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C: Surfaces, Interfaces, Porous Materials, and Catalysis 2

Edge States Enhanced CO Electroreduction on Topological Nodal-Line Semimetal CuSi Nanoribbons 2

Mengyu Tang, Haoming Shen, Yu Qie, Huanhuan Xie, and Qiang Sun J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b08871 • Publication Date (Web): 04 Jan 2019 Downloaded from http://pubs.acs.org on January 5, 2019

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The Journal of Physical Chemistry

1

Edge States Enhanced CO2 Electroreduction on Topological Nodal-line Semimetal

2

Cu2Si Nanoribbons

3

Mengyu Tang,a Haoming Shen,a Yu Qie,a Huanhuan Xie,a and Qiang Sun*a,b

4

a Department

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b Center

of Materials Science and Engineering, Peking University, Beijing 100871, China.

for Applied Physics and Technology, Peking University, Beijing 100871, China

6 7 8

ABSTRACT

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It is of great importance to explore new materials beyond conventional ones for CO2

10

conversions. Inspired by the edge-state enhanced conductivity in topological nodal line

11

semimetals (NLSs) and the recent advances in synthesizing NLS Cu2Si sheet, we report

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the super performance of CO2 reduction on Cu2Si nanoribbons. Using first-principles

13

calculations, we have found that Cu2Si nanoribbons with the armchair edge (labelled as

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A>CuSi) and zigzag edge ending with Cu or Si (labeled as Z>Cu and Z>Si) have a

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strong reduction ability to activate CO2 to *COOH with low barriers. Especially, Z>Si

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is most effective for further hydrogenation, displaying a capability of transferring eight

17

electrons to produce CH4 with a low free energy change of 0.24 eV. Furthermore, the

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side reaction of hydrogen evolution reaction (HER) can also be suppressed on Z>Si,

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exhibiting excellent performance and good selectivity for CO2 reduction.

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1. INTRODUCTION 1 ACS Paragon Plus Environment

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The electrochemical reduction of carbon dioxide (CO2)1-4

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using effective

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catalysts has been regarded as a potential method to decrease the elevated level of CO2

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in the atmosphere. It is also helpful to develop the sustainable carbon-based economy.

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However, electroreduction of CO2 into high-value chemicals faces some challenges5-6

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including large overpotentials due to the weak reduction of electrocatalysts, and low

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selectivity because of the competing HER. To overcome these obstacles, extensive

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studies have been carried out to improve the electrocatalytic performances, and some

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feasible strategies have been proposed7-8, such as reducing the catalyst dimension8-9,

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introducing p-block atoms10 and inducing adsorption sites with oxophilicity.11-12 In

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addition to these conventional strategies, using topologic materials for quantum

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catalysis has attracted great attentions recently.11-14

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Topological materials have fascinating surface states or edge states, which

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stimulates the catalytic applications of topological insulator (TI)13-15 and topological

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semimetal (TS)16. For example, two distinct families of Weyl semimetal (WSM)17

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including 1T′-MoTe2 and NbP are reported to act as excellent electrocatalysts for H2

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evolution reaction, where the surfaces of these materials are robust and there are no

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significant changes in chemical composition during the catalytic process. Recently

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HER on nodal line semimetal (NLS) TiSi family18 is also reported by using first-

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principles calculations, and the results indicate that the high activity is mainly due to

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the high carrier mobility and the large density of states around Fermi level, and both

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of them are originated from the linear bands of Dirac cones in the NLS. The (0 1 0)

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surfaces of the TiSi, TiGe and TiSn are theoretically demonstrated to display an

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outstanding performance with the energy barrier of almost zero. Compared with these

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3D systems, the two dimensional (2D)19-20 ones feature high surface area with more

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low-coordinated active sites, which adds merits for utilizing 2D electrocatalysts. Then

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an intriguing question arises naturally: Is the edge state of 2D TS effective enough for

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CO2 conversion?

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Recently, a 2D Dirac NLS, Cu2Si21-22 nanosheet, is reported, and the node-line

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fermions in monolayer Cu2Si have been discovered by Angle Resolved Photo Electron 2 ACS Paragon Plus Environment

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Spectroscopy (ARPES). These new advances stimulate us to systematically investigate

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the electrochemical activity of Cu2Si nanoribbons with different edges. We first explore

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the possible configurations of all intermediates for finding the optimum

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electroreduction pathways, and then calculate the free energy changes of the side

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reaction HER to check its effect on the target reaction.

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2. METHODS

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All calculations are based on the density functional theory (DFT) using in Vienna

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Ab-initio Software Package (VASP)23. The Perdew-Burke-Ernzerhof (PBE) functional

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within the generalized gradient approximation (GGA)24 is used to find the preferable

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reaction pathway. A more reliable exchange-correlation functional, the revised Perdew-

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Burke-Ernzerhof (RPBE)25, is used to determine the free energy changes in the

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optimum pathway. The electron-ion interaction is considered in the form of the

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projector-augmented-wave (PAW) method26 with the kinetic energy cutoff up to 400

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eV (Supporting Information Fig. S1). The reciprocal space is sampled using 8×1×1 and

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7×1×1 Monkhorst−Pack27 meshes for the armchair nanoribbon and the zigzag

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nanoribbon, respectively. The intermediate structures are fully relaxed with the total

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energy and the force components less than 1×10−4 eV and 0.01 eV/Å, respectively. The

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Bader analysis28-29 is used to calculate the partial atomic charges. The density of states

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(DOS) is calculated using Gaussian smearing and the broadening factor is set as 0.05

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eV. The binding energy30-31 Eb of adsorbate A is calculated as the following equation

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(1).

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Eb  E* A  E*  E A

(1)

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Where E*A is the energy of the substrate with adsorbed A species, E* is the energy of

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the substrate, and EA represents the energy of the single A species.

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Computational Hydrogen Electrode (CHE) calculation model32 (in Supporting

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Information) is employed to elucidate the electrochemical reaction pathways and

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estimate the voltage required for different chemical pathways. The Gibbs free energy

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change (ΔG) for all of the elementary steps are defined as the following equation (2). 3 ACS Paragon Plus Environment


G  E  EZPE  T S

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(2)

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where E is the difference of energies calculated with DFT; EZPE is the difference

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of zero-point energies between reactants and products, which can be calculated using

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1 EZPE  h ; T S is the energy difference caused by the entropy effect. Because the 2

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values of T S (T = 298.15 K) for the adsorbates are much smaller than those of the

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gas-phase species, we only considered the entropy effects of the gas-phase molecules.

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The corresponding corrections for species with PBE and RPBE functional are listed in

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Table S1 and S2, respectively. The solution effects are also taken into account by

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correcting the Gibbs free energy based on the work of Peterson et al.33, and more details

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can be found in Supporting Information. The van-der-Waals corrections are not

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included in our system as its influence on reaction energies is negligible as shown in

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Table S3.

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3. RESULTS AND DISCUSSION

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3.1 Catalyst structures. As shown in Fig. 1(a) and Fig. 1(b), Cu2Si nanosheet is a

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2D hexacoordinate metal compound. The primitive cell of Cu2Si nanosheet (as show in

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Fig. 1(a) with blue dashed lines) contains one Si atom and two Cu atoms with the

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optimized lattice constants a = b = 4.123 Å and the angle of 120° between two vectors.

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Cu2Si nanosheet possesses D6h1 space group symmetry (No.191, P6/mmm) and each

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Si atom coordinates with six Cu atoms. The thermodynamic stability of this nanosheet

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has been proven in previous work21-22. Interestingly, the stable structures of the

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hypercoordinate 2D materials are usually buckled, while Cu2Si nanosheet is completely

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flat. This special planar structure is mainly contributed by the 4C-2e σ bonds22.

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Similar to the graphene nanoribbons, the Cu2Si nanoribbon can either be in the

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armchair configuration or in the zigzag configuration. The geometric structure of the

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armchair ribbon (labelled as A>CuSi) is shown in Fig. 1(c). As for zigzag ribbon, Cu

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terminated ribbon (Z>Cu) and Si terminated ribbon (Z>Si) are shown in Fig. 1(d) and

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Fig. 1(e) respectively. Considering the CPU time limitation in DFT calculations, we 4 ACS Paragon Plus Environment

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utilize 2×2, 2×1 and 2×2 unit cells for A>CuSi, Z>Cu and Z>Si respectively, and the

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corresponding width of nanoribbon is 8.320, 9.521 and 14.086 Å. The distances

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between the neighboring active sites are dA = 2.482 Å for A>CuSi, and dZ = 4.123 Å for

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Z>Cu and Z>Si.

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Figure 1. Geometric structures. (a) The top view and (b) the side view of Cu2Si

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nanosheet. The top views of (c) A>CuSi nanoribbon, (d) Z>Cu nanoribbon and (e) Z>Si

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nanoribbon. Copper and Silicon are in red and yellow, respectively.

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3.2 Electronic Structures. The electronic structures of the Cu2Si nanosheet, as well

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as the armchair and zigzag ribbons are investigated using the PBE functional. The band

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structure and the DOS of Cu2Si nanosheet are shown in Fig. 2. As one can see, Cu2Si

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nanosheet shows quasi-linear band crossing points within 0.8 eV bellow the Fermi level

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along the M-Γ and Γ-K high symmetry lines. Those band touch points form two closed

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rings in the momentum space21, which is the feature of the NLS. Additionally, the DOS

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per atom in Cu2Si nanosheet is in the range of 0.30 to 0.50 eV-1atom-1 around ±0.2 eV

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near the Fermi energy as plotted in Fig. 3, where as shown in shaded regions, DOS of

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nanoribbons A>CuSi and Z>Si near the Fermi energy is much higher than that of 2D

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Cu2Si nanosheet, suggesting the possibility of high catalytic activity in nanoribbons18.

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Figure 2. Electronic structures of Cu2Si nanosheet. The left figure is the band structure

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and the right one is the total DOS. The red dashes show the linear dispersions near the

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Fermi level.

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142 143

Figure 3. DOS comparisons between 2D Cu2Si nanosheet and (a) A>CuSi, (b) Z>Cu

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and (c) Z>Si.

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3.3 Reaction pathways. After the investigation of electronic structures of Cu2Si

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nanoribbons, we discuss the electrocatalytic performances of Cu2Si nanoribbons. CO2

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chemisorption on three nanoribbons without a proton transfer is considered, and we

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find *CO2 is stable for A>CuSi and Z>Cu, while it is slightly difficult for Z>Si to

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stabilize CO2 without a proton transfer (Fig. S2). As the free energy changes of

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*+CO2→*CO2 on A>CuSi and Z>Cu are much larger than the values of

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*+CO2→*COOH, the first elementary step for the electrochemical reduction is one

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electron transfer from the catalyst to CO2 simultaneously coupling with a proton from 6 ACS Paragon Plus Environment

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the electrolyte to form *COOH or *OCHO (Supporting Information). In our

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calculations, we consider not only the configuration *COOH with C-end adsorption

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and C-O bridge adsorption, but also the configuration *OCHO with both O atoms

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adsorbed on the active sites. The full free energy diagrams of the reaction pathways

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based on the PBE functional are shown in Fig. S4-S6 in Supporting Information, and

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the refined reaction pathways with RPBE functional are shown in Fig. 4. The

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comparison of the free energy changes using PBE and RPBE functional for the

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optimum reaction pathway is shown in Table S4. The free energy change for the

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reaction pathway of CO2→*OCHO→HCOOH is much larger than that of the pathway

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starting from *COOH, thus the reaction starting from *COOH is more possible.

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For CO2 reduction, the first electron and proton transfer to the chemically stable

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CO2 usually has a high overpotential34. In our system, however, the free energy changes

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of CO2→*COOH for A>CuSi, Z>Cu and Z>Si are only 0.10 eV, 0.28 eV and 0.18 eV

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respectively, which is much smaller as compared to that of 2D Cu2Si nanosheet (ΔG =

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0.51 eV) (Fig. S3) and many other reported electrocatalyst like metal Cu (ΔG = 0.41

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eV). Matching the order of the free energy differences in CO2→*COOH, the binding

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energies of *COOH for A>CuSi, Z>Cu and Z>Si are -0.79 eV, -0.61 eV, -0.71 eV,

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respectively. To further assess *COOH adsorptions on these catalysts, we perform

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Bader charge analysis and plot the charge density differences as shown in Fig. 5, where

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significant electron transfers occur mainly from the active sites to COOH. Furthermore,

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Bader charge analyses suggest that nanoribbons donate 0.47, 0.56 and 0.47 e to COOH

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for A>CuSi, Z>Cu and Z>Si, respectively, leading to a good binding of COOH with

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the catalysts. In addition, the numbers of transferred electrons on the nanoribbons are

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more than that of 2D Cu2Si sheet (0.39 e). More details on the binding behaviors are

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given in Fig. S7. Based on the discussions above, one can see that the edge states of the

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nanoribbons exhibit a strong reductive ability.

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In the second electron-transfer step, *COOH couples with a proton and

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simultaneously releases a H2O molecule to form *CO. CO binding should not be too

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strong for the facile desorption from the active site as well as for further hydrogenation, 7 ACS Paragon Plus Environment


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otherwise the strong binding on active sites would result in catalyst poisoning. However,

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the scaling relationship between the binding energies of the *COOH and *CO with

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similar bonding atoms is positively correlated35-36, and the strong binding energy of

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*COOH makes a strong CO adsorption. Among three nanoribbons, COOH binding

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energy on A>CuSi is the strongest, resulting in a largest binding energy of *CO (Eb = -

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1.25 eV). This strong binding energy causes a high free energy change for *CO to

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desorb and further hydrogenate. Thus, as one can see in Fig. 4(a), the thermodynamics

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barrier is 0.1 eV for *CO formation while 0.65 eV for *CO desorption from the

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substrate. In contrast, as for zigzag ribbons (Z>Cu and Z>Si), the *COOH binding

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energy is not as strong as that of the armchair nanoribbon A>CuSi, thus free energy

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changes are different and the relevant optimum reaction pathways on Z>Cu and Z>Si

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are shown in Fig. 4(b) and Fig. 4(c) respectively. On Z>Cu, the free energy change is

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0.40 eV to produce CO gas, which indicates a weaker CO adsorption than that on

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A>CuSi.

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For Z>Si, the situations are very different from what we discussed above. The

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binding energy of *COOH with Z>Si is moderate among three nanoribbons, and the

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binding energy of *CO is -0.72 eV, which is also moderate and suitable for further

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hydrogenation. Additionally, the free energy change of the potential-determining step

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(*CO→*CHO) for deep hydrogenation on Z>Si is only 0.24 eV. A possible reaction

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pathway is shown in Fig. 4(c) and the final product is CH4. Strikingly, different from

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the conventional situations where the overpotentials are usually quite high in deep

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hydrogenation37, the Si terminated zigzag ribbon (Z>Si) exhibits an excellent

205

performance on reduction CO2 to CH4 through eight-electron charge transfer process

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with a low overpotential of 0.24 V. This low overpotential is about one third of the

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overpotential on Cu (211) (0.74 V)33 and is also lower than the value of 0.38 V on Mo

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edged MoSe2 nanoribbon30, indicating a high catalytic activity of Z>Si for CO2

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reduction. More details can be found in Table 1.

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To better understand these results, we need to go back to examine the electronic

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structures as shown in Fig. 3, from which one can see that the catalytic performances 8 ACS Paragon Plus Environment

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of the studied nanoribbons are closely related to their intrinsic electronic structures. The

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DOS of A>CuSi or Z>Si near the Fermi level is obviously higher than that of Cu2Si

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nanosheet while the situation is different for Z>Cu. This is the main reason for the better

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catalytic performance of A>CuSi (the overpotential is 0.10 V for CO2→*COOH) and

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Z>Si (the overpotential is 0.18 V for CO2→*COOH) than Z>Cu (the overpotential is

217

0.28 V for CO2→*COOH). In addition, in the range of -0.2 eV to -0.15 eV, the DOS

218

of A>CuSi is even higher than that of the Z>Si, resulting in the lowest free energy

219

change in catalyzing CO2 to *COOH and the strongest adsorption energy of CO for

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A>CuSi among three nanoribbons. However, the strongest CO adsorption on A>CuSi

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is not suitable for further desorption (ΔG = 0.65 eV) and hydrogenation (ΔG = 0.86 eV)

222

as we have discussed.



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Figure 4. Free-energy diagrams and the related configurations of the intermediates for

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CO2 reduction on catalysts (a) A>CuSi, (b) Z>Cu and (c) Z>Si.

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Figure 5. Isosurface plots with a value of 0.015 eV/Å3 of the charge density difference

229

for COOH adsorption on (a) A>CuSi, (b) Z>Cu and (c) Z>Si. The regions with purple

230

dotted lines indicate charge accumulation and the regions with green dotted lines

231

indicate charge depletion.

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Table 1. Comparison of final reduction product and the corresponding overpotential

234

for CO2 reduction (‘*’ represents Ni-doped S edged MoS2, ‘**’ represents the Mo

235

edged MoSe2). Materials

Dimension

Overpotential, V

Products

Electronic band

Z>Si

1D ribbon

-0.24

CH4

NLS

3D bulk

-0.74

CH4

Metal

MoS2*30

1D ribbon

-0.28

CH4

Semiconductor

MoSe2**30

1D ribbon

-0.38

CH4

Semiconductor

AGNR>Cu38

1D ribbon

-0.48

CH3OH

Semiconductor

Cu (2 1 1)33

236 237

3.4 Side reactions. Many electrocatalysts are hampered by low Faradic efficiency

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due to the side reaction HER. A promising electrocatalyst should not only display a low

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overpotential for CO2 electroreduction, but also can effectively suppress the side

240

reactions. In our work, we have also studied the side reaction HER. Hydrogen evolution

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follows either the Volmer-Tafel or the Volmer-Heyrovsky mechanism. The Tafel

242

reaction represents the process that two adsorbed H atoms react to form H2, whereas

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the Heyrovsky reaction is the process that the adsorbed H atom reacts with another H+

244

to form H2. Those two processes can be described as the following equations (3)~(5).

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* + H+ + e− ↔ *H (Volmer process)

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*H+ + H+ + e− ↔ * + H2 (Heyrovsky process)

248

*H + *H ↔ H2 + 2* (Tafel process)

249 11 ACS Paragon Plus Environment

(3) (4) (5)


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According to Marcus theory39, the active energy of Volmer-Tafel process with two

251

electrons transferred at the same time is four times larger than that of the Volmer-

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Heyrovsky process. In addition, the distances of the neighboring active sites for Z>Cu,

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Z>Si (4.123 Å) and A>CuSi (2.482 Å) are significantly larger than the bond length of

254

H2 (0.74 Å), making it difficult for *H to bind with the neighboring one. In this sense,

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we focus on the Volmer-Heyrovsky process. As shown in Fig. 6(a), the free energy

256

changes of HER for A>CuSi and Z>Cu are 0.38 eV and 0.07 eV respectively, which

257

are lower than that of the target reaction as shown in Fig. 6(b). The lower

258

thermodynamics barrier of the HER would affect the target reaction. However, different

259

from the situations on A>CuSi and Z>Cu, the free energy change of HER on Z>Si is

260

0.36 eV, which is larger than the value of 0.24 eV for the target reaction. Therefore, the

261

side reaction HER will be effectively suppressed and hence the side reaction has little

262

influence on the target reaction for Z>Si.

263 264

Figure 6. (a) Side reaction profiles of nanoribbons. (b) Free energy change comparisons

265

between the target reaction and the competition reaction.

266 267

4. CONCLUTIONS

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In summary, we have carried out comprehensive calculations to explore the

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performance of CO2 reduction on topological node-line semimetal Cu2Si nanoribbons.

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We find that the armchair nanoribbon (A>CuSi) and the zigzag nanoribbon (Z>Cu,

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Z>Si) display strong electrocatalytic activities for CO2→*COOH with small free

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energy changes of 0.10, 0.28 and 0.18 eV, respectively. For A>CuSi and Z>Cu, the 12 ACS Paragon Plus Environment

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most possible product is CO(g), while for the Si terminated zigzag nanoribbon Z>Si, it

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exhibits a super performance of CO2 reduction to CH4 through eight electrons transfer

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with a low free energy change of 0.24 eV. Moreover, the free energy change of the side

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reaction HER is 0.36 eV which is larger than that of the target reaction, thus HER can

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be effectively hindered. Our study not only sheds insight into CO2 quantum catalysis

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by using topological nodal-line semimetal but also expands the applications of

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topological quantum materials. We hope that this study can stimulate experimental

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effort on applying quantum materials for effective CO2 conversion going beyond the

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conventional catalysts.

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AUTHOR INFORMATION

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Corresponding Author

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*E-mail: [email protected]

289

ORCID

290

Qiang Sun: 0000-0003-3872-7267

291 292

COMPETING INTRESTS

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The authors declare no competing financial interests.

294 295

Supporting Information

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Supporting Information is available free of charge on the ACS Publications website:

297

CHE model, the solvent corrections and entropy corrections used in our calculations,

298

the energy cutoff, van-der-Waals contributions, the thermodynamic stability of *CO2,

299

the comparison of free energy changes at PBE and RPBE levels, the pathways with



300

PBE results, The PDOS profiles of the *COOH, the INCAR file and the POSCAR files

301

used in our paper.

302 303 304 305 306

ACKNOWLEDGMENTS

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This work is partially supported by grants from the National Natural Science

308

Foundation of China (21573008, 21773003), and from the Ministry of Science and

309

Technology of China (2017YFA0204902). The calculations are supported by High-

310

performance Computing Platform of Peking University.

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DATA AVAILABILITY

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The data that support the findings of this study are available for the corresponding

314

author, Professor Qiang Sun of the Peking University (email: [email protected])

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upon reasonable request.

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REFERENCES

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