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Article
First-Principles Calculations of TiB MBene
Monolayers for Hydrogen Evolution
Fuhua Li, and Qing Tang
ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.9b01718 • Publication Date (Web): 28 Oct 2019
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4 First-Principles Calculations of TiB MBene Monolayers for
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7 Hydrogen Evolution
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9 Fuhua Li and Qing Tang*
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12 School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of
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Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331,
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17 China
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20 *To whom correspondence should be addressed. E-mail: [email protected].
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25 ABSTRACT
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In the recent years, the sustained growth of attention on MXenes and their
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30 derivatives (such as MBenes) encourages this 2D material to be a rising star, thereby
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33 attracting more researchers' interests on their properties. The recent advance has shown
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35 that a layered MBene, TiB, has been successfully synthesized in experiment. This
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38 newly-discovered 2D material adds to a very recent member of the MBene materials
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family, however, there are few reports revealing its properties and applications. In this
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43 account, we utilize first principle techniques to investigate this newly-discovered
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46 MBene towards its mechanical and electronic properties as well as its catalytic activity
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48 for hydrogen evolution reaction (HER). The results show that TiB monolayer is
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51 electronically metallic, and possesses excellent mechanical and dynamical stability.
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Particularly, the slight presence of surface 2DEG-FS (two-dimensional electron gas in
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56 free space) state indicates that TiB monolayer could be potentially used in electronic
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59 devices for a low-barrier electron transport channel. Additionally, for the catalytic
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4 applications, the TiB monolayer with O-termination (TiB-O*) demonstrates thermo-
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neutral Gibbs free energy of atomic hydrogen adsorption ( GH* , about 0.03 eV),
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9 approaching the ideal value of 0 eV and suggesting that it can be a promising 2D
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12 electrocatalyst to promote HER. The thermodynamic HER activity of TiB-O* is higher
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than those of most carbide-based MXenes. Our predictions on this newly-synthesized
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17 MBene material reveal it would hold great promise in electronic and electrocatalytic
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20 applications.
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22 Keywords: TiB, MBene, density functional theory, electronic structures, mechanical
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25 stability, electrocatalytic HER
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30 TOC Graphic
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4 Introduction
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7 The transition metal carbides or nitrides (MXenes), generally known as the
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9 formula of Mn+1XnTx (n = 1-3), where M denotes early transition metals such as Ti and
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12 V, X is N or/and C element, and Tx is the surface functional group, e.g. OH, O, and F,
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is a class of unique material combining metallic and ceramic properties, as well as the
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17 mix of metallic and covalent bonding.1-8 Since the discovery of the first two-
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20 dimensional (2D) Ti3C2 MXene in 2011,9 this new type of 2D material has attracted
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22 widespread attentions, and MXenes with different compositions have been synthesized
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25 one after another, such as Ti2C, Ta4C3, TiNbC, (V0.5Cr0.5)3C2, Ti3CNx (x < 1), Nb2C,
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V2C, Nb4C3, V4C3, Zr3C2, Hf3C2, Mo2C.10-16 Besides the monometallic and solid-
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30 solution MXenes, in 2015, Anasori et al.17 synthesized the Mo2TiC2Tx, Mo2Ti2C3Tx,
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33 and Cr2TiC2Tx MXenes with two different transition metals sandwiched between each
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35 other. This pioneering work in fabricating series of ordered and double-metal 2D
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38 MXenes is of critical importance for the expansion of MXenes family by moving
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toward increasing the structural complexity and diversity.18 The large family of 2D
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43 MXene materials exhibit excellent magnetic, electronic, mechanical and hydrophilic
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46 properties,19 and have been widely explored for use as electrode materials in Li-ion
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48 (Na-ion) batteries and supercapacitors.20-23 In addition to their use in electrochemical
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51 energy storage, MXenes have also been explored in electromagnetic interference
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shielding24 and are predicted to be promising topological insulators.25 Moreover, 2D
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56 MXene also shows great potential in nanocatalysis, which displays excellent
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59 electrocatalytic activity for hydrogen evolution reaction (HER), mainly due to its broad
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4 basal plane with multiple catalytic activity sites instead of the merely active edge site
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7 of other 2D materials (e.g. 2H-MoS2).26 For example, Wang et al. theoretically
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9 suggested the great potential of oxidized Ti2C, W2C and TiVC MXene as highly
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12 effective HER electrocatalysts,27 and the HER activity can be further tuned by transition
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metal doping and strain.28 Vojvodic et al. demonstrated from both theory and
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17 experiment that Mo2CTx is an active and stable catalyst for the HER in acid.29 In the
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20 work of Wang et al., the Ti2CO2 MXene modified with sulfur or phosphor doping is
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22 proved to possess excellent conductivity and high activity on HER.30 Overall, the
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25 intriguing large family of MXene with diverse characteristics serve as an ideal
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configuration space for the exploration of advanced materials with broad applicability,
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30 thus, seeking for novel MXenes materials and their derivatives with exotic properties
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33 poses an imminent challenge to us.
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35 Of note, owing to the limitation of MXenes merely involving the carbides and
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38 nitrides with C or N as the X component, synthesizing new MXene-like phase beyond
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the C/N elements remains us a grand challenge. Encouragingly, the recent experimental
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43 successes in the synthesis of novel transition metal borides monolayers such as MoB,31
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46 CrB,32 and Fe2B233 have extended the MXene-like family to boron-containing
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48 derivatives, named as MBenes. In addition, different from the traditional MXenes
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51 which are usually fabricated by selectively etching the A-containing group (e.g., Al, Ga)
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from the parent MAX phase using a solution of HF, NH4HF2, LiF or HCl, the more
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56 recent MBene, TiB monolayer, with Cmcm symmetry was obtained by the removal of
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59 the In-layer through dealloying the Ti2InB2 MAB precursor.34 The obtained TiB
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4 exhibited high stability and maintained its layered structure at high temperature. DFT
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7 calculations also predicted that the conductive TiB shows superior potential as an anode
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9 material for Li/Na ion batteries than the conventional carbide MXenes (e.g., Ti3C2).26
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12 As an emerging new member of the MXene-like family, the physics and chemistry
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of the MBene remain unknown and are fascinating the scientific communities,
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17 especially those properties of its monolayer morphology. Therefore, it should be of both
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20 fundamental and technological importance to reveal their physiochemical properties
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22 and potential applications. Herein, the TiB monolayer as a representative is utilized to
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25 carry out first-principles calculations to investigate its structural stability, electronic and
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mechanical properties, as well as the chemical reactivity. Moreover, inspired by the
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30 recent progress and promising applications of MXenes as electrocatalysts for the
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33 hydrogen evolution reaction, we also evaluated the potential electrocatalytic activity of
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35 the newly-discovered TiB for HER and compared its activity with other 2D carbide
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38 MXenes. The main processes are shown in Scheme 1.
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31 Scheme 1. Sketch of the HER process catalyzed by TiB: (a) The bulk TiB; (b) The TiB
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34 monolayer cleaved from bulk TiB for the study of electronic properties and reactivity;
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37 (c) The TiB layer with surface functionalization for HER.
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42 Computational methods
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44 In this simulation, several periodic rectangle supercells of 2D MXenes/MBenes
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47 are built, and a vacuum with 20 Å is set in the z-axis direction to eliminate the spurious
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50 interactions between adjacent periodic units. All the spin-polarized density functional
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52 theory (DFT) calculations are carried out with the Vienna ab initio simulation package
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55 (VASP 5.4.4).35 The projector augmented-wave method is adopted to describe the
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57 ion-electron interactions, and the electron exchange-correlation is depicted with the
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60 form of Perdew, Burke and Ernzerhof (PBE)36,37 in generalized gradient approximation

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4 (GGA). The cutoff energy of 600 eV and the sampled Brillouin zone of 5×5×1 k-points
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7 employing Monkhorst-Pack mesh are utilized for the geometry optimization and
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9 self-consistent calculations. The convergence tolerance is set to be 0.01 eV/ Å in force
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12 and 10−5 eV in energy. The empirical DFT-D3 correction38 is employed to describe the
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Van der Waals interaction between non-bonding atoms.
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17 The binding energy (Ebind) is defined as the energy difference between combined
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20 system and the sum of the separated component systems, as the equation of
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22 Ebind = Ecomb  ( Eads  Esub ) , where Ecomb indicates the energy of the combined system, while
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25 Eads and Esub are the energies of the adsorbate and substrate, respectively. In addition,
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the activation barrier (Eact) is calculated with the climbing-image nudged elastic band
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30 (CI-NEB) method.39
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33 Adsorption Free Energy of Hydrogen. In this work, the entire HER mechanism under
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35 standard condition is described as the following equation (1).
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37 1
38 H + (aq) +e-  H 2 (g) ; ΔG 0 =0 eV (1)
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Herein the Gibbs free energy of the intermediate hydrogen adsorbed on the catalyst
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( GH* ) is critical to evaluate the catalyst activity towards HER, and it can be calculated
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46 based on this equation;40
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48 GH*
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= EH  EZPE  T SH (2)
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51 Where the ΔE, ΔEZPE and ΔSH represent the changes of electronic energy, the
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zero-point energy, and the entropy, in each adsorption step. The ΔEZPE can be calculated
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56 according to equation (3), which neglects the contributions from the catalysts. The SH
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59 is approximately to be half the entropy of H2 in standard condition,41 i.e.,
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4 S H  -1/2 S H0 .
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nH
- EZPE - EZPE (3)
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9 nH ( n 1)H
Where EZPE and EZPE denote the zero-point energy of catalyst adsorbed with
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12 n and n-1 atomic hydrogen, respectively, while EZPE is the zero point energy of
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gaseous hydrogen. In this work, all the detailed electronic energy, zero-point energy,
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17 and entropy corrections of the important structures or critical step were provided in
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20 Supporting Information (Table S1).
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22 Surface Pourbaix Diagrams. The most stable surface of MXenes or MBenes under
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25 different USHE and pH values is depicted to construct the surface Pourbaix diagram
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which is usually used to evaluate the thermal stability of terminated 2D
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30 MXenes/MBenes. Thereinto, USHE represents the standard hydrogen electrode at the
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33 condition of pH=0 and P(H2) = 1 bar. According to the previous reports,42,43 the
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35 mechanism of water splitting on MXenes/MBenes surface occurs via the following
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38 elementary steps.
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H 2 O + *  OH* + H 2 ; G40 (4)
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43 OH*  O* + H 2 ; G50 (5)
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Where G4 and G5 are calculated based on equation 6, which is similar to
0 0
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48 equation 2.
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51 G 0 = EH  EZPE  T S (6)
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Importantly, when taking the effects of potential U and pH into account, the free
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56 energy change of MXene/MBene at various coverage of O* and OH* terminations can
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59 be calculated with the following formula (equation 7). Herein the MXene/MBene is
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4 assumed to be mixed with oxygen O* and OH* terminations, i.e., MnCn-1(OH)xOy (x +
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7 y ≤ 2).
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9 Gmix = (x +y )G40  yG50  ( x  2 y )  eU SHE  kBT ln10  pH  (7)
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12 Volcano Curve. In our work, the exchange current density (i0) is calculated as a
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function of GH* (i.e. average hydrogen adsorption Gibbs free energy, calculated based
a
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on the derivation of equation 2: GH* = EH  EZPE  T S H , as well as the formula of
a a
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2 H2
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22 catalyst) for further depiction of the volcano curve, based on the assumption by
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25 Nørskov et al.44 The exchange current density at pH = 0 can be expressed as:
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 ek0 1  exp(G a / k T ) for GH* 0
a
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29  H* B
i0   (8)
ek exp(GH* / kBT )
30 a

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0
 0 1  exp(GHa * / kBT ) H*
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34 Where k0 and kB represent the rate constant and Boltzmann constant, respectively,
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37 and k0 is set as 1.
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42 Results and discussion
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44 Stability of TiB Monolayer. Each 2D TiB monolayer consists of two atomic boron
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47 layers sandwiched with two atomic titanium layers, as shown in Figure 1a. Each surface
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50 Ti atom is coordinated to six B atoms, while each B is covalently bonded to eight Ti
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52 atoms. The optimized lattice parameter of the TiB monolayer is a = 2.963 Å and 3.175
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55 Å, and the optimized Ti-B and B-B bonds are 2.300 (2.283) and 1.724 Å, respectively.
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57 The stability of the structure framework is a prerequisite for long-term operation,
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60 therefore we first have to estimate the stability of TiB single-layer. To this end, we carry

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4 out phonon band structure calculation as well as the ab initio molecular dynamics
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7 (AIMD) simulations to investigate the dynamic, thermodynamic, and geometric
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9 stability of TiB monolayer. The TiB unit cell contains four atoms, and about 12 phonon
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12 bands corresponding to the optical and the acoustic modes are generated. As shown in
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Figure 1b, no imaginary frequency appears in any wave vector of the phonon dispersion,
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17 confirming the dynamic stability of the TiB monolayer. In addition, a canonical
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20 ensemble (NVT) AIMD simulation of a 4 × 4 TiB supercell layer is performed at 1000
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22 K for 5 picoseconds (ps). The temperature and energy are slightly oscillated near the
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25 equilibrium configuration, and no notable geometry buckling is found (Figure 2),
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suggesting the excellent thermodynamic stability of TiB at high temperature. Moreover,
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30 the mean square displacement (MSD) of B and Ti as a function of time is given in
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33 Figure S1, indicating a small atomic displacement during the AIMD simulations. In
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35 practice, the capability to form a freestanding membrane is pivotal for the geometric
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38 stability of a 2D nano-crystal. Thus we investigate the in-plane stiffness of TiB single-
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layer by using the 2D Young's modulus (Y2D) to test its mechanical strength. The Y2D is
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43 calculated according to equation 9, and the corresponding strain energy curve is
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46 presented in Figure S2.
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48 1  2 ES
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52 Herein A0 is the surface area of equilibrium TiB unit cell (2.96 Å × 3.18 Å = 9.41
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55 Å2), ε and ES are the axial strain (in this work is y axis) and strain energy per unit cell.
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57 Based on the strain energy curve, the Y2D is fitted to be 0.36 eV/Å2 (see Figure S2 in
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4 under gravity based on the elastic theory.45 The relative out-of-plane deformation is
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7 evaluated with the following expression:
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9   gl 
10 h/l   (10)
11  Y2D 
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13 Where h/l stands for the ratio between the vertical deformation and dimension of
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16 the free-standing TiB, ρ = 1.88 × 10-6 kg m-2, l is the edge length of the TiB flake, and
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18 g represents the gravitational acceleration. The calculated h/l is about 3.18 ×10-3 for a
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21 moderate size TiB monolayer with an edge length of 100 μm, which is comparable with
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24 the rigid Ca2N monolayer.46 Such a small value indicates that TiB monolayer is strong
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26 enough to withstand the deformation caused by self-weight or large extra load to keep
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57 Figure 1. The side and top views of TiB single-layer after geometry optimization (a),
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33 Figure 2. The oscillation of energy and temperature against the time in AIMD
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38 snapshots of the TiB nanolayer after the AIMD simulation. Note that the relative energy
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of initial stable structure is set as zero for simplicity.
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43 Electronic properties and potentiality for 2DEG-FS State. In this section, we will
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46 investigate the electronic properties of the 2D TiB single-layer. The calculated ground-
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48 state band structure is shown in Figure 3a. Note that a partially occupied energy band
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51 crosses the Fermi level with a large in-plane dispersion, which indicates the metallic
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property of the TiB monolayer. In addition, the projected density of states (PDOS)
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59 allow us to investigate the electronic structure in more detail, as shown in Figure 3b. It
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4 is clearly observed that the occupied states around the Fermi level are mainly
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7 contributed by the d electrons of Ti atoms, indicating the contribution of surface Ti to
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9 the conductivity of TiB layer. In addition, the valence band below the Fermi level is
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12 mainly attributed by the orbital hybridization of Ti-3d and B-2p states, leading to the
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formation of strong Ti-B chemical bonds to minimize the energy of TiB layer.
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17 Additionally, the high-energy areas above the Fermi level are primarily contributed by
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20 the unoccupied Ti-3d states. Especially, the electron localization function (ELF)
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22 analysis shows that electron is slightly delocalized above the surface of the TiB
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25 monolayer (Figure 3c). This implies that the 2D slice of TiB nanosheet exhibits a weak
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nucleus-free two-dimensional electron gas in free space (2DEG-FS). The special
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30 2DEG-FS of TiB may be caused by the d-orbital coupling of the surface unsaturated
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33 dangling bonds of the surface Ti atoms, as indicated by the highest occupied molecular
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35 orbital (HOMO) distribution (Figure S3). Note that the surface nearly free electron
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38 (NFE) state has also been previously discovered in other 2D materials such as graphene
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single-layer,48 fullerenes,49 nanotubes50 and electrides (e.g., Ca2N).46 The NFE is
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43 usually in an unoccupied state and is required to shift the electron doping toward the
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46 Fermi level to achieve electron transport, thus 2DEG-FS located at the Fermi level not-
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48 relying on doping is more promising than that of the occupied NFE state. Interestingly,
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51 when one valence electron is removed to form [TiB]+, the delocalized ELF feature
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almost completely disappears (Figure 3d). Therefore electron transfer from TiB single-
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56 layer to other species can be used to vacate the 2DEG-FS state. Particularly, the
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59 interesting feature of 2DEG-FS state found for the TiB single-layer is potentially useful
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4 for minimizing heat generation and electron resistance, and can be probably used as an
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7 effective transport channel.34 In addition, we have calculated the ELF distribution of
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9 TiB single layer covered by O and OH, as depicted in Figure S4. One can see that the
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12 electrons become more localized around the O and OH groups, indicating that the
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2DEG-FS state found in the bare TiB monolayer has disappeared with surface
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17 functionalization.
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37 Figure 3. The band structure (a) and corresponding partial density of states (PDOS) (b)
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39 of TiB single-layer, as well as the ELF maps of TiB single-layer (c) and the [TiB]+(d).
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42 Applications for Electrocatalysis. Previous studies on the carbide and nitride MXenes
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44 showed that the bare MXene surface is chemically too reactive to survive in the ambient
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47 conditions, and functional groups such as O, OH are usually present to stabilize the
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50 surface. Similarly, the TiB single-layer MBene with exposed surface Ti atoms is also
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52 expected to have high surface reactivity, and thus investigating the air stability of the
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55 TiB single-layer is necessary for its realistic applications. Herein, several ambient
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57 molecules (N2, CO2, O2, H2O, and H2) are considered to examine their adsorptions on
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4 TiB layer surface, and we considered all the possible adsorption sites including top,
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7 bridge and hollow sites of surface Ti and B. The most stable adsorption geometries and
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9 binding energies were provided in Figure S5 and Table 1. Clearly, the adsorptions of
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12 these molecules are energetically very negative, and the adsorbed N2, CO2, O2 and H2O
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are strongly activated, indicating a strong thermodynamic driving force of the TiB
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17 surface for chemisorption. Specifically, upon adsorption, the N2 molecule is strongly
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20 bound to both the B and Ti atoms with a large charge transfer of 2.17 e from TiB to N2,
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22 and the N-N bond is significantly stretched from 1.12Å in the free N2 state to 1.42 Å.
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24
25 The CO2 adsorption forms highly bended CO2* on the surface hollow site, and the C
26
27
atom is located above the sub-surface B atom, while the two O atoms are bonded to the
28
29
30 surface Ti atoms. Moreover, the H2O molecule is adsorbed above the bridge site of two
31
32
33 Ti atoms, while H2 prefers to adsorb on top site of Ti atom, and the corresponding
34
35 charge transfers are 1.82 e and -0.17 e respectively. The adsorbed N2, O2, H2O and H2
36
37
38 can be easily dissociated into two atoms/groups and bind strongly onto the TiB surface.
39
40
The dissociation barrier is quite small, about 0.34 eV for N2, 0.09 eV for H2O and 0.22
41
42
43 eV for H2 (see Figure S6). Particularly, O2 can be directly dissociated into two O* atoms
44
45
46 adsorbed on the TiB monolayer almost without barrier, indicating the high affinity for
47
48 O functionalization. These results indicate that the bare surface of TiB is chemically
49
50
51 reactive and tend to be easily functionalized by oxygen and other functional groups.
52
53
We should note that the layered bulk TiB MBene has been experimentally realized by
54
55
56 a solid-state reaction and vacuum dealloying at a high temperature.34 Due to the high
57
58
59 surface reactivity of the TiB monolayer, we hypothesized that it is more likely to
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2
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4 achieve the synthesis of ultrathin TiB layers via chemical vapor deposition (similar to
5
6
7 the synthesis of 2D TiC or Mo2C51 with the free of surface functional groups or directly
8
9 exfoliated from layered bulk TiB by mechanical methods under vacuum conditions).
10
11
12
13
14
Table 1. The binding energy of several molecules adsorbed on the surface of bare TiB
15
16
17 monolayer, as well as the Bader charge transferred from the TiB substrate to adsorbed
18
19
20 molecule during the interaction.
21
22 species N2 CO2 O2 H2O H2
23
24
25 Ebind (eV) -1.96 -3.22 -8.79 -0.84 -0.32
26
27
28
Charge (e) 2.17 2.06 2.04 1.82 -0.17
29
30 On the other hand, for the electrocatalytic applications, HER is one of the most
31
32
33 important energy conversion process in clean energy technologies such as water
34
35 splitting. Motivated by the recent development of carbide MXenes as effective
36
37
38 electrocatalysts to catalyze hydrogen evolution, it is of great importance to explore the
39
40
41
potential and catalytic activity of the new member of TiB MBene for HER.
42
43 Thermal Stability. Firstly, we will investigate the thermodynamic stability and most
44
45
46 stable surface state of the functionalized TiB under different USHE and pH conditions.
47
48 When it is applied in liquid environment, the bare MBene is prone to suffer from attacks
49
50
51 from O* and OH* groups. In order to check the thermal stability of O* or OH*
52
53
54
terminated TiB, we plot the surface Pourbaix diagram of TiB monolayer under the
55
56 relevant USHE and pH values, as shown in Figure 4a. In the strong acid environment
57
58
59 (pH = 0), the minimum potential (USHE) required to protect TiB monolayer from
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2
3
4 oxidation of water is -1.92 V. Note that with the increase of pH (the slope is -0.059
5
6
7 V/pH), we need negatively larger USHE (more reducing environment) to protect the bare
8
9 2D TiB from oxidation. Once the USHE is above the minimum cathodic protection
10
11
12 potential (-1.92 V), the TiB surface begins to be oxidized with H2O to form OH* groups
13
14
(1/8 ML OH* at USHE of -1.66 V). With the increase of USHE, the TiB surface would be
15
16
17 covered by more and more OH* until it is fully saturated (1 ML), which corresponds to
18
19
20 the USHE of -0.16 V. As the USHE continues to increase, the OH* groups will be partially
21
22 oxidized to form O*, and the TiB surface would be terminated with the mixture of OH*
23
24
25 and O* groups (0.5 ML OH* & 0.5 ML O* at USHE of 0.06 V). In the extremity, all
26
27
OH* groups will convert to O* when we keep increasing the USHE, and the fully
28
29
30 oxidized O*-terminated TiB appears at the potential above 0.06 V. Moreover, since
31
32
33 both the activity and stability are critical factors for a promising HER catalyst, we then
34
35 investigate the relative stability of TiB MBenes against the pH under the potential-free
36
37
38 condition, i.e. USHE = 0 V. From Figure 4b, it can be clearly seen that when the pH is
39
40
lower than 3.6, the mixed O*-OH*-terminated TiB has slightly higher stability, while
41
42
43 when the pH increases to above 3.6, the fully O*-terminated TiB becomes much more
44
45
46 stable. This indicates that in realistic aqueous environments within a large range of pH
47
48 values, the functionalized TiB would exist mainly in the form of fully oxidized state.
49
50
51 Thus, in our following discussion, we will focus on the fully oxidized TiB (TiB-O*)
52
53
for the investigation of HER activity.
54
55
56
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1
2
3
4 2
5 0
6 1 ML O*
7 1/8 ML OH*
8 -6

Relative Stability (eV)

1 ML OH*
9 0 0.5 ML O* & 0.5 ML OH*
0.5 ML O
10 * & 0.5 M 1 ML O*
USHE (V)

L OH* -12
11
12 1 ML OH*
13 1/8 ML OH* -18
14 -2
15
16 -24
17
TiB
18
19 -4 -30
20 0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
21 pH pH
22
23
24 Figure 4. The surface Pourbaix diagrams for TiB MBene (a), and the relative stability
25
26 of OH* and O* terminated TiB at the USHE of 0 V (b).
27
28
29 Catalytic activity of HER. As mentioned above, we first cover the entire surface with
30
31 oxygen atoms (TiB-O*),52,53 which are located at the bridge site and coordinated to two
32
33
34 surface Ti atoms, as shown in Figure 5a. The calculated band structure of TiB-O*
35
36
37 (Figure 5b) shows that the oxidized TiB has a very small band gap of around 0.06 eV,
38
39 which is different from the metallic feature of the bare 2D TiB. The excellent electrical
40
41
42 conductivity with a close-to-zero band gap is critical for the fast electron transport
43
44 during the electrochemical procedures.
45
46
47
48
49
50
51
52
53
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55
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4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25 Figure 5. The geometry structure of oxygen terminated TiB (TiB-O*) (a) and its band
26
27
structure (b), herein Fermi level is set as zero.
28
29
30
31
32
The Gibbs free energies for atomic hydrogen adsorption ( GH* ) on the O site of
0
33
34
35 TiB-O* at various H coverage are calculated and displayed in Figure 6. It has been
36
37
38 well-known that an ideal HER catalyst should have a close-to-zero free energy of H
39
40
adsorption (i.e., GH*  0 ). Considering that there are totally 16 O* atoms terminated
0
41
42
43 on the surface of the 4 × 4 TiB-O* supercell, we can simulate the adsorption under
44
45
46 different H coverage with the increment of 1/16. For TiB-O* at the hydrogen coverage
47
48 of 1/16, the GH* is 0.00 eV, which is closely perfect for HER. We also investigated
0
49
50
51 the H adsorption on the surface Ti atom of TiB-O*, and the calculated Gibbs free energy
52
53
of H adsorption is 0.68 eV (the adsorption geometry is shown in Figure S7), which is
54
55
56 much higher than that on the surface O site. Hence, the protonation would most likely
57
58
59 occur at the O site. As the coverage further increases to 2/16, the adsorption of H*
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2
3
4 approaches 0.01 eV, as shown in Figure 6. With the continuous increase of H coverage,
5
6
7 the adsorption of H* over TiB-O* is calculated to be 0.03 eV (3/16), 0.10 eV (4/16),
8
9 0.03 eV (5/16), -0.04 eV (6/16), 0.08 eV (7/16) and 0.06 eV (8/16), respectively. Note
10
11
that such a small GH* value (≤0.10 eV) for H coverage below 8/16 indicates that the
0
12
13
14
TiB-O* monolayer is an potentially efficient HER electrocatalyst over a wide range of
15
16
17 H coverage. Moreover, the H adsorption geometries at different surface coverage are
18
19
20 presented in Figure S8, a notable hydrogen bonding between the adsorbed H* and the
21
22 neighboring O-functional group is observed.
23
24 0.12
25
26 0.1
27 0.08
28 0.08
29
0.06
Free Energy (eV)

30
31 0.04 0.03
32 0.03
33 0.01
34 Ideal
35 0.00
36 0.00
37
38 -0.04 -0.04
39
40
41 1/16 2/16 3/16 4/16 5/16 6/16 7/16 8/16
42 H-Coverage
43
44 Figure 6. The Gibbs free energies for atomic hydrogen adsorption on the O site of
45
46
47 TiB-O* at various H coverage.
48
49
50
51
52 Noteworthy, we have additionally investigated the influence of surface
53
54
55 fluorination on the H adsorption over TiB MBene. At the surface F coverage of 25%,
56
57 50%, 75% and 100%, the corresponding H binding free energies are 0.06, -0.06, 0.05,
58
59
60 and 1.07 eV, respectively (their adsorption structures are depicted in Figure S9). These

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2
3
4 values are less favorable than that of H binding with fully O-terminated TiB (close to
5
6
7 0.00 eV). This indicates that fluorination will decrease the HER activity of
8
9 functionalized TiB.
10
11
12 To compare the catalyst performance of bare and oxygen-covered 2D TiB with
13
14
other MXenes, a volcano curve was plotted in Figure 7. Noteworthy, for the carbide
15
16
17 MXenes, previous theoretical studies predicted that the oxidized Ti2C, Nb2C, Mo2TiC2,
18
19
20 Cr2TiC2, and Cr2C MXenes can be used as promising HER electrocatalysts,41,54,55 and
21
22 they will be selected herein as references for comparison with TiB-O*. The average
23
24
Gibbs free energy of hydrogen adsorption ( GH* )41 on TiB-O* with hydrogen coverage
a
25
26
27
of θ =1/2 and that on bare TiB with hydrogen coverage of θ =1 was calculated to obtain
28
29
30 the theoretical exchange current (i0), as shown in Table 2 (their free energies with
31
32
33 different hydrogen coverage are shown in Figure S10). The catalyst performance on
34
35 HER can be quantitatively evaluated with the position of GH* and i0, and the position
a
36
37
38 closer to the volcano peak corresponds to a better catalytic performance. From Figure
39
40
7, the H is strongly adsorbed on the bare TiB single-layer with a very negative GH*
a
41
42
43 of -0.37 eV, which is located at the bottom left of the volcano curve with a very low i0
44
45
46 (highlighted in pink). This suggests that the bare TiB sheet is not an appropriate
47
48 electrocatalyst for HER. However, this situation can be significantly improved with the
49
50
51 surface oxygen termination. Once the surface is fully covered by oxygen, the adsorption
52
53
of H on TiB-O* becomes significantly weakened with GH* close to zero (0.03 eV,
a
54
55
56 highlighted in yellow around the volcano peak). This behavior balances the adsorption
57
58
59 and release of hydrogen resulting in a much higher exchange current i0, which is
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2
3
4 favorable for HER. Thus, TiB-O* is expected to exhibit a better catalytic performance
5
6
7 on HER than the bare one. By comparing with other carbide MXenes, we note that TiB-
8
9 O* is a very promising HER electrocatalysts close to the peak of the volcano plot, which
10
11
12 is comparable to the oxidized Ti2C MXene.
13
14
15
16
Table 2. The GH* (eV) of hydrogen adsorption on oxygen terminated TiB, Ti2C,
a
17
18
19
Nb2C, Mo2TiC2, Cr2TiC2, and Cr2C, with the coverage of θ = 1/2, as well as the GH*
a
20
21
22 on the bare TiB surface with the coverage of θ = 1. The calculated exchange currents,
23
24
25 log(i0/A cm-2), marked as B, are listed here.
26
27
28
species TiB TiBO Ti2CO2 Nb2CO2 Mo2TiC2O2 Cr2TiC2O2 Cr2CO2
29
30 GH*
a
(eV) -0.37 0.03 0.01 0.22 0.16 0.07 0.21
31
32
33 log(i0/A cm-2) -6.23 -0.63 -0.39 -3.70 -2.69 -1.20 -3.53
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
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1
2
3
4
5 Ideal
6 0
7
8
Ti2CO2
9 TiBO
10 Cr2TiC2O2
11
-2

om
12
Log(i0/A cm )
-2

13

at
14 Mo2TiC2O2

O
15 Cr2CO2

ith
16

w
17 -4
d
Nb2CO2
te
18 a
in
19
rm

20
Te

21
22
23 -6
TiB
24
25
26
27 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3
28
29 ΔGH*/eV
30
31 Figure 7. The calculated exchange current (log i0) plotted as a function of H* adsorption
32
33
34 free energy on different MXenes/MBenes.
35
36
37 In order to get a deeper insight into the underlying mechanism of HER on TiB-O*
38
39 MBene, we further investigated the two possible HER mechanisms, Volmer-Tafel or
40
41
42 Volmer-Heyrovsky reactions, to drive H2 formation (Figure S11). Their main
43
44 difference lies in the second elementary step, i.e. H* + H*  H 2 for Tafel reaction and
45
46
47 H3O+ + e- + H*  H 2  H 2O for the Heyrovsky reaction. The activation barriers are
48
49
50 calculated based on the 3×3×1 TiB-O* supercell with the surface covered by H*. Note
51
52 that here we use six H2O molecules to simulate the liquid environment based on the
53
54
55 model in previous reports.56,57 The calculated barrier for the Tafel step (2.91 eV) is
56
57 much higher than that of the Heyrovsky mechanism (0.93 eV). Thus the HER prefers
58
59
60 to follow the Heyrovsky mechanism on oxygen-terminated TiBO. To further

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2
3
4 understand the outstanding HER performance of oxidized TiB monolayer, we
5
6
7 performed the Bader charge and density of states (DOS) analysis of the O-H interaction
8
9 in TiB-O* with one H adsorption. Prior to H adsorption, the surface O atom gains about
10
11
12 0.89 e from the TiB substrate. After the H adsorption, the bonded O atom gains an
13
14
increased charge of about 1.21 e, where 0.72 e is from H and 0.49 e is from the TiB
15
16
17 substrate. Moreover, the PDOS plot (Figure S12) indicates that the orbital interaction
18
19
20 between H and O leads to a fully occupied H 1s state and a partially occupied O 2p state
21
22 around the Fermi level. In principle, the balance between the bonding state and the anti-
23
24
25 bonding state would cause a favorable H adsorption approaching zero, which could be
26
27
the possible reason of high HER catalytic performance.
28
29
30 Conclusions
31
32
33 In summary, in this work, we performed theoretical studies to explore the stability,
34
35 electronic properties, mechanical properties and electrocatalytic applications of the
36
37
38 recently newly-discovered 2D MBene, TiB monolayer, belonging to one of the MXene
39
40
derivatives. The absence of imaginary modes in phonon dispersion and the structural
41
42
43 rigidity under high temperature from AIMD simulation indicated the high stability
44
45
46 of the free-standing TiB monolayer. Our calculations showed that TiB has a high
47
48 mechanical strength and stability. Moreover, the 2D TiB is electronically metallic from
49
50
51 band structure calculations, and especially, this material has slight 2DEG-FS state on
52
53
the TiB monolayer surface featured by the nearly free electron state. Thus, the TiB
54
55
56 monolayer would be expected to act as a promising low-barrier electron transport
57
58
59 material. Like the traditional carbide MXenes, the bare TiB monolayer has very high
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1
2
3
4 surface reactivity, which has strong interaction with the ambient molecules that can be
5
6
7 easily dissociated onto the TiB surface. In addition, our DFT finding demonstrated that
8
9 the TiB monolayer fully covered by oxygen (TiB-O*) is expected to be a potentially
10
11
12 efficient catalyst for the electrocatalytic HER. The surface O acts as the active site for
13
14
the favorable H binding, and the close-to-zero Gibbs free energy of H adsorption as
15
16
17 well as the high exchange current density are approaching the peak site of the volcano
18
19
20 plot. Overall, our investigations highlight a new paradigm in exploring the electronic
21
22 properties and electrocatalytic applications of the novel TiB monolayer, which provide
23
24
25 useful guidelines for the further exploration of the fascinating properties of this newly-
26
27
discovered MBene material from both experiment and theory.
28
29
30
31
32
33
34 Supporting Information
35
36
37 The MSD change of B and Ti atom, the strain energy curve, HOMO state, the
38
39
ELF map, the adsorption geometries of molecules and H, the HER pathway,
40
41
42 DOS analysis, and the energy data of the reaction intermediates.
43
44
45
46
47
48 Notes
49
50
51 The authors declare no competing financial interests.
52
53
54
55
56
57 Acknowledgements
58
59
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2
3
4 This work was supported by the start-up fund of Chongqing University
5
6
7 (No.0220001104473). This research used resources of the National Supercomputer
8
9 Center in Guangzhou.
10
11
12
13
14
References
15
16
17 (1) Ng, V. M. H.; Huang, H.; Zhou, K.; Lee, P. S.; Que, W. X.; Xu, J. Z.; Kong,
18
19
20 L. B. Recent Progress in Layered Transition Metal Carbides and/or Nitrides (MXenes)
21
22 and their Composites: Synthesis and Applications. J. Mater. Chem. A 2017, 5, 3039-
23
24
25 3068.
26
27
(2) Zhu, J. W.; Wang, M.; Lyu, M. Q.; Jiao, Y. L.; Du, A. J.; Luo, B.; Gentle, I.;
28
29
30 Wang, L. Z. Two-Dimensional Titanium Carbonitride MXene for High-Performance
31
32
33 Sodium Ion Batteries. ACS Appl. Nano Mater. 2018, 1, 6854-6863.
34
35 (3) Cheng, Y.; Dai, J.; Song, Y.; Zhang, Y. Single Molybdenum atom Anchored
36
37
38 on 2D Ti2NO2 MXene as a Promising Electrocatalyst for N2 Fixation. Nanoscale 2019,
39
40
11, 18132-18141.
41
42
43 (4) Handoko, A. D.; Steinmann, S. N.; Seh, Z. W. Theory-Guided Materials
44
45
46 Design: Two-Dimensional MXenes in Electro- and Photocatalysis. Nanoscale Horiz.
47
48 2019, 4, 809-827.
49
50
51 (5) Cheng, Y. W.; Zhang, Y. M.; Li, Y.; Dai, J. H.; Song, Y. Hierarchical
52
53
Ni2P/Cr2CTx (MXene) Composites with Oxidized Surface Groups as Efficient
54
55
56 Bifunctional Electrocatalysts for Overall Water Splitting. J. Mater. Chem. A 2019, 7,
57
58
59 9324-9334.
60

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Page 27 of 34 ACS Applied Nano Materials

1
2
3
4 (6) Chen, J. N.; Yuan, X. L.; Lyu, F. L.; Zhong, Q. X.; Hu, H. C.; Pan, Q.; Zhang,
5
6
7 Q. Integrating MXene Nanosheets with Cobalt-Tipped Carbon Nanotubes for an
8
9 Efficient Oxygen Reduction Reaction. J. Mater. Chem. A 2019, 7, 1281-1286.
10
11
12 (7) Kuznetsov, D. A.; Chen, Z.; Kumar, P. V.; Tsoukalou, A.; Kierzkowska, A.;
13
14
Abdala, P. M.; Safonova, O. V.; Fedorov, A.; Muller, C. R. Single Site Cobalt
15
16
17 Substitution in 2D Molybdenum Carbide (MXene) Enhances Catalytic Activity in the
18
19
20 Hydrogen Evolution Reaction. J. Am. Chem. Soc. 2019, 10.1021/jacs.1029b08897.
21
22 (8) Di, J.; Yan, C.; Handoko, A. D.; Seh, Z. W.; Li, H. M.; Liu, Z. Ultrathin Two-
23
24
25 Dimensional Materials for Photo- and Electrocatalytic Hydrogen Evolution. Mater.
26
27
Today 2018, 21, 749-770.
28
29
30 (9) Naguib, M.; Kurtoglu, M.; Presser, V.; Lu, J.; Niu, J.; Heon, M.; Hultman, L.;
31
32
33 Gogotsi, Y.; Barsoum, M. W. Two-Dimensional Nanocrystals Produced by Exfoliation
34
35 of Ti3AlC2. Adv. Mater. 2011, 23, 4248-4253.
36
37
38 (10)Zhou, J.; Lin, S.; Huang, Y.; Tong, P.; Zhao, B.; Zhu, X.; Sun, Y. Synthesis
39
40
and Lithium ion Storage Performance of Two-dimensional V4C3 MXene. Chem. Eng.
41
42
43 J. 2019, 373, 203-212.
44
45
46 (11)Naguib, M.; Mashtalir, O.; Carle, J.; Presser, V.; Lu, J.; Hultman, L.; Gogotsi,
47
48 Y.; Barsoum, M. W. Two-Dimensional Transition Metal Carbides. ACS Nano. 2012, 6,
49
50
51 1322-1331.
52
53
(12)Naguib, M.; Halim, J.; Lu, J.; Cook, K. M.; Hultman, L.; Gogotsi, Y.; Barsoum,
54
55
56 M. W. New Two-Dimensional Niobium and Vanadium Carbides as Promising
57
58
59 Materials for Li-Ion Batteries. J. Am. Chem. Soc. 2013, 135, 15966-15969.
60

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1
2
3
4 (13)Ghidiu, M.; Naguib, M.; Shi, C.; Mashtalir, O.; Pan, L. M.; Zhang, B.; Yang,
5
6
7 J.; Gogotsi, Y.; Billinge, S. J. L.; Barsoum, M. W. Synthesis and Characterization of
8
9 Two-Dimensional Nb4C3 (MXene). Chem. Commun. 2014, 50, 9517-9520.
10
11
12 (14)Meshkian, R.; Naslund, L.-A.; Halim, J.; Lu, J.; Barsoum, M. W.; Rosen, J.
13
14
Synthesis of Two-Dimensional Molybdenum Carbide, Mo2C, From the Gallium Based
15
16
17 Atomic Laminate MO2Ga2C. Scripta Mater. 2015, 108, 147-150.
18
19
20 (15)Zhou, J.; Zha, X.; Chen, F. Y.; Ye, Q.; Eklund, P.; Du, S.; Huang, Q. A Two-
21
22 Dimensional Zirconium Carbide by Selective Etching of Al3C3 from Nanolaminated
23
24
25 Zr3Al3C5. Angew. Chem. Int. Edit. 2016, 55, 5008-5013.
26
27
(16)Urbankowski, P.; Anasori, B.; Makaryan, T.; Er, D.; Kota, S.; Walsh, P. L.;
28
29
30 Zhao, M.; Shenoy, V. B.; Barsoum, M. W.; Gogotsi, Y. Synthesis of Two-Dimensional
31
32
33 Titanium Nitride Ti4N3 (MXene). Nanoscale 2016, 8, 11385-11391.
34
35 (17)Anasori, B.; Xie, Y.; Beidaghi, M.; Lu, J.; Hosler, B. C.; Hultman, L.; Kent,
36
37
38 P. R. C.; Gogotsi, Y.; Barsoum, M. W. Two-Dimensional, Ordered, Double Transition
39
40
Metals Carbides (MXenes). ACS Nano. 2015, 9, 9507-9516.
41
42
43 (18)Tan, T. L.; Jin, H. M.; Sullivan, M. B.; Anasori, B.; Gogotsi, Y. High-
44
45
46 Throughput Survey of Ordering Configurations in MXene Alloys Across Compositions
47
48 and Temperatures. ACS Nano. 2017, 11, 4407-4418.
49
50
51 (19)Khazaei, M.; Arai, M.; Sasaki, T.; Chung, C.-Y.; Venkataramanan, N. S.; Estili,
52
53
M.; Sakka, Y.; Kawazoe, Y. Novel Electronic and Magnetic Properties of Two-
54
55
56 Dimensional Transition Metal Carbides and Nitrides. Adv. Funct. Mater. 2013, 23,
57
58
59 2185-2192.
60

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2
3
4 (20)Ghidiu, M.; Lukatskaya, M. R.; Zhao, M.-Q.; Gogotsi, Y.; Barsoum, M. W.
5
6
7 Conductive Two-dimensional Titanium Carbide 'clay' with High Volumetric
8
9 Capacitance. Nature 2014, 516, 78-81.
10
11
12 (21)Luo, J.; Zhang, W.; Yuan, H.; Jin, C.; Zhang, L.; Huang, H.; Liang, C.; Xia,
13
14
Y.; Zhang, J.; Gan, Y.; Tao, X. Pillared Structure Design of MXene with Ultralarge
15
16
17 Interlayer Spacing for High-Performance Lithium-Ion Capacitors. ACS Nano. 2017, 11,
18
19
20 2459-2469.
21
22 (22)Xie, Y.; Dall'Agnese, Y.; Naguib, M.; Gogotsi, Y.; Barsoum, M. W.; Zhuang,
23
24
25 H. L.; Kent, P. R. C. Prediction and Characterization of MXene Nanosheet Anodes for
26
27
Non-Lithium-Ion Batteries. ACS Nano. 2014, 8, 9606-9615.
28
29
30 (23)Anasori, B.; Lukatskaya, M. R.; Gogotsi, Y. 2D Metal Carbides and Nitrides
31
32
33 (MXenes) for Energy Storage. Nat. Rev. Mater. 2017, 2, 16098.
34
35 (24)Shahzad, F.; Alhabeb, M.; Hatter, C. B.; Anasori, B.; Hong, S. M.; Koo, C.
36
37
38 M.; Gogotsi, Y. Electromagnetic Interference Shielding with 2D Transition Metal
39
40
Carbides (MXenes). Science 2016, 353, 1137-1140.
41
42
43 (25)Khazaei, M.; Ranjbar, A.; Arai, M.; Yunoki, S. Topological Insulators in the
44
45
46 Ordered Double Transition Metals M-2 ' M '' C-2 MXenes (M ' = Mo, W; M '' = Ti, Zr,
47
48 Hf). Phys. Rev. B 2016, 94, 125152.
49
50
51 (26)Jaramillo, T. F.; Jorgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.;
52
53
Chorkendorff, I. Identification of Active Edge Sites for Electrochemical H2 Evolution
54
55
56 from MoS2 Nanocatalysts. Science 2007, 317, 100-102.
57
58
59 (27)Ling, C.; Shi, L.; Ouyang, Y.; Wang, J. Searching for Highly Active Catalysts
60

ACS Paragon Plus Environment

 ACS Applied Nano Materials Page 30 of 34

1
2
3
4 for Hydrogen Evolution Reaction Based on O-Terminated MXenes through a Simple
5
6
7 Descriptor. Chem. Mater. 2016, 28, 9026-9032.
8
9 (28)Ling, C.; Shi, L.; Ouyang, Y.; Chen, Q.; Wang, J. Transition Metal-Promoted
10
11
12 V2CO2 (MXenes): A New and Highly Active Catalyst for Hydrogen Evolution
13
14
Reaction. Adv. Sci. 2016, 3, 1600180.
15
16
17 (29)Seh, Z. W.; Fredrickson, K. D.; Anasori, B.; Kibsgaard, J.; Strickler, A. L.;
18
19
20 Lukatskaya, M. R.; Gogotsi, Y.; Jaramillo, T. F.; Vojvodic, A. Two-Dimensional
21
22 Molybdenum Carbide (MXene) as an Efficient Electrocatalyst for Hydrogen Evolution.
23
24
25 ACS Energy Lett. 2016, 1, 589-594.
26
27
(30)Wang, S.; Chen, L.; Wu, Y.; Zhang, Q. Surface Modifications of Ti2CO2 for
28
29
30 Obtaining High Hydrogen Evolution Reaction Activity and Conductivity: A
31
32
33 Computational Approach. ChemPhysChem. 2018, 19, 3380-3387.
34
35 (31)Alameda, L. T.; Moradifar, P.; Metzger, Z. P.; Alem, N.; Schaak, R. E.
36
37
38 Topochemical Deintercalation of Al from MoAIB: Stepwise Etching Pathway, Layered
39
40
Intergrowth Structures, and Two-Dimensional MBene. J. Am. Chem. Soc. 2018, 140,
41
42
43 8833-8840.
44
45
46 (32)Zhang, H. M.; Dai, F. Z.; Xiang, H. M.; Wang, X. H.; Zhang, Z. L.; Zhou, Y.
47
48 C. Phase Pure and Well Crystalline Cr2AlB2: A Key Precursor for Two-dimensional
49
50
51 CrB. J. Mater. Sci. Technol. 2019, 35, 1593-1600.
52
53
(33)Guo, Z.; Zhou, J.; Sun, Z. New Two-Dimensional Transition Metal Borides
54
55
56 for Li ion Batteries and Electrocatalysis. J. Mater. Chem. A 2017, 5, 23530-23535.
57
58
59 (34)Wang, J.; Ye, T.-N.; Gong, Y.; Wu, J.; Miao, N.; Tada, T.; Hosono, H.
60

ACS Paragon Plus Environment

Page 31 of 34 ACS Applied Nano Materials

1
2
3
4 Discovery of Hexagonal Ternary Phase Ti2InB2 and its Evolution to Layered Boride
5
6
7 TiB. Nat. Commun. 2019, 10, 2284.
8
9 (35)Kresse, G.; Furthmuller, J. Efficient Iterative Schemes for ab initio Total-
10
11
12 energy Calculations Using a Plane-wave Basis Set. Phys. Rev. B 1996, 54, 11169-11186.
13
14
(36)Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation
15
16
17 Made Simple. Phys. Rev. Lett. 1996, 77, 3865-3868.
18
19
20 (37)Hammer, B.; Hansen, L. B.; Norskov, J. K. Improved Adsorption Energetics
21
22 within Density-functional Theory Using Revised Perdew-Burke-Ernzerhof Functionals.
23
24
25 Phys. Rev. B 1999, 59, 7413-7421.
26
27
(38)Grimme, S. Semiempirical GGA-type Density Functional Constructed with a
28
29
30 Long-range Dispersion Correction. J. Comput. Chem. 2006, 27, 1787-1799.
31
32
33 (39)Henkelman, G.; Uberuaga, B. P.; Jonsson, H. A climbing Image Nudged
34
35 Elastic Band Method for Finding Saddle Points and Minimum Energy Paths. J. Chem.
36
37
38 Phys. 2000, 113, 9901-9904.
39
40
(40)Cheng, Y. W.; Wang, L. J.; Song, Y.; Zhang, Y. M. Deep Insights into the
41
42
43 Exfoliation Properties of MAX to MXenes and the Hydrogen Evolution Performances
44
45
46 of 2D MXenes. J. Mater. Chem. A 2019, 7, 15862-15870.
47
48 (41)Gao, G.; O'Mullane, A. P.; Du, A. 2D MXenes: A New Family of Promising
49
50
51 Catalysts for the Hydrogen Evolution Reaction. ACS Catal. 2017, 7, 494-500.
52
53
(42)Bajdich, M.; Garcia-Mota, M.; Vojvodic, A.; Norskov, J. K.; Bell, A. T.
54
55
56 Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical
57
58
59 Oxidation of Water. J. Am. Chem. Soc. 2013, 135, 13521-13530.
60

ACS Paragon Plus Environment

 ACS Applied Nano Materials Page 32 of 34

1
2
3
4 (43)Hansen, H. A.; Rossmeisl, J.; Norskov, J. K. Surface Pourbaix Diagrams and
5
6
7 Oxygen Reduction Activity of Pt, Ag and Ni(111) Surfaces Studied by DFT. Phys.
8
9 Chem. Chem. Phys. 2008, 10, 3722-3730.
10
11
12 (44)Norskov, J. K.; Bligaard, T.; Logadottir, A.; Kitchin, J. R.; Chen, J. G.;
13
14
Pandelov, S.; Norskov, J. K. Trends in the Exchange Current for Hydrogen Evolution.
15
16
17 J. Electrochem. Soc. 2005, 152, J23-J26.
18
19
20 (45)Booth, T. J.; Blake, P.; Nair, R. R.; Jiang, D.; Hill, E. W.; Bangert, U.; Bleloch,
21
22 A.; Gass, M.; Novoselov, K. S.; Katsnelson, M. I.; Geim, A. K. Macroscopic Graphene
23
24
25 Membranes and their Extraordinary Stiffness. Nano Lett. 2008, 8, 2442-2446.
26
27
(46)Zhao, S.; Li, Z.; Yang, J. Obtaining Two-Dimensional Electron Gas in Free
28
29
30 Space without Resorting to Electron Doping: An Electride Based Design. J. Am. Chem.
31
32
33 Soc. 2014, 136, 13313-13318.
34
35 (47)Becke, A. D.; Edgecombe, K. E. A Simple Measure of Electron Localization
36
37
38 in Atomic and Molecular-systems. J. Chem. Phys. 1990, 92, 5397-5403.
39
40
(48)Silkin, V. M.; Zhao, J.; Guinea, F.; Chulkov, E. V.; Echenique, P. M.; Petek,
41
42
43 H. Image Potential States in Graphene. Phys. Rev. B 2009, 80, 121408.
44
45
46 (49)Feng, M.; Zhao, J.; Petek, H. Atomlike, Hollow-core-bound Molecular
47
48 Orbitals of C60. Science 2008, 320, 359-362.
49
50
51 (50)Okada, S.; Oshiyama, A.; Saito, S. Nearly Free Electron States in Carbon
52
53
Nanotube Bundles. Phys. Rev. B 2000, 62, 7634-7638.
54
55
56 (51)Xu, C.; Wang, L. B.; Liu, Z. B.; Chen, L.; Guo, J. K.; Kang, N.; Ma, X. L.;
57
58
59 Cheng, H. M.; Ren, W. C. Large-Area High-Quality 2D Ultrathin Mo2C
60

ACS Paragon Plus Environment

Page 33 of 34 ACS Applied Nano Materials

1
2
3
4 Superconducting Crystals. Nat. Mater. 2015, 14, 1135.
5
6
7 (52)Handoko, A. D.; Fredrickson, K. D.; Anasori, B.; Convey, K. W.; Johnson, L.
8
9 R.; Gogotsi, Y.; Vojvodic, A.; Seh, Z. W. Tuning the Basal Plane Functionalization of
10
11
12 Two-Dimensional Metal Carbides (MXenes) To Control Hydrogen Evolution Activity.
13
14
ACS Appl.Energy Mater. 2018, 1, 173-180.
15
16
17 (53)Li, P. K.; Zhu, J. G.; Handoko, A. D.; Zhang, R. F.; Wang, H. T.; Legut, D.;
18
19
20 Wen, X. D.; Fu, Z. H.; Seh, Z. W.; Zhang, Q. F. High-Throughput Theoretical
21
22 Optimization of the Hydrogen Evolution Reaction on MXenes by Transition Metal
23
24
25 Modification. J. Mater. Chem. A 2018, 6, 4271-4278.
26
27
(54)Cheng, Y.-W.; Dai, J.-H.; Zhang, Y.-M.; Song, Y. Transition Metal
28
29
30 Modification and Carbon Vacancy Promoted Cr2CO2 (MXenes): a New Opportunity
31
32
33 for a Highly Active Catalyst for the Hydrogen Evolution Reaction. J. Mater. Chem. A
34
35 2018, 6, 20956-20965.
36
37
38 (55)Cheng, Y.-W.; Dai, J.-H.; Zhang, Y.-M.; Song, Y. Two-Dimensional, Ordered,
39
40
Double Transition Metal Carbides (MXenes): A New Family of Promising Catalysts
41
42
43 for the Hydrogen Evolution Reaction. J. Phys. Chem. C 2018, 122, 28113-28122.
44
45
46 (56)Skulason, E.; Karlberg, G. S.; Rossmeisl, J.; Bligaard, T.; Greeley, J.; Jonsson,
47
48 H.; Norskov, J. K. Density Functional Theory Calculations for the Hydrogen Evolution
49
50
51 Reaction in an Electrochemical Double Layer on the Pt(111) Electrode. Phys. Chem.
52
53
Chem. Phys. 2007, 9, 3241-3250.
54
55
56 (57)Tang, Q.; Jiang, D.-E. Mechanism of Hydrogen Evolution Reaction on 1T-
57
58
59 MoS2 from First Principles. ACS Catal. 2016, 6, 4953-4961.
60

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