Taming the challenges of activity and selectivity in the electrochemical nitrogen reduction reaction using graphdiyne-supported double-atom catalysts

Xu, Yongkang; Cai, Zhewei; Du, Pan; Zhou, Jiaxing; Pan, Yonghui; Wu, Ping; Cai, Chen

doi:10.1039/d1ta00262g

Cited by 36 publications

(30 citation statements)

References 66 publications

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“…Graphdiyne (GD), , a new single-layer carbon allotrople, was first obtained on the copper surface via a cross-coupling reaction in 2010 . Upon its appearance, GD has been seen to have many applications in various fields (for example, catalysis, − lithium-ion batteries, , and solar cells , ) because of its outstanding properties (e.g., exceptional semiconducting properties and high mechanical and electrical properties).…”

Section: Introductionmentioning

confidence: 99%

Density Functional Theory Study of a Graphdiyne-Supported Single Au Atom Catalyst for Highly Efficient Acetylene Hydrochlorination

Ali

Lian

2021

ACS Appl. Nano Mater.

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In this work, supported single Au on graphdiyne is examined as an efficient catalyst for acetylene hydrochlorination. The adsorption of reactants C2H2 and HCl has a paramount influence on the reaction mechanism. It is indicated that C2H2 adsorption is much stronger than the counterpart of HCl for most of the investigated cases. An Eley–Rideal (E–R) mechanism is first investigated, which is initiated with C2H2 adsorption. In the following steps, the adsorbed C2H2 becomes the site to bind and activate HCl, which leads to formation of the product. It is also revealed that single Au experienced a redox cycle along the reaction pathway. The largest barrier is calculated to be 0.57 eV, corresponding to the product desorption. On the other hand, a novel Langmuir–Hinshelwood (L–H)-like mechanism is also reported, which started with coadsorption of HCl and C2H2. It is noted that the barriers of the LH mechanism are smaller than those of the ER mechanism. Moreover, supported single Au on graphdiyne has much improved performance than the counterpart on pristine graphene and single-walled carbon nanotube support. This work clearly demonstrated the superior performance of supported single Au in acetylene hydrochlorination and the potential of novel support graphdiyne in single-atom catalysis.

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Section: Introductionmentioning

confidence: 99%

Density Functional Theory Study of a Graphdiyne-Supported Single Au Atom Catalyst for Highly Efficient Acetylene Hydrochlorination

Ali

Lian

2021

ACS Appl. Nano Mater.

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“…When it comes to co‐doping, there are also lots of related theoretical studies [79] and experimental progress [34a,80] . For example, the Fe‐N co‐doped GDY catalysts that our group had synthesized with different contents of Fe (0.1 wt%∼2 wt %) all exhibited similar onset potentials close to 1.0 volt versus reversible hydrogen electrode (Figure 4g), which was comparable to commercial Pt/C [60] .…”

Section: Electrochemical Applicationsmentioning

confidence: 65%

Post‐modified Strategies of Graphdiyne for Electrochemical Applications

Gao

Yang

et al. 2021

Chemistry An Asian Journal

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The new carbon material graphdiyne (GDY) has been verified to have a great application prospect in electrochemical field. In order to study its properties and expand its scope of application, various experiments including structural control tests are imposed on GDY. Among them, as one of the most commonly used methods to modify the structure, heteroatom doping is favored for its advantages in synthesis methods and the control of mechanical, electrical and even magnetic properties of carbon materials. According to the published studies, the top‐down methods of doping heteroatoms for GDY only need cheap raw materials, simple synthetic route and strong controllability, which is conducive to rapid performance breakthroughs in electrochemical applications. This review selects the typical cases in the development of that post‐modification method from the application of GDY in the electrochemical field. Here, based on the existed reports, the commonly used non‐metal elements (such as nitrogen, sulfur) and metal elements (such as iron) have been introduced to post‐modify GDY. Then, a detailed analysis is made for corresponding electrochemical applications, such as energy storage and electrocatalysis. Finally, the challenges and prospects of post‐modified GDY in synthesis and electrochemical applications are proposed. This review provides us a useful guidance for the development of high‐quality GDY suitable for electrochemical applications.

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“…It is known that NRR is a complex process involving six consecutive proton–electron pair (H + /e – ) transfer processes, which can occur through different mechanisms, such as alternating, distal, enzymatic, mixed mechanisms, and so on. , There is no doubt that it is very inefficient to conduct a systematic study for all the reaction channels to determine possible pathways and theoretical onset potentials. Therefore, a simple descriptor that can reasonably describe the activity is desirable for effective screening of the NRR catalysts. , Generally, the PDS of NRR is believed as the step of *N 2 + H + + e – → *N 2 H or *NH 2 + H + + e – → *NH 3 , both of which require a large energy to compensate. − As shown in Figure d, Δ G (*N 2 – *N 2 H) and Δ G (*NH 2 – *NH 3 ) were calculated for the seven screened candidates. Here, a U L of −0.98 V on the stepped Ru(0001) is set as the benchmark, as Ru has the highest theoretical activity among bulk metal surfaces.…”

Section: Resultsmentioning

confidence: 99%

Transition Metal-Modified Co₄ Clusters Supported on Graphdiyne as an Effective Nitrogen Reduction Reaction Electrocatalyst

Luo

Dai

et al. 2021

Inorg. Chem.

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Conversion of N 2 into NH 3 through the electrochemical nitrogen reduction reaction (NRR) under ambient conditions represents a novel green ammonia synthesis method. The main obstacle for NRR is lack of efficient, stable, and costeffective catalysts. In this work, by using density functional theory calculations, 16 transition metal-modified Co 4 clusters supported on graphdiyne (GDY) as potential NRR catalysts were systematically screened. Through the examinations of stability, N 2 activation, selectivity, and activity, Ti-, V-, Cr-, Mn-, and Zr-Co 3 @GDY were identified as the promising candidates toward NRR. Further explorations on the NRR mechanisms and the Pourbaix diagrams suggest that Ti-Co 3 @GDY was the most promising candidate catalyst, as it has the lowest limiting potential and high stability under the working conditions. The high activities originate from the synergy effect, where the Co 3 cluster acts as the electron donor and the heteroatom serves as the single active site throughout the NRR process. Our results offer a new perspective for advancing sustainable NH 3 production.

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Taming the challenges of activity and selectivity in the electrochemical nitrogen reduction reaction using graphdiyne-supported double-atom catalysts

Abstract: Constructing graphdiyne-supported transition metal double-atom catalysts to address the challenges of activity and selectivity in the electrochemical nitrogen reduction reaction.

Cited by 36 publications

References 66 publications

Density Functional Theory Study of a Graphdiyne-Supported Single Au Atom Catalyst for Highly Efficient Acetylene Hydrochlorination

Density Functional Theory Study of a Graphdiyne-Supported Single Au Atom Catalyst for Highly Efficient Acetylene Hydrochlorination

Post‐modified Strategies of Graphdiyne for Electrochemical Applications

Transition Metal-Modified Co₄ Clusters Supported on Graphdiyne as an Effective Nitrogen Reduction Reaction Electrocatalyst

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Taming the challenges of activity and selectivity in the electrochemical nitrogen reduction reaction using graphdiyne-supported double-atom catalysts

Abstract: Constructing graphdiyne-supported transition metal double-atom catalysts to address the challenges of activity and selectivity in the electrochemical nitrogen reduction reaction.

Cited by 36 publications

References 66 publications

Density Functional Theory Study of a Graphdiyne-Supported Single Au Atom Catalyst for Highly Efficient Acetylene Hydrochlorination

Density Functional Theory Study of a Graphdiyne-Supported Single Au Atom Catalyst for Highly Efficient Acetylene Hydrochlorination

Post‐modified Strategies of Graphdiyne for Electrochemical Applications

Transition Metal-Modified Co4 Clusters Supported on Graphdiyne as an Effective Nitrogen Reduction Reaction Electrocatalyst

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Product

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Transition Metal-Modified Co₄ Clusters Supported on Graphdiyne as an Effective Nitrogen Reduction Reaction Electrocatalyst