Electroreduction on Topological Nodal-Line Semimetal Cu

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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

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Edge States Enhanced CO2 Electroreduction on Topological Nodal-line Semimetal

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Cu2Si Nanoribbons

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

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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

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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

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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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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

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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

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

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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)

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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

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

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

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indicate charge depletion.

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

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

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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

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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

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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

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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+

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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)

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*H + *H ↔ H2 + 2* (Tafel process)

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(3) (4) (5)


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

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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

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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

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

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

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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

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

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

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influence on the target reaction for Z>Si.

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

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between the target reaction and the competition reaction.

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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

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Qiang Sun: 0000-0003-3872-7267

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COMPETING INTRESTS

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The authors declare no competing financial interests.

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Supporting Information

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

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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.

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ACKNOWLEDGMENTS

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

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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

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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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