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Tunable Catalytic Performance of Single Pt Atom on the Doped Graphene in Direct Dehydrogenation of Propane by Rational Doping: A Density Functional Theory Study XiaoYing Sun, Peng Han, Bo Li, and Zhen Zhao J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.7b09736 • Publication Date (Web): 03 Jan 2018 Downloaded from http://pubs.acs.org on January 3, 2018

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The Journal of Physical Chemistry

Tunable Catalytic Performance of Single Pt atom on the Doped Graphene in Direct Dehydrogenation of Propane by Rational Doping: a Density Functional Theory Study XiaoYing Sun1, Peng Han1, Bo Li3, Zhen Zhao1,2∗ 1. Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical

Engineering, Shenyang Normal University, Shenyang 110034, China 2. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing, 102249, China 3. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, Liaoning, China.

E-mail: [email protected], [email protected], [email protected]

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Abstract

The catalytic reaction pathways and performance of supported single Pt atom on the nitrogen and boron-doped graphene in the direct dehydrogenation of propane (PDH) are investigated by using first principle calculations. The different dopants on graphene have distinct effects on the electronic structure of the supported Pt atom. The nitrogen on the support withdraws electrons from Pt, but boron donates electrons to Pt. Consequently, the d-band center of Pt atom is modified by either nitrogen or boron doping. The nitrogen doping shifts the d-band center of Pt atom closer to the Fermi level compared with the boron doping and the pristine ones. On the other hand, the d-band center has a significant influence on the C−H bond dissociation energy and reaction barrier. Therefore, better reactivity of Pt is found on the support with more nitrogen dopants as the d-band center is closer to Fermi level. Also the calculated dissociation energy and the first C−H bond activation barrier obey the BEP rule. The different ratios between nitrogen and boron on the co-doped graphene can continuously adjust the electronic structure of supported Pt and deliver the dissociation energy and reaction barrier in between the pure nitrogen and boron doped cases. Among various investigated supports, the graphene doped by pyridine nitrogen is predicted to be the most effective for enhancing Pt catalytic performance. The current work shows the promising catalytic performance of supported single Pt atom in PDH. More importantly, the tunable properties of the supported metal catalysts on the carbon materials are achieved by the rational doping which provides a practical strategy for the catalyst optimization.

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Introduction

Many single metal atom catalysts have been successfully synthesized and applied in various reactions such as Au, Fe, Pd, Pt. 8 Among them, the single Pt atom has an important status due to the prominent role of Pt catalysts in a wide range of catalytic reactions9-10. Zhu et al successfully confined the single Pt atom within the lattice of layered double hydroxides which is induced by Sn promoter. 11 The obtained Pt single atom catalyst show remarkable performance in heptane reforming reaction. In particularly, the obtained catalyst has a good selectivity because of the resistance to the hydrogenolysis side reaction. Zhang et al. used the modified active carbon as the single Pt atom catalyst support. The single Pt atom is fixed by the four oxygens on the support and has good catalytic performance in the hydrogenation of nitrobenzene and cyclohexanone. 12 These studies indicate the potential importance of the single Pt atom catalysis.

The direct dehydrogenation of propane (PDH) is one of the most important industrial reactions to produce propylene.1 The platinum and chromium oxide are the conventional catalysts used in PDH. 2,3 Especially, Pt is the industrial catalyst in Oleflex process of UOP company.4 The PDH reaction catalyzed by Pt supported on Al2O3 is performed above 500 ◦C and Sn is added as the promoter for the Pt catalyst. The current biggest challenge of Pt catalysts in PDH is the deactivation caused by coking and side reactions. 5,6 The coke formation is inevitable in PDH which will gradually cover the active sites and deactivate the catalysts. Generally, the Pt catalysts are periodically regenerated to remove coke. Many efforts are devoted to enhance the Pt’s ability to resist the coke formation. Pt particle size, promoter, and catalyst support etc. are all proposed to have a major impact on the coke formation. The further improvements in PDH require the rational design of geometrical and electronic structures of Pt catalysts. Recently, the single atom catalysis has aroused intense interests due to the reduction of using precious metal and the excellent catalytic performance. 7

The support has an obvious importance in the single atom catalyst. The single atom catalyst is very mobile under the reaction condition and inclines to the sinter and aggregation in particular at high temperature. The stability of the single atom catalyst is mainly dependent on the interaction with the support. Jones et al. mixed Pt/Al2O3 with CeO2 powder aging


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nanotube, graphehe etc. appeared to be a new class of materials as the metal catalyst support. 21 Compared with the conventional carbon support, carbon nanotube and graphene have well-defined nanostructure, good thermal conductivity, and controllable surface properties which make them more suitable as the support for metal catalysts. Even more, the heteroatom doping gives another method to optimize the property of the nanostructured carbon support. 22-24 Nitrogen, boron, and sulfur are the most often used dopants for the nanostructured carbon materials. In particular, nitrogen and boron has one more and less valence electron compared with carbon. They are resembling a n and p doping, respectively. It is well documented in literature that the either nitrogen or boron doping can greatly enhance the catalytic performance of supported metal catalysts25. In a recent study26, the DFT calculations demonstrate that the dopants, nitrogen and boron on the carbon nanotube support can significantly modify the charge state and electronic structure of gold catalysts in CO oxidation. Consequently, the adsorption of reactants and reaction mechanism behave differently on nitrogen and boron doped support. The authors of this work clearly described the relation among the dopants on the support, catalytic property of metal catalysts, and the mechanism. In current work, the first principle calculations are performed on the supported single Pt atom on the nitrogen and boron-doped graphene. There are two major goals for the current study. Firstly, we want to examine the catalytic performance of the single Pt atom on the graphene support in PDH. The catalytic performance of single Pt atom is proved in several different reports as mentioned above. It is of great importance to explore the properties of single Pt atom in PDH in order to further improve the catalytic performance. On the other hand, the origin of the enhanced catalytic performance of the single atom catalysis is still matter of debate. The current study can also accumulate the evidence for the deep understandings of the catalytic property of single atom catalyst. Secondly, the support has a major

at 800 ◦C and led to the trapped atomic Pt catalysis.13 The treatment at high temperature ensures the removal of unstable species. In their followed work14, they tested atomic PtSn catalysts supported on CeO2 in PDH. The catalysts show a remarkable catalytic performance which is much better than the conventional Al2O3-supported one. More importantly, CeO2 support can redisperse Pt catalyst and restore the original reactivity after mild oxidative regeneration. In the other study, the single Pt atom catalysis is obtained in the framework of MCM-22 support during the growth from 2D to 3D. 15 The Pt catalysts show exceptional stability under the oxidation-reduction cycles at 650 ◦C. More interestingly, the single Pt atom and subnanometer Pt catalysts have a good performance in the dehydrogenation of propane. In fact, the interaction between the single atom catalyst and the support not only gives the mechanical strength for the catalysts but also has a major effect on the catalytic performance. For example, the recent study reveals that Al2O3 nanosheet as the PtSn support in PDH shows a 99% selectivity of propylene. More importantly, the PtSn catalysts on the Al2O3 nanosheet reveals a superior ability of anticoking and antisintering. 16 The analysis indicates that Al3+ on the nanosheet leads to a strong interaction with Pt. The strong metal-support interactions not only stabilize catalysts but also engineer the d-band structure of Pt, which leads to the excellent selectivity17. Furthermore, the nanostructure carbon materials also appear to be an effective support for Pt catalyst in PDH. Liu et al. used a nanodimaond core and defective graphene shell as Pt support in PDH. It is indicated that the Pt on carbon support does not have any noticeable deactivation for a 100 h test, however the conventional Pt/ Al2O3 shows severe deactivation after 20 h18. Overall, the support optimization is one of the most effective strategies to enhance the Pt catalytic performance for PDH19. The carbon materials such as active carbon has a long history to use as the metal support in various industrial applications due to the unique properties including the large surface area, the chemical inertness, and stable in acid/base media etc.20 With the further development, the nanostructured carbon materials such as carbon


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when the force residue on the atom was smaller than 0.05 eV/Å. The reaction pathways and barriers were calculated by using the climbing image nudged elastic band (CINEB) method.31 The dissociation energy (Edisso) was calculated as, Edisso= EC3H7-H/pt/graphene - Epropane– Ept/graphene where EC3H7-H/pt/graphene is the total energy of the dissociated propane on Pt/graphene catalyst, Epropane is the energy of the propane molecule in gas phase, and Ept/graphene is the energy of clean Pt/graphene. The reaction barrier was calculated as the energy difference between the initial state and the highest image from CINEB calculations.

effect on the performance of Pt catalyst in PDH. One of the possible ways to improve Pt catalyst is resulted from the optimization of support. The doping is an effective way to tune the properties of the carbon support. However, there is still lacking the working principle for the rational doping to maximize the catalytic performance. By explicitly considering the several different configurations of nitrogen and boron dopants, this work could lay out the basis for the general frame of doping practice for the carbon support.

2. Computational Setup

3. Result and Discussion

The calculations reported here were performed by

Figure 2: Bader charge analysis on the single Pt atom supported on the undoped and doped graphene.

Figure 1: The configurations of the doped graphene support considered in current work. The dopants, nitrogen and boron, are varied around a mono-vacancy on graphene. The xNyBG notation indicates the number of nitrogen (x) and boron (y) on the doped graphene. 3NG represents three nitrogens occupy the vacancy site and 2NBG represents two nitrogens and one boron (1 is omitted in this case). The undoped graphene with a mono vacancy is labeled as VacG.

There are several different configurations of the dopants on the graphene. For example, nitrogen can be in the form of pyridine, graphitic, and pyrrolic on the nanostructured carbon materials. Among them, the pyridine nitrogen has been experimental observed.32 Three nitrogens in pyridine group are distributed around a mono carbon vacancy as shown in Figure 1. By using this configuration as the starting point, a serial dopant configurations on the graphene are built as the support for the single Pt atom. Not only the pure nitrogen or boron doping is considered, but also the dual dopants of nitrogen and boron are included. The dopant configurations shown in Figure 1 with the continuous varying of nitrogen/boron ratio can clearly reveal the effects of doping on the catalytic performance. Three carbon atoms around the mono vacancy can be

using periodic, spin-polarized DFT as implemented in the Vienna ab initio program package (VASP).27,28 The electron-ion interactions were described by the projector augmented wave (PAW) method proposed by Blöchl and implemented by Kresse.29,30 The PBE functional was used as an exchange-correlation functional approximation and a plane wave basis set with an energy cutoff of 400 eV was used. The graphene was modeled with a 6x6 unit cell and a 3x3 K point mesh was used for the Brillouin zone sampling. All the atoms in the cell were allowed to relax during the structure optimization and the optimization was stopped


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electronegativity difference between nitrogen and boron as the nitrogen is more electrophilic. Therefore, the charge is transferred from Pt to nitrogen and the opposite transfer is found on the boron doping case. The charge analysis clearly indicates that the different doping strategy can tune the electronic structure of supported Pt atom in a wide range. It is well known that the charged Pt has the different property from the metallic state which has the consequence on the catalytic performance. It is interesting to examine the performance of Pt with the different charges in PDH which is discussed below. Propane molecule has a strong C−H bond with the bonding energy of 409 kJ/mol. Therefore, the activation of the first C−H bond is generally considered as the rate-limiting step which is also verified in our previous work. 33,34 The dissociation energy (Edisso) and the barrier (Ea) of the first C−H bond breaking are good indicators to evaluate the catalytic performance of the single Pt atom on the various supports as the first one is used to describe thermodynamics and the second one is used to calibrate kinetics. The reaction pathway of the first C−H bond breaking in propane is shown in Figure 3. The single Pt atom on the graphene with high nitrogen dopants has more exothermic dissociation energy and lower reaction barrier. The activation of the first C−H bond is most favorable on the 3NG and 2NG support which is a nearly barrierless process. Also the structures of transition state share the similar feature for Pt catalysts on the different supports. At transition state, both hydrogen and carbon has a bonding with Pt and the distance between hydrogen and carbon is around 1.5 Å, which is more like a later transition state. As only single Pt atom as the catalyst, the better catalytic performance on 3NG and 2NG support can be attributed to the support effect. Therefore, the nitrogen doping on the graphene support brings higher reactivity for C−H bond activation than boron doping. Furthermore, we found that there is a linear relation between dissociation energy, reaction barrier and the charges on Pt atom as shown in Figure 4. It is suggested that positive charged Pt atom is more active for breaking C−H bond, and the Pt atoms on the 3BG and 3NG supports have the lowest and highest activity,

replaced with the different amount of nitrogen or boron dopants. Specifically, there are three nitrogen/boron (3NG, 3BG), two nitrogen/boron (2NG, 2BG), one nitrogen/boron (NG, BG), respectively, for single element doping. Furthermore, the co-doping is also considered in current work including two nitrogens and one boron (2NBG); one nitrogen and two borons (N2BG); one nitrogen and one boron (NBG), respectively, as shown in Figure 1. The optimized bond distances between Pt single atom and dopants on the catalyst are shown in Table S1. The bond distance between Pt and the atoms the support is around 2.0 Å. Considering the covalent radius of Pt (1.28 Å), N (0.75 Å) B (0.82 Å), C (0.77 Å), it is indicated that Pt has a covalent-like bonding with the N, B, and C on the support at the anchoring position. However, the bond distance between Pt and N is a little longer than the counterparts of B and C. More interestingly, the charge of Pt atom generally has a trend from the positive charge state to the negative charge state from nitrogen doping, codoping of nitrogen and boron to boron

Figure 3: Reaction pathway of the first C−H bond breaking in propane molecule on the supported single Pt catalyst. The important structures along pathway are also shown at bottom (Initial, Transition, Final states from left to right)

doping as shown in Figure 2. The Pt on 3NG and 2NG support has the most positive charges, while the Pt on 3BG support has the most negative charges. This phenomenon can be understood as the


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Figure 4: (a) The relation between the charges on Pt and the dissociation energy (E disso) of first C−H bond in propane. (b) The relation between the charges on Pt and the barrier (Ea) of first C−H bond breaking in propane.

respectively, for C−H bond activation by considering both dissociation energy and reaction barrier. The Pt atom at mono vacancy on the undoped graphene show intermediate performance between the catalysts on 3NG and 3BG support, which is not unexpected. The linear relation is further improved when calculation data are categorized into three groups which is purely N or B doping and N, B codoping cases as shown in Figure S2. To explore the origin of the observed relations among Pt charges and the activity, the d-band center of the supported Pt atom is calculated as shown in Figure 5. It is well documented in

literature that d-band center of transition metal is a key factor to influence the catalytic performance. 35,36 It has been proposed that transition metal has a better reactivity when the d-band center is more closer to Fermi level. The center of d band close to the Fermi level will shift the antibonding states upwards and become empty which will strengthen the adsorption energy. The relation among d-band center of supported Pt atom on the nitrogen-doped and undoped graphene with the dissociation energy, activation barrier is shown in Figure 5. It is clearly demonstrated that the d-band center indeed is a useful descriptor on the reactivity in C−H activation.

Figure 5: The relation between the d-band center of single Pt atom on various supports with the dissociation energy and reaction barrier.

Figure 6: The linear relation between the calculated dissociation energy and barrier for the activation of the first C−H bond.


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different supports which are 3NG, vacG, and BG, respectively, as shown in Table S2. In the related temperature range (600-800K), the rate constant on 3NG was at least one magnitude larger than the others. More importantly, the calculated barrier on the single Pt atom is comparable or even lower than the calculated barriers on the Pt(111), Pt(211), and Pt clusters. 40–42 It is also worth to point out that the reported barrier in these studies do not explicitly consider the support effect mostly. The selectivity in PDH is partly resulted from the competition between the desorption and the deep dehydrogenation of propylene. To investigate the performance of predicted the best 3NG support on the selectivity, the deep dehydrogenation of propylene is explored which the third hydrogen is abstracted. As shown in Figure S3 the barrier of the deep dehydrogenation is calculated to be 1.5 eV. On the other hand, the desorption energy of propylene is less than 0.5 eV as shown in Figure 7. The difference between the desorption energy and barrier of deep dehydrogenation indicates that the supported Pt on 3NG also has a good selectivity. Other side reaction pathway on Pt/3NG catalysts was also considered as shown in Figure S4 which starts from the primary hydrogen abstraction and leads to the formation of CH3CH2C. As shown in Figure S4, the second hydrogen abstraction barrier is 0.79 eV which is much bigger than the one on the pathway leading to the ethylene formation as shown in Figure 7. This further indicate the better selectivity for Pt on 3NG support.

useful descriptor on the reactivity in C-H activation. With the d-band center moving to the Fermi level, both the dissociation energy and reaction barrier are becoming more exothermic and smaller. Hence the electronic structure of the supported Pt is continuously tuned by doping, which consequently modify the catalytic capabilities to break the C−H bond. Moreover, the dissociation energy and the activation barrier also have a linear relation as shown in Figure 6, which suggests that BEP is applicable to the single supported Pt atom catalysis. BEP rule is a very useful scaling relation between the reaction enthalpy and reaction barrier. It has been reported that BEP is valid for the activations of a bunch of gas phase small molecules on the metal and metal oxide catalysts, which indicates the importance in heterogeneous catalysis. 37,38 It is also suggested that BEP rule is useful for the C−H bond activation on the doped carbon catalysts.39 Hence the current calculations indicate that BEP rule is potentially useful for the C−H activation on single metal atom supported on the carbon support. This conclusion further expands the scope of BEP rule. The ideal product from PDH is propylene which indicates that two hydrogen atoms are abstracted from propane. After the first C−H breaking, the dissociated fragment C3H7 is also adsorbed on Pt site. The reaction pathways for the second C−H activation and the desorption of propylene are shown in Figure 7. There are two important steps in Figure 7 for the propylene release. The first one is that the secondary hydrogen is abstracted from C3H7 as shown in transition state in Figure 7. It is noted that the single Pt on 3NG support has the lowest barrier among the different catalysts. The second one is is the desorption of propylene which single Pt on 3NG is also favorable. Overall, the calculations indicate that the single Pt atom on 3NG support has a higher reactivity for both the first and second C−H activation compared with the other investigated supports. Furthermore, the largest barrier during the whole process on the 3NG support is calculated to be 0.4 eV which is corresponded the second hydrogen abstraction. To further verify the reactivity of supported Pt on 3NG, the rate constant of the rate limiting step was calculated for PDH on single Pt at three

4. Conclusions To conclude this work, the catalytic performance and reaction pathways of PDH on the supported single Pt atom are revealed from the first principle calculations with the emphasis on the tunable effects from the doping of graphene support. The calculation indicates that the supported single Pt is an effective catalyst for propane activation with the largest barrier of 0.4 eV, which is comparable with the other Pt catalysts. This suggests that the experimentally synthesized single Pt atom catalyst can deliver the excellent catalytic performance in PDH with much less noble metal usage. Furthermore, the different support doping strategy can


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Acknowledgements

Figure 7: The second hydrogen abstraction from propane and propylene desorption on various supported Pt atom catalyst. The important structures along pathway are shown at the bottom (Initial, Transition, Intermediate, Final states from left to right).

effectively modify the electronic structure of supported Pt atom. The nitrogen and boron dopings have the opposite effect on the charged state of Pt atom, which leads to the shift of the d-band center. The dissociation energy and reaction barrier of the first C−H bond breaking in propane are related to the d-band center of supported Pt atom. It is therefore suggested that support doping is an effective method to tune the electronic structure of supported metal catalysts and consequently influence the catalytic performance. The pyridine nitrogendoped support is predicted to be the most active one for single Pt atom by comparing the first and second C−H bond activation. Moreover, the deep dehydrogenation at single Pt on 3NG support requires more energy than that for the desorption of propylene, which indicates a good selectivity is guaranteed. Overall, the current work predicts that the single Pt on 3NG support is a novel and effective catalyst for PDH and the support engineering by doping can optimize the property of the metal catalysts in a controllable way. Supporting Information: The calculated bond distance between supported Pt and substrate. The rate constant of the ratelimiting step, DOS analysis, deep dehydrogenation pathway analysis.

This work is supported by Liaoning Natural Science Foundation (No. 201602676) and NSFC (No. 91545117). The current work is partly supported by Special Fund of Liaoning Provincial Universities’ Fundamental Scientific Research Projects (No. LQN201703) and Shenyang Normal University (No. 51600308). The supports from Engineering Technology Research Center of Catalysis for Energy and Environment, Major Platform for Science and Technology of the Universities in Liaoning Province, Liaoning Province Key Laboratory for Highly Efficient Conversion and Clean Utilization of Oil and Gas Resources and Engineering Research Center for Highly Efficient Conversion and Clean Use of Oil and Gas Resources of Liaoning Province are highly appreciated.

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