Carbon nitride embedded with transition metals for selective electrocatalytic CO2 reduction

Ding, Chunmei; Feng, Chengcheng; Mei, Yuhan; Liu, Fengyuan; Wang, Hong; Dupuis, Michel; Li, Can

doi:10.1016/j.apcatb.2019.118391

Cited by 74 publications

(45 citation statements)

References 64 publications

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“…Double-atom catalysts (DACs), especially heteronuclear DACs, with synergetic interatomic interactions and flexible active sites, can maximize the potentials of SACs for multistep reactions, which makes the optimization of activity and selectivity feasible. For example, NiMn and NiCu anchored on g-C 3 N 4 were found to suppress the competing HER more efficiently than their monometallic counterparts and therefore delivered high Faradaic efficiency and selectivity for the CO 2 reduction reaction (CO 2 RR) into CO. 17 The CuAu/g-C 3 N 4 bimetallic photocatalyst could efficiently catalyze the hydroxylation of benzene via C–H activation under visible light irradiation. 18 Heteronuclear dual metals (CoPt, FeCo, ZnCo) embedded on N-doped carbon enhanced the binding ability of oxygen (O 2 ) and facilitated the activation of O=O bond, which were served as efficient O 2 reduction reaction (ORR) catalysts with outstanding activity.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Photo-/Electrocatalytic Reduction of Nitrogen into Ammonia by Dual-Metal Sites

et al. 2020

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The photo-/electrocatalytic nitrogen reduction reaction (NRR) is an up and coming method for sustainable NH 3 production; however, its practical application is impeded by poor Faradaic efficiency originating from the competing hydrogen evolution reaction (HER) and the inert N≡N triple bond activation. In this work, we put forth a method to boost NRR through construction of donor–acceptor couples of dual-metal sites. The synergistic effect of dual active sites can potentially break the metal-based activity benchmark toward efficient NRR. By systematically evaluating the stability, activity, and selectivity of 28 heteronuclear dual-atom catalysts (DACs) of M1M2/g-C 3 N 4 candidates, FeMo/g-C 3 N 4 is screened out as an effective electrocatalyst for NRR with a particularly low limiting potential of −0.23 V for NRR and a rather high potential of −0.79 V for HER. Meanwhile, TiMo/g-C 3 N 4 , NiMo/g-C 3 N 4 , and MoW/g-C 3 N 4 with suitable band edge positions and visible light absorption can be applied to NRR as photocatalysts. The excellent catalytic activity is attributed to the tunable composition of metal dimers, which play an important role in modulating the binding strength of the target intermediates. This work may pave a new way for the rational design of heteronuclear DACs with high activity and stability for NRR, which may also apply to other reactions.

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Section: Introductionmentioning

confidence: 99%

Highly Efficient Photo-/Electrocatalytic Reduction of Nitrogen into Ammonia by Dual-Metal Sites

et al. 2020

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“…[ 15 ] The electronic structures of single‐atom catalysts can be engineered to optimize the activation energy of a reaction and alter the reaction pathway, leading to changes in activity and selectivity. [ 16–19 ] In particular, single‐atom 3d transition metal (mainly Fe, Co, Ni) catalysts have achieved highly selective electroreduction of CO 2 to CO. [ 18–21 ] However, the most well‐known 3d metal for the CRR, Cu, has rarely been reported in its single‐atom form. This is likely because bulk Cu and its derivatives are expected to produce highly reduced products instead of C 1 products such as CO. [ 22–24 ] However, the study of single‐atom Cu catalysts for the CRR is essential for understanding the catalytic mechanism as the active site is more easily identified in a single‐atom catalyst.…”

Section: Introductionmentioning

confidence: 99%

Highly Selective Two‐Electron Electrocatalytic CO₂ Reduction on Single‐Atom Cu Catalysts

et al. 2020

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Cu‐based electrocatalysts with high catalytic selectivity for the CO2 reduction reaction present a significant technological challenge. Herein, a catalyst comprised of Cu single atoms in a nitrogen‐doped graphene matrix (Cu–N4–NG) is developed for highly selective electrocatalytic reduction of CO2 to CO. The single‐atom structure and coordination environment of Cu–N4–NG are identified by synchrotron‐based characterization. Compared to a conventional bulk Cu catalyst, Cu–N4–NG achieves a Faradaic efficiency of 80.6% toward CO under a moderate applied potential of −1.0 V versus reversible hydrogen electrode (RHE). Kinetic experiments show that 1) the Cu–N4 moiety favors the CO2 activation step and 2) the moiety‐anchoring graphene facilitates water dissociation, which supplies protons for CO2 reduction. Moreover, density functional theory (DFT) calculations reveal that CO2 reduction is less hindered thermodynamically on Cu–N4–NG compared to the competing hydrogen evolution reaction (HER) due to their limiting potential differences. Therefore, the highest CO selectivity is observed on Cu–N4–NG over the bulk Cu catalyst due to more favorable kinetics and thermodynamics.

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“…Recently, Li and colleagues demonstrated that the NiMn–C 3 N 4 –CNT and the NiCu–C 3 N 4 –CNT diatomic metal catalysts showed superior CO 2 ‐to‐CO performance with the FE above 90% over a wide potential range (−0.6 to −0.9 V) compared with the (Ni, Cu, Mn)‐C 3 N 4 ‐CNT monometallic counterparts. [ 219 ] XPS analysis showed that the Ni, Cu, and Mn in the catalysts have higher valence states, suggesting that their electronic structures may be influenced by the adjacent secondary metal atoms and consequently resulting in higher CO 2 RR activity. Meanwhile, DFT calculations exhibited that the average bond length of metal‐N is shorter in NiMn–C 3 N 4 and NiCu–C 3 N 4 than those in mono‐metal counterparts.…”

Section: Performance Of Carbon‐based Sacs Toward Co2rrmentioning

confidence: 99%

Atomically Structural Regulations of Carbon‐Based Single‐Atom Catalysts for Electrochemical CO₂Reduction

Han

Zhu

2021

Small Methods

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Carbon nitride embedded with transition metals for selective electrocatalytic CO2 reduction

Cited by 74 publications

References 64 publications

Highly Efficient Photo-/Electrocatalytic Reduction of Nitrogen into Ammonia by Dual-Metal Sites

Highly Efficient Photo-/Electrocatalytic Reduction of Nitrogen into Ammonia by Dual-Metal Sites

Highly Selective Two‐Electron Electrocatalytic CO₂ Reduction on Single‐Atom Cu Catalysts

Atomically Structural Regulations of Carbon‐Based Single‐Atom Catalysts for Electrochemical CO₂Reduction

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Carbon nitride embedded with transition metals for selective electrocatalytic CO2 reduction

Cited by 74 publications

References 64 publications

Highly Efficient Photo-/Electrocatalytic Reduction of Nitrogen into Ammonia by Dual-Metal Sites

Highly Efficient Photo-/Electrocatalytic Reduction of Nitrogen into Ammonia by Dual-Metal Sites

Highly Selective Two‐Electron Electrocatalytic CO2 Reduction on Single‐Atom Cu Catalysts

Atomically Structural Regulations of Carbon‐Based Single‐Atom Catalysts for Electrochemical CO2Reduction

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Highly Selective Two‐Electron Electrocatalytic CO₂ Reduction on Single‐Atom Cu Catalysts

Atomically Structural Regulations of Carbon‐Based Single‐Atom Catalysts for Electrochemical CO₂Reduction