferred ORR dissociative mechanism that led to a significant improvement of its kinetics. , On the basis of this result, we thus anticipate that the same scenario can lower the overpotential of CO 2 RR and consequently enhance its rate.…”

Section: Introductionmentioning

confidence: 84%

Two-Electron Electrochemical Reduction of CO₂ on B-Doped Ni–N–C Catalysts: A First-Principles Study

et al. 2021

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We evaluate the electrocatalytic activity of graphene-supported NiN4 active center in facilitating two-electron CO2 electrochemical reduction into CO and HCOOH, as well as the competing hydrogen evolution reaction. NiN4 center is found to be more stable in zigzag-edge and armchair-edge proximity of graphene, confirming experimental evidence. In an attempt to reduce the CO2 reduction overpotential, we construct a neighboring-site environment of NiN4 center and BN substitutional defect. B-doped structures are found to be capable of reducing the CO2 reduction energy barrier through direct (HCOOH pathway) or indirect (CO pathway) participation in facilitating CO2 reduction-related key intermediates. In most Ni sites, the presence of adjacent BN site is also discovered to change the product selectivity from CO to HCOOH. Our result predicts that B-doped NiN4 sites on the interior side (NiN4BN-G) and on the armchair-edge side of tilted orientation (t-NiN4BN-AGNR) are HCOOH-selective. Although the rest of zigzag-edge and armchair-edge sites have a tendency to selectively produce CO and HCOOH, respectively, the undesirable hydrogen evolution reaction is found to be more dominant and therefore obscuring the potential. Our result demonstrates that the hydrogen evolution reaction is most likely to occur on top of a neighboring C atom instead of on the Ni center, in contrast to the commonly understood mechanism. To ultimately suppress the activity of the hydrogen evolution reaction, we predict that an effective electrocatalyst optimization cannot be realized by only selecting the best metal center and dopant pair but also by altering the neighbor’s electronic structure.

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Section: Introductionmentioning

confidence: 84%

Two-Electron Electrochemical Reduction of CO₂ on B-Doped Ni–N–C Catalysts: A First-Principles Study

et al. 2021

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“…Additionally, Zhao and Chen 21 found that the metallic atoms doped two‐dimensional boron nitride (2D‐BN) materials is a suitable candidate for ORR in replacing Pt‐based catalysts. Saputro et al 22 prepared the B‐doped FeNC catalyst pyrolyzed, exhibiting the better performance compare to the B un‐doped. Furthermore, they chose the most stable active site configuration, indicating that the active site could reduce the activation energy of oxygen dissociation with DFT calculations.…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of oxygen reduction reaction on B doped FeN ₄ G and FeN ₄ CNT catalysts for proton‐exchange membrane fuel cells

Niu

et al. 2021

Int J Energy Res

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Density functional theory (DFT) was used to calculate the stability, oxygen reduction reaction (ORR) mechanism and activity of B-doped FeN 4 CNT (carbon nano-tube [CNT]) and FeN 4 G (G, graphene). The B-doped catalysts are more stable and active than that of the un-doped, especially for FeN 4 B2 G and FeN 4 B2 CNT. Based on the Mulliken charge and electrostatic potential surface of these catalysts, Fe atom is found to be the most active site for the adsorption of O-contained species. It is shown that their adsorption energies decrease in the range: O > OH > Co-ad OH > OOH > O 2 > H 2 O > H 2 O 2 on these catalysts. H 2 O 2 will be directly dissociated into two co-adsorbed OH* or O* + H 2 O* instead of H 2 O 2 on the graphene series catalysts, and the process of reaction (H 2 O 2 + * ! 2OH*) on the active sites of the CNT series catalysts is strongly exothermic. Hence, desorption of H 2 O 2 * into the solution is difficult to proceed during the oxygen reduction process. All the catalysts are expected to promote a single site four electron process through the reaction path of I (O 2 ! O 2 * ! OOH* ! O* ! OH* ! H 2 O) except for the catalyst of FeN 4 CNT. The rate-determining step (RDS) for ORR process on FeN 4 B2 G is the first reduction step (O 2 * ! OOH*), while the RDS is the fourth reduction step (OH* ! H 2 O) for the other catalysts. FeN 4 B2 G exhibits the largest onset potentials of 0.53 V, which is larger than the on-set potential of un-doped B FeN 4 G catalyst (0.39 V). In addition, the B-doped FeN 4 CNT catalyst shows the better activity compared to the un-doped ones.

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“…Details of the microkinetic model derivation for typical hydrogenation reaction can be found in our recent works [13,[16][17][18].…”

Section: Dft Calculations and Microkinetic Modelingmentioning

confidence: 99%

Theoretical Study of Direct Carbon Dioxide Conversion to Formic Acid on Transition Metal-doped Subnanometer Palladium Clusters

Saputro

Maulana

Aprilyanti

et al. 2021

J. Eng. Technol. Sci.

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We studied the direct conversion of CO2 to HCOOH through hydrogenation reaction without the presence of base additives on the transition metal-doped subnanometer palladium (Pd7) cluster (PdxM: M = Cu, Ni, Rh) by using a combination of density functional theory and microkinetic calculations. It was shown that the CO2 hydrogenation on Pd7 and Pd6M clusters are more selective towards the formate pathway to produce HCOOH than the reverse water gas shift pathway to produce CO. Inclusion of Ni and Rh doping in the subnanometer Pd7 cluster could successfully enhance the turnover frequency (TOF) for CO2 hydrogenation to formic acid at low temperature. The order of TOF for formic acid formation is as follows: Pd6Ni > Pd6Rh > Pd7 > Pd6Cu. This order can be explained by the trend of the activation energy of CO2 hydrogenation to formate (HCOO*). The Pd6Ni cluster has the highest TOF value because it has the lowest activation energy for the formate formation reaction. The Pd6Ni system also has a superior TOF profile for HCOOH formation compared to several metal surfaces in low and high-temperature regions. This finding suggests that the subnanometer PdxNi cluster is a promising catalyst candidate for direct CO2 hydrogenation to formic acid.

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Dissociative Oxygen Reduction Reaction Mechanism on the Neighboring Active Sites of a Boron-Doped Pyrolyzed Fe–N–C Catalyst

Cited by 37 publications

References 35 publications

Two-Electron Electrochemical Reduction of CO₂ on B-Doped Ni–N–C Catalysts: A First-Principles Study

Two-Electron Electrochemical Reduction of CO₂ on B-Doped Ni–N–C Catalysts: A First-Principles Study

Mechanisms of oxygen reduction reaction on B doped FeN ₄ G and FeN ₄ CNT catalysts for proton‐exchange membrane fuel cells

Theoretical Study of Direct Carbon Dioxide Conversion to Formic Acid on Transition Metal-doped Subnanometer Palladium Clusters

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Dissociative Oxygen Reduction Reaction Mechanism on the Neighboring Active Sites of a Boron-Doped Pyrolyzed Fe–N–C Catalyst

Cited by 37 publications

References 35 publications

Two-Electron Electrochemical Reduction of CO2 on B-Doped Ni–N–C Catalysts: A First-Principles Study

Two-Electron Electrochemical Reduction of CO2 on B-Doped Ni–N–C Catalysts: A First-Principles Study

Mechanisms of oxygen reduction reaction on B doped FeN 4 G and FeN 4 CNT catalysts for proton‐exchange membrane fuel cells

Theoretical Study of Direct Carbon Dioxide Conversion to Formic Acid on Transition Metal-doped Subnanometer Palladium Clusters

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Resources

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Two-Electron Electrochemical Reduction of CO₂ on B-Doped Ni–N–C Catalysts: A First-Principles Study

Two-Electron Electrochemical Reduction of CO₂ on B-Doped Ni–N–C Catalysts: A First-Principles Study

Mechanisms of oxygen reduction reaction on B doped FeN ₄ G and FeN ₄ CNT catalysts for proton‐exchange membrane fuel cells