An oxidized magnetic Au single atom on doped TiO 2 (110) becomes a high performance CO oxidation catalyst due to the charge e ﬀ ect † 2017 Journal of Materials Chemistry A

Catalysis using gold nanoparticles supported on oxides has been under extensive investigation for many important application processes. However, how to tune the charge state of a given Au species to perform a speci ﬁ c chemical reaction, e.g. CO oxidation, remains elusive. Here, using ﬁ rst-principles calculations, we show clearly that an intrinsically inert Au anion deposited on oxygen-de ﬁ cient TiO 2 (110) (Au@TiO 2 (110)) can be tuned and optimized into a highly e ﬀ ective single atom catalyst (SAC), due to the depletion of the d-orbital by substrate doping. Particularly, Ni- and Cu-doped Au@TiO 2 complexes undergo a reconstruction driven by one of the two dissociated O atoms upon CO oxidation. The remaining O atom heals the surface oxygen vacancy and results in a stable bow-shaped surface “ O – Au – O ” species; thereby the highly oxidized Au single atom now exhibits magnetism and dramatically enhanced activity and stability for O 2 activation and CO oxidation, due to the emergence of high density of states near the Fermi level. Based on further extensive calculations, we establish the “ charge selection rule ” for O 2 activation and CO oxidation on Au: the positively charged Au SAC is more active than its negatively charged counterpart for O 2 activation, and the more positively charged the Au, the more active it is.


Introduction
Gold (Au) is considered to be extremely catalytically inert in many chemical processes, as manifested by the high resistance to oxidation of the surface Au atoms and the weak binding with many other gas phase molecules. 1,2 However, since the discovery of the excellent catalysis of Au nanoparticles (NPs) 3 on metal oxide substrates, extensive studies have been devoted to the understanding of the underlying mechanisms operative for the high activities of the supported Au NPs for a variety of important catalytic reactions. [4][5][6][7][8][9][10] Accordingly, a number of mechanisms have been proposed to elucidate the enhanced activities of Au NPs, including an odd number of electrons, 11 the quantum size effect, 11,12 metal-nonmetal transitions in a given cluster size regime, 13 and the presence of poorly coordinated edge or corner atoms. [14][15][16] Moreover, it is also widely recognized that the interactions between the Au and the support, including the strain effect, 17 the charge state [18][19][20][21] of the Au atom, and particularly the charge transfer between the Au NPs and the substrates 22 have been regarded to be crucial in determining the performance of the Au NPs. For instance, Au clusters located at the F-centers on MgO(001) were reported to be negatively charged and highly active for CO oxidation. 5,21,23 In contrast, recent investigations suggest that the active sites for CO oxidation are comprised of positively charged Au atoms and metallic Au nanoparticles appear to be spectators that do not participate in the reaction. 8,[24][25][26] In addition, there are also several reports indicating that metallic Au is the active species that is highly reactive for O 2 activation and CO oxidation. 19,27 Therefore, a fundamental question regarding the catalysis mechanism of a given Au structure is whether the negatively or positively charged state is more favorable for O 2 activation. The answer to this question is important for highly efficient catalyst design for many industrial processes, such as CO oxidation. Intuitively, a negatively charged Au species with excessive electron charge may be more favorable for O 2 binding via electron charge transfer, facilitating the O 2 activation and CO oxidation. However, such a scenario has so far not been rigorously examined using state-of-the-art theoretical and/or experimental approaches, especially when several other factors as mentioned above cannot be convincingly excluded from Au NPs.
A gold single-atom catalyst with a well-dened simple structure and a highly dispersed single active center provides an ideal platform for illustrating the above question, i.e., the charge effect in Au catalysis. Note that as a new concept in heterogeneous catalysis, SACs are now widely expected to maximize the efficiency of noble metals and offer great potential for enhanced chemical activity and selectivity. Recently, various highly efficient SACs with excellent stability and selectivity have been fabricated and theoretically investigated, such as Pt, Ti, Rh, Pd, and Ru on FeO x supports for CO oxidation 28,29 and an Fe SAC on a silica matrix for methane activation. 30 It has been reported that, as the ultimate small size limit of noble Au, a single Au atom supported on rutile TiO 2 (110) was rather inert to CO oxidation, 21,29,31 like its bulk Au counterpart. Despite complete experimental and theoretical analysis, the charge state effect on its chemical activity still remains unclear, whilst the system also offers a contrasting case for further understanding, design and development of effective SACs.
Using rst-principles calculations on the simple model of Au SACs, we clearly demonstrate the role of charge state in determining the activities of the Au species supported on oxide substrates with the Au SAC on rutile TiO 2 (110) as a prototype example. Here, the Au SAC is conrmed to preferably occupy the surface oxygen vacancy (V O ) site of the TiO 2 (110) substrate 32 and its charge states and chemical activity toward O 2 activation and CO oxidation can be tuned via the substrate doping approach. The results show that the catalytically inert Au SAC on rutile TiO 2 (110) is negatively charged, i.e., Q(Au) ¼ À0.38 e. Intriguingly, the catalysis of the essentially inert Au SAC can be triggered by substitution of a neighboring Ti atom by another transition metal element with a relatively large electronegativity (such as Ru, Rh, Pt, Cu, or Ni). The key point is that such a dopant gradually tunes the Au anion to become a positively charged cation with a signicantly reduced occupation of the d orbital. Consequently, a monotonically increased activity of the Au SAC as a function of its charge state can be established, that is, the more positively charged the Au SAC, the higher the d-band of the Au SAC, and consequently the more active the Au SAC. More specically, upon the rst CO oxidation via an adsorbed O 2 molecule, the Ni-doped Au@TiO 2 (110) complex (denoted as Au@(Ni)TiO 2 (110) (Q(Au) ¼ +0.03 e)) undergoes a local reconstruction, driven by one of the dissociated O atoms, healing the surface oxygen vacancy and resulting in a novel bowshaped surface O-Au-O species. Thus, such an oxidized Au cation in O-Au-O (Q(Au) ¼ +0.64 e) exhibits much enhanced activity and stability for continued CO oxidation, in contrast to previous observations that the healing of the oxygen vacancy usually reduces the catalysis capability of the adsorbed transition metal SACs because of clustering. 29,33,34

Methods
The present work was carried out using rst-principles calculations within the density functional theory 35 adopting the spinpolarized generalized gradient approximation as implemented in the VASP code. The interactions of the valence electrons with the ionic cores were described by the projector augmented wave (PAW) method. 36 For the exchange-correlation functional, we used the generalized gradient approximation of Perdew, Burke, and Ernzerhof. 37 The electronic wave functions were expanded in a plane wave basis with an energy cutoff of 500 eV. To obtain the correct band gap of the TiO 2 , we used the DFT + U method with U ¼ 4.5 eV, leading to a band gap of about 2.4 eV. Note that our tests show that the choice of U values around 5.0 eV leads to negligible differences for the calculated results, such as the adsorption energy of the O 2 molecule and reaction barrier for CO oxidation. The calculated lattice parameters for the primitive rutile TiO 2 unit cell are a ¼ b ¼ 4.662Å and c ¼ 2.959Å, respectively, in good agreement with experimental results. 38 The rutile TiO 2 (110) surface was simulated by a periodic four-layer c (4 Â 2) slab model consisting of 192 atoms with $13Å of vacuum in between the slabs (for details, see Fig. S1 and the structural data in S1, ESI †). The k-space integration was carried out using a Monkhorst-Pack grid of 2 Â 3 Â 1 k points in the surface Brillouin zone of the c (4 Â 2) unit cell. All atoms except those in the bottom layer were allowed to relax along the calculated forces until all the residual force components were lower than 0.01 eVÅ À1 . In consideration of the experimental conditions and previous calculations, we performed calculations which showed that the Au adatom is located in the vicinity of the surface oxygen vacancy (V O ) site of the rutile TiO 2 (110) which is denoted as Au@TiO 2 (110) throughout the document. For the interaction of the O 2 (CO) molecule with the Au@TiO 2 (110) catalyst, we initially placed the O 2 (CO) molecule about 4.5Å away from the Au atom followed by full structural optimization. Bader charge analysis 39 is applied to evaluate the charge transfer.

Results and discussion
As a starting point, we conrm that the Au atom prefers to occupy the surface V O site on TiO 2 (110) with binding energy E b (Au) ¼ 206.093 kJ mol À1 (for details, see Fig. S2 in the ESI †), which is in accordance with the experimental observation that surface V O sites play a dominant role in stabilizing Au atoms 32 and Pd atoms. [40][41][42] Based on this, we examined the adsorption and activation of an O 2 molecule on Au@TiO 2 , which is usually the ratedetermining step for CO oxidation. Our results show that the O 2 molecule can only very weakly adsorb on the supported Au monomer (see Fig. S3, ESI †), with an exothermic energy of 5.114 kJ mol À1 . The bond length of the adsorbed O 2 molecule remains almost the same as compared with that in its gas phase, 1.24Å, indicating that the Au SAC is highly inert to O 2 . In addition, an incoming CO will further push the weakly adsorbed O 2 away from the Au atom, and occupy the top site of the Au atom, with an exothermic energy of 48.725 kJ mol À1 . Therefore, the preference of the CO adsorption on the Au SAC thoroughly blocks the O 2 activation and hence prevents the CO from being oxidized by O 2 , in line with experimental observations. 31 To understand the highly inert nature of the Au atom on TiO 2 (110) for O 2 activation, we analyzed its local projected density of states (LPDOS) in Fig. 1(a). Evidently, the main peaks of the d-orbital are positioned below À1.6 eV, and the highest-occupied molecular orbital (HOMO) hybridizes with its neighboring Ti atoms at about 0.57 eV below the Fermi level. Furthermore, the symmetric spin-majority and spin-minority LPDOS conrm that there are no unpaired electrons located on the Au atom. All these features strongly indicate that the Au monomer is negatively charged, and the Bader analysis 39 further conrms that the Au anion is charged by about 0.38 e, which shis the d-orbital of the Au downward relative to the Fermi level. Additional calculations show that the energy gap between the HOMO(Au) and the lowest-unoccupied molecular orbital of the incoming O 2 (LUMO(O 2 )) is very large, about 1.527 eV, prohibiting their orbital hybridization and charge transfer from the HOMO(Au) to the 2pp*-like LUMO(O 2 ). 41 Therefore, the O 2 can be hardly activated because of the repulsion between orbitals of the adsorbate, 1 and the Au monomer acting as a "spectator" in CO oxidation. 31 Next, inspired by our central question, we examined the possibility of modifying the catalytic performance of the Au SAC on TiO 2 (110) by tuning the charge states of the Au SAC site via the substrate doping approach. For doing this, rst, a relatively electronegative Ni atom was employed as a substitutional dopant for the Ti atom. [43][44][45] It was found that the Ni dopant favors the substitution of a Ti atom close to the V O site, and this conguration is about 13.508 kJ mol À1 more stable than the case when the Ni atom substitutes for one of the subsurface Ti atoms (see Fig. S4, ESI †). Signicantly, Ni-doping modulates the electronic structure of the Au@TiO 2 (110) around the Fermi level, as seen in the LPDOS in Fig. 1(b). First, the orbital hybridization between Au and Ni considerably broadens the LPDOS of the Au atom and shis its d-orbitals upward to the Fermi level. Second, the HOMO of the Au SAC is spinminority dominated, and the spin-majority orbitals are totally unoccupied. Such features strongly indicate that the electron charge accumulated on the Au single atom is signicantly reduced; indeed, Bader charge analysis conrms that the Au monomer is now slightly oxidized and positively charged by about 0.03 e.
To examine whether the anion-cation transition of the Au single atom can promote the catalytic activity, we then further investigated the adsorption and activation of an O 2 molecule on the Au SAC supported on an Ni-doped TiO 2 (110) substrate. Based on further extensive calculations, we identied the most stable adsorption conguration of the O 2 molecule on the oxidized Au SAC. The O 2 molecule prefers an end-on structure, forming an angle :O-O-Au ¼ 107.63 (see Fig. S5(A), ESI †). The binding of the O 2 molecule with the Au SAC is mainly accompanied by the hybridization of the oxygen 2pp* orbital with the HOMO of Au. Note that part of the antibonding 2pp* electronic state of O 2 is now shied downward below the E F (for more details, see Fig. S5(B and C) and S5 †), conrming a charge transfer from the Au SAC to the O 2 molecule, which results in an extended O-O bond length (1.31Å) and leads to an exothermic adsorption energy of 97.643 kJ mol À1 . Furthermore, the calculated stretching vibrational frequency of the adsorbed O 2 species has been red-shied to 1158.9 cm À1 from a value of 1560.8 cm À1 for the case of the gas phase. Convincingly, these results demonstrate that the O-O bond is considerably activated on the positively charged Au cation due to Ni-doping in the substrate.
Having clearly illustrated the critical step for O 2 activation by the Au cation on the Ni-doped TiO 2 (110) complex, we now investigate the kinetic processes of CO oxidation using the optimized NEB method. 46 Note that three CO oxidation mechanisms proposed by recent theoretical investigations 47,48 have been examined in the present study. We conrmed that the CO oxidation surprisingly prefers a quasi-Langmuir-Hinshelwood (L-H) process in this case, namely, CO can adsorb relatively weakly on the single Au atom close to the adsorbed O 2 molecule and the co-adsorbed molecules undergo a bimolecular reaction through the formation of a CO 2 precursor, which is subsequently released upon further activation, and the optimized substrate structure upon CO 2 desorption is shown as the initial state (IS) conguration in Fig. 3. The minimum energy path (MEP) and energetics for the oxidation of the rst CO molecule on the Au single atom catalyst is shown in Fig. 2. Specically, we identied that the rst CO molecule adsorbs in the vicinity of the O 2 molecule on the Au catalyst via the well-known backdonation charge transfer mechanism, 49,50 i.e., donation of CO 5s electrons to the Au@TiO 2 (110) substrate and back-donation from the Au SAC into the unoccupied 2p* orbital of CO, as conrmed by the additional electronic charge density analysis detailed in Fig. S6, ESI. † We emphasize that one important issue in the CO oxidation on Au clusters supported on metal oxides is the formation of carbonate species that poison the active sites. 51 However, one can see that the formation of a carbonate-like species (see the TS state in Fig. 2) is 385.652 kJ mol À1 less stable than the formation of CO 2 on Au@(Ni)TiO 2 (110), indicating good catalytic properties of the present system. Here, we note that, upon Ni-doping, the oxidized Au atom contributes signicantly to the LPDOS by the Fermi level, which promotes such a back-donation process for CO adsorption with an exothermic adsorption energy of 12.157 kJ mol À1 , see Fig. 2. Consequently, the bond length of the adsorbed CO species is slightly enlarged to 1.15Å from 1.14Å of the gas phase, and correspondingly the C-O vibrational frequency is red shied to 2069.5 cm À1 from 2120.6 cm À1 . For the transition state (TS), a low activation barrier of E bar ¼ 49.015 kJ mol À1 is identied in the process of CO 2 formation, as shown in Fig. 2. Subsequently, a linear CO 2 product can be readily released with an exothermic energy of 336.637 kJ mol À1 , as shown in the nal state (FS). It is clear that even such a modest activation 52 of the CO by Au@TiO 2 (110) doped with Ni renders the Au monomer a good SAC candidate in avoiding the important issue of CO poisoning in heterogeneous catalysis.
More intriguingly, a novel stable SAC surface structure is generated aer the release of the rst CO 2 molecule, see FS in Fig. 2. Specically, the surface V O is spontaneously "healed" by the remaining O atom from the O 2 reactant, and now the whole catalyst complex can be viewed as Au@TiO 2 (110) doped with an O-Ni pair, i.e., Au@(O-Ni)TiO 2 (110). Here, we note that a previous investigation also predicted a similar phenomenon on a defective oxide surface, 29 where the healing of the oxygen vacancy is believed to promote the adsorbed metal SAC clustering, and hence to reduce the selectivity and performance of the SAC. 34 On the contrary, in the present case, the remaining O atom healing the V O renders the Au atom to form a very stable bow-shaped surface O-Au-O species, with an exothermic energy of 300.069 kJ mol À1 . Therefore, the Au atom is now highly stabilized and oxidized, i.e., Q(Au) ¼ +0.64 e. Note that, recently, Wang et al. 53 found that single Au cation active sites can be generated from adsorbed Au 20 clusters on TiO 2 (110), exhibiting excellent catalysis for CO oxidation. In the present structure, the d-orbital-dominated HOMO (LUMO) of the Au cation is located right below (above) the Fermi level, as presented in Fig. 1(c). The Au cation is now surprisingly spin polarized, i.e., possessing a magnetic moment about 0.5 mB. Consequently, the high LPDOS assigned to the HOMO (Au) strongly implies that the magnetic and oxidized Au atom with unpaired electron in the O-Au-O may exhibit high preference in catalysis for successive rounds of O 2 activation and CO oxidation from the spin-selection point of view, 54,55 i.e., a system with high spin state is generally more active toward spin-triplet O 2 activation.
The catalytic cycle of CO oxidation over the bow-shaped magnetic Au cation in Au@(O-Ni)TiO 2 (110) (see Fig. 3(i)) obtained by NEB calculations is summarized in Fig. 3. The extensive calculations show that the rst incoming CO oxidation prefers the L-H process, see Fig. 3(ii). Similarly, the O 2 molecule is rst signicantly activated on the Au@(O-Ni) TiO 2 (110), with an exothermic energy of 72.460 kJ mol À1 , which is slightly smaller than that calculated for a previous structure shown in Fig. S5(A). † However, we note that the relatively smaller binding energy of the O 2 molecule in the present bow- (step (ii)). Our calculations show that, in the minimum energy path, to form a CO 2 precursor, a CO 3 species (carbonate, see Fig. 3(iv)) will be rstly formed as a local minimum which is only 6.561 kJ mol À1 higher in energy than the conguration shown in (ii), by overcoming a small energy barrier of 60.40 kJ mol À1 (see Fig. 3(iii) denoted as TS1). Based on that, when further overcoming an activation barrier of 37.919 kJ mol À1 (see Fig. 3(v) denoted as TS2), a linear CO 2 species can be formed. When nishing the above steps, an O atom dissociated from the adsorbed O 2 molecule is still le on the Au monomer, as seen from step (vi). When the second CO molecule approaches the deposited Au site (step (vii)), a new reaction of CO ad + O ad ¼ CO 2 process (step (vii) and TS3) can  readily proceed via the Eley-Rideal (E-R) reaction mechanism. The calculated barrier of this reaction is only 54.418 kJ mol À1 , shown in TS3. Aer releasing the second CO 2 upon overcoming a negligible energy barrier (around 14.473 kJ mol À1 ), the catalyst system is recovered to the initial bow-shaped Au SAC (step i).
Here, we emphasize that the high performance of the above Au@(O-Ni)TiO 2 (110) SAC in CO catalytic oxidation, to the negatively charge Au anion counterpart in Au@TiO 2 (110), is essentially due to the positively charged electronic state (of the Au single atom), which effectively contributes to the d-orbitaldominated LPDOS near the Fermi level and facilitates O 2 activation via the charge transfer mechanism. These ndings on the one hand illustrate that Au single cations rather than anions can exhibit excellent catalysis for O 2 activation and CO oxidation, and on the other hand support previous statement that the active sites of Au NPs should be localized on these positively charged Au atoms. 8,22,[24][25][26]53 To further validate such a charge state effect on the activity of the Au SAC on TiO 2 (110) and gure out a simple approach for further optimizing its catalysis in O 2 activation and CO oxidation, we carried out more extensive calculations to examine the effects of doping with other transition metals on the capability of Au@TiO 2 (110) for O 2 activation. Here, four additional TM elements (Ru, Rh, Pt, and Cu) with different values of electronegativity were considered as the dopants. Similar to the structures presented in Fig. S8, † these elements are found to prefer the same site to stabilize the Au atom. As expected, we note that, with Bader charge analysis, these dopants result in different charge states for the Au atom. Therefore, the doped Au@(TM)TiO 2 (110) complexes can serve as an ideal platform to demonstrate the trend of the charge-state effect on catalysis. Briey, we show that the activation rate of the O 2 molecule is almost exactly monotonically increased as a function of the charge depletion of the Au atom. Specically, the more positively charged the Au atom, the stronger the activation of the O 2 molecule on it, as reected by the values of the red-shied n(O-O) shown in Fig. 4.
Finally, we note that there are already many experimental studies establishing various approaches for improving the photocatalysis of TiO 2 (110), such as by doping metal 56-59 and non-metal elements, 43 and co-doping methods as well. 60 In addition, in the ESI (Fig. S9 and S8 †), we have also presented a comparison of the formation energies of the dopant elements in TiO 2 (110); one can see that all the investigated elements (Pt, Ru, Rh, Cu, and Ni) possess comparable formation energies lying between those of Co and Al which can be readily doped in both anatase and rutile TiO 2 . 58,61 Here, we note that both Cu and Ni dopants possess relatively low formation energies relative to Pt, Ru, and Rh, and only the former two can stabilize the bowshaped O-Au-O structure. These interesting results indicate that Cu and Ni are much preferred dopants for enhancing the chemical activity of Au on TiO 2 (110). Correspondingly, we expect that the present theoretical work will motivate future experimental efforts in this eld.

Conclusions
Herein, by means of extensive rst-principles calculations on a very simple Au SAC model, we have clearly elucidated the role of charge state in determining the activity of the Au species supported on a TiO 2 (110) oxide substrate for O 2 activation and CO oxidation. Intriguingly, the intrinsically inert Au anion SAC on rutile TiO 2 (110) can be tuned into a highly efficient Au cation SAC by the depletion of the d-orbital of the Au atom via substrate doping with a transition metal atom, whilst the more positively charged the Au atom, the higher its activation of the O 2 molecule, supporting the most recent ndings that the catalytically active site of Au NPs should be localized on these poorly coordinated Au cations. Such ndings shed new insight into gold catalysis and are expected to be instrumental in the design of highly efficient and costeffective noble-metal-based catalysts for many O 2 -involved chemical reactions.

Conflicts of interest
There are no conicts to declare.