Temperature-Controlled Selectivity of Hydrogenation and

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Temperature-controlled selectivity of hydrogenation and hydrodeoxygenation in the conversion of biomass molecule by the Ru1/mpg-C3N4 catalyst Shubo Tian, Ziyun Wang, Wanbing Gong, Wenxing Chen, Quanchen Feng, Qi Xu, Chun Chen, Chen Chen, Qing Peng, Lin Gu, Huijun Zhao, Peijun Hu, Dingsheng Wang, and Yadong Li J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b06029 • Publication Date (Web): 30 Aug 2018 Downloaded from http://pubs.acs.org on August 30, 2018

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Journal of the American Chemical Society

Temperature-controlled selectivity of hydrogenation and hydrodeoxygenation in the conversion of biomass molecule by the Ru1/mpgC3N4 catalyst Shubo Tian1†, Ziyun Wang2†, Wanbing Gong3†, Wenxing Chen1, Quanchen Feng1, Qi Xu1, Chun Chen3, Chen Chen1, Qing Peng1, Lin Gu4, Huijun Zhao3, P. Hu2, Dingsheng Wang1*, and Yadong Li1 1

Department of Chemistry, Tsinghua University, Beijing 100084, China School of Chemistry and Chemical Engineering The Queen’s University of Belfast Belfast BT9 5AG (UK) 3 Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, P. R. China 4 Insitute of Physics, Chinese academy of Science Beijing 100190 (China) 2

Supporting Information Placeholder ABSTRACT: Hydrogenation and hydrodeoxygenation

are significant and distinct approaches for the conversion of biomass and biomass-derived oxygenated chemicals into high value-added chemicals and fuels. However, it remains a great challenge to synthesize catalysts that simultaneously possess excellent hydrogenation and hydrodeoxygenation performances. Herein, we report a catalyst made of isolated single-atom Ru supported on mesoporous graphitic carbon nitride (Ru1/mpg-C3N4), fabricated by a wet impregnation method. The asprepared Ru1/mpg-C3N4 catalyst shows excellent hydrogenation and hydrodeoxygenation performances. First-principles calculations reveal that the Ru atom is mobilized, and the active site is induced by adsorption of the reactants. A systematic reaction mechanism is proposed, suggesting that vanillyl alcohol is the deoxygenation prohibited product, while 2-methoxy-pcresol is the deoxygenation allowed product. Thus, the excellent selectivity for the hydrogenation or hydrodeoxygenation of vanillin at different temperatures are results from switching between the two types of products.

As energy systems and the chemical economy gradually shift from fossil fuels to renewable resources, it becomes urgent to develop technologies to promote the transformation of renewable biomass and their derivatives to safe energy fuel and final economic products of industrial relevance.1-4 The high selectivity of hydrogenation and hydrodeoxygenation makes these reactions effective and distinct approachs to realize those goals.5,6 As an effective approach, hydrodeoxygenation plays an important role in upgrading the biofuel7-9, and hydrogenation is one of the most important processes for producing final economic

products10,11. Until now, commercial catalysts of hydrogenation and hydrodeoxygenation generally contain toxic metal elements and require harsh reaction conditions.12 Hence, it is urgent to develop an eco-friendly and high performance catalyst. Different types of eco-friendly catalysts, including noble metals and non-noble metals, have been developed for the liquid-phase hydrogenation or hydrodeoxygenation of biomass.7,11,13 However, non-noble metal catalysts often require harsh conditions and noble metal catalysts are expensive, impeding their wide use. Recently, isolated single-atom catalysts have sparked much interest in heterogeneous catalysis due to their high catalytic activity, selectivity, and total atom utilization.14-21 However, the synthesis of such catalysts is still a challenge because isolated single atoms are very mobile and easily agglomerate. Graphitic carbon nitride is nitrogen rich and anchor metal atoms to resist metal sintering22-25, making it an ideal support for single-atom catalysts.26-29 In this rapidly developing research field, isolated single-atom catalysts have been demonstrated to be highly active catalysts for many reactions, including the water-gas shift reaction, CO oxidation and energy conversion reactions.30-35 Nevertheless, upgrading biofuel through isolated single-atom catalysis has rarely been studied. Herein, we used a simple wet impregnation method to synthesize a mesoporous carbon nitride supported isolated single-atom Ru catalyst (Ru1/mpg-C3N4). The as-prepared Ru1/mpg-C3N4 catalyst exhibits excellent activity and selectivity for both the hydrogenation and hydrodeoxygenation of vanillin. First-principles calculations reveal that the Ru atom is mobilized and that the excellent selectivity of Ru1/mpg-C3N4 at different temperatures is due to switching between the deoxygenation prohibited and deoxygenation allowed products.

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Mpg-C3N4 was first synthesized by the thermallyinduced self-condensation of cyanamide using colloidal silica as a template according to a previous method.36 The as-prepared mpg-C3N4 exhibited mesoporous structure and the pore diameters were approximately 10–15 nm (Figure S1). As shown by the X-ray powder diffraction (XRD) patterns in Figure S2, the as-prepared sample showed the typical crystal pattern of mpg-C3N4.36 The infrared spectrum (Figure S3) demonstrates the formation of extended C-N-C networks.37,38 Subsequently, mpg-C3N4 was homogeneously dispersed in water and adjusted to a PH of 1 by hydrochloric acid (note: hydrochloric acid can prevent hydrolysis of Ru3+. Otherwise, the Ru nanoparticles will be formed (Figure S4)), followed by the injection of RuCl3 aqueous solution. Through the co-precipitation method, the Ru precursor was uniformly dispersed on mpg-C3N4. Afterward, this mixture was pyrolyzed at 300 °C under the protection of a flow of N2, during which the Ru precursor was partly reduced and anchored by the nitrogen of mpg-C3N4. Upon deposition of the Ru element, transmission electron microscopy (TEM) (Figure 1a) and high-angle annular darkfield scanning TEM (HAADF-STEM) images (Figure 1b) reveal that the as-prepared sample retains the initial mesoporous structure. The XRD pattern does not show any additional diffraction peaks of Ru (Figure S2), and there are no obvious Ru nanoclusters or nanoparticles in the TEM images (Figure 1a). The homogeneous distribution of Ru atoms is further supported by the HAADF-STEM image (Figure 1b) and the corresponding energy-dispersive X-ray (EDX) mapping analysis (Figure 1c). The content of Ru is estimated to be approximately 0.10 wt% according to inductively coupled plasma optical emission spectrometry analysis. These results preliminarily indicate that Ru atoms do not agglomerate and disperse well on the mpg-C3N4 support during the pyrolysis process. To verify the isolated single atom Ru on mpg-C3N4, we performed aberrationcorrected HAADF-STEM (AC HAADF-STEM) measurements on Ru1/mpg-C3N4. The AC HAADF-STEM image (Figure 1d) with atomic resolution elucidates the small bright dots homogeneously distributed on the mpg-C3N4 substrate. Due to the remarkable difference in Z-contrast between Ru and N/C, the small bright dots can be determined to be Ru atoms, beyond which, no Ru nanoclusters or nanoparticles were observed in the AC HAADF-STEM image, further indicating that the Ru exists as isolated single atom. Element-selective X-ray absorption fine structure (XAFS) analysis is a powerful method for determining the coordination environment and chemical state of the absorbing species with high sensitivity.39 To investigate the electronic structure and coordination configuration of the Ru element, the Ru1/mpg-C3N4 sample was further identified by XAFS analysis. Figure 2a shows the Ru K-edge X-ray absorption near-edge structure (XANES) spectra of the Ru1/mpg-C3N4 sample along with those of Ru foil and RuO2 as references. The absorption edge of single-atom Ru is located between that of Ru and RuO2, suggesting that the Ru atom valence is situated between that of Ru0 and Ru4+. The partly positive valence results from the interaction between Ru and the support. Figure 2b shows the Fourier

transformed (FT) k3-weighted extended X-ray absorption fine structure (EXAFS) spectrum of Ru1/mpg-C3N4 and the reference spectra of Ru and RuO2 at the Ru K-edge. There is only one prominent peak at 1.6 Å, which can be assigned to the Ru-N contribution, but no peaks are observed at ~2.6 Å corresponding to the Ru-Ru contribution, confirming the sole presence of isolated-single atom Ru in the Ru1/mpgC3N4 catalyst. Therefore, combining the XRD, TEM, AC HAADF-STEM, and XAFS results, we can conclude that Ru atoms are atomically dispersed on Ru1/mpg-C3N4. To obtain the quantitative chemical configuration of the Ru atom, EXAFS fitting was also performed to extract the structure parameters. According to the fitting parameters given in Figure 2c, 2d, Figures S5-8 and Table S1, the coordination numbers of Ru-C/N within Ru1/mpg-C3N4 is approximately 3.8, and the mean bond length of Ru−N is 2.06 Å.

Figure 1 (a) TEM and (b) HAADF-STEM images of the Ru1/mpg-C3N4 sample. (c) Corresponding EDX element maps showing the distributions of Ru, C and N. (d) AC HAADF-STEM images of the Ru1/mpg-C3N4 sample.

Figure 2. (a) XANES spectra at the Ru k-edge of Ru1/mpg-C3N4, RuO2 and Ru foil. (b) Fourier transform (FT) at the Ru k-edge of Ru1/mpg-C3N4, RuO2 and Ru foil. (c, d) Corresponding fits of the EXAFS spectrum of Ru1/mpg-C3N4 in R space and K space, respectively.


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Journal of the American Chemical Society Then, we investigated the catalytic properties of the asprepared Ru1/mpg-C3N4 sample. Vanillin, as a model biomass molecule can be effectively hydrogenated into vanillyl alcohol and hydrodeoxygenated into 2-methoxy-pcresol or methoxyphenol.7,40 By optimizing the reaction temperature, the Ru1/mpg-C3N4 sample shows excellent selectivity for both the hydrogenation and hydrodeoxygenation of vanillin in water. As shown in Table 1, we achieved a selectivity of ~100% and conversion of 95% in the hydrogenation of vanillin into vanillyl alcohol at 60 °C. When the temperature rises to 120 °C, the product contains both vanillyl alcohol and 2-methoxy-p-cresol. However, again we obtained a selectivity of ~100% and conversion of ~100% into 2-methoxy-p-cresol at 140 °C. Therefore, the excellent selectivity of both hydrogenation and hydrodeoxygenation can be achieved on the same catalyst. That is one of the best results for both hydrogenation and hydrodeoxygenation of vanillin using the same catalyst with only trace precious metal elements (Table S3). There is no performance difference between the different pore size of Ru1/mpg-C3N4 (Figure S9-10, Table S4). Under the same condition, by contrast, the mpg-C3N4 substrate itself is nearly reactively inert. When Ru NPs/mpg-C3N4 or Ru1/NC as catalyst, the conversion and selectivity is worse than the Ru1/mpg-C3N4, reflecting the superior catalytic performance of the Ru1/mpg-C3N4 catalyst (Figure S12-14, Table S2). After 5 cycles, the Ru1/mpg-C3N4 catalyst exhibits good recycling capability with well-retained activity and selectivity (Figures S15-16). Besides, the structures were unchanged from the fresh samples, as identified by XRD, AC HAADF-STEM and EXAFS, which corroborates the stability of the catalyst (Figure S17). Table 1. The hydrogenation and hydrodeoxygenation of vanillin at different temperatures, (a: vanillyl alcohol; b: 2methoxy-p-cresol). Catalyst

Temp.

Time

(°C)

(h)

Con.

Selectivity a (%)

b (%)

a

Ru1/C3N4

20

72

N.R.

-

-

a

Ru1/C3N4

40

72

15

~100

0

a

Ru1/C3N4

60

72

~95

~100

0

a

Ru1/C3N4

80

4

14

85

15

a

Ru1/C3N4

100

4

40

27

73

a

Ru1/C3N4

120

4

72

19

81

a

Ru1/C3N4

140

4

~100

0

~100

a

Ru1/C3N4

160

2

~100

0

~100

160

6

~100

0

~100

b a

Ru1/C3N4

substrate/catalyst=500, 4 MPa H2; bsubstrate/catalyst=2000,

stability of four possible structures of single-atom Ru (Figure S18). The stabilities of three structures (a, b, and c in Table S5 and Figure S19) range from -4.36 eV to -4.43 eV, and the structures in Figure S18 (a-c) are similar. These results suggest that the Ru atom is mobilized on carbon nitride and can diffuse between the site bonding with two N (Figure S18 (a)) to the site bonding with two N and one C (Figure S18 (c)). The adsorption energies of the reactants (vanillin and H2) on structure b (inset of Figure 3) are much stronger than those on a and c, indicating that structure b is likely dominant under the reaction conditions. (more details can be found in computational section 3 in SI). On structure b, we investigated four different reaction pathways from vanillin to 2-methoxyl-p-creosol as illustrated in Figure S20. The most favorable pathway is shown in Figure 3 and the comparison of different reaction pathways are systematically discussed in section 2 of the computation details in the SI. The hydrogenation of vanillin starts with the adsorption of vanillin on the Ru site, with a free energy adsorption energy of -0.42 eV at 60 °C and 0.21 eV at 140 °C. Then, the dissociated hydrogen couples with oxygen in the CHO group to form IM1, which possesses the highest barrier from vanillin to vanillyl alcohol. The barrier of IM1 hydrogen is very small, and the adsorption state of vanillyl alcohol is slightly unstable compared to IM1. As shown in Figure 3, the adsorbed vanillyl alcohol can desorb from the Ru site forming a gas-phase vanillyl alcohol product (dashed lines). Alternatively, the C-O bond in the CH2OH group in vanillyl alcohol can break to form IM2 (adsorbed OH and C7H7O2CH2 on the Ru site), which is higher than the energy change of during vanillyl alcohol desorption. The hydrogenation of OH is found to be more favorable as illustrated in Figure S22, and IM3 is then hydrogenated to form the product 2-methoxy-p-cresol. From the reaction profiles (Figure 3), the overall hydrogenated product, 2-methoxy-p-cresol, is much more thermodynamically stable than the partially hydrogenated product, vanillyl alcohol. However, the energetics increased from the adsorbed state of vanillyl alcohol to the transition state of IM2 hydrogenation (Figure 3), making the further deoxygenation of vanillyl alcohol difficult. Thus, vanillyl alcohol is the deoxygenation prohibited product, while 2-methoxylp-cresol is the deoxygenation allowed product. These results are in good agreement with our experimental results: at 60 °C the only product is vanillyl alcohol, because at low temperature the barrier of vanillyl alcohol hydrogenation is too high resulting in only the deoxygenation prohibited product. With increasing temperature, further hydrogenation is possible, and the products are mixed at 80, 100 and 120 °C. At 140 °C, only the deoxygenation allowed product, 2-methoxyl-p-cresol, is found.

TOF=330; TON=2000 To understand the dramatic difference in selectivity at different temperatures, we carried out a systematic investigation of the reaction mechanism of vanillin hydrogenation on single-atom Ru using first-principles calculations (computation details can be found in the SI). First, we tested the



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Figure 3. Free energy diagrams of vanillin hydrogenation to vanillyl alcohol and 2-methoxy-2-methoxy-p-cresol at 60 °C (blue) and 140 °C (red). The structures of reactant and products are shown above the energy profiles, while the intermediate state structures are shown below the energy profiles. The geometry of Ru1/mpg-C3N4 is shown in the upper right. In summary, we report an isolated single atom Ru1/mpgC3N4 catalyst. The as-prepared sample shows excellent selectivity in both the hydrogenation and hydrodeoxygenation of vanillin in aqueous media. First-principles calculations reveal the vanillyl alcohol and 2-methoxy-p-cresol are the deoxygenation prohibited and deoxygenation allowed products, respectively. The excellent selectivity of Ru1/mpg-C3N4 at different temperatures originates from switching between the two products.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Computational and experimental details (PDF)

AUTHOR INFORMATION

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Corresponding Authors *[email protected]

Author Contributions †

(10) Wang, C.; Wang, L.; Zhang, J.; Wang, H.; Lewis, J. P.; Xiao, F. S. J. Am. Chem. Soc. 2016, 138, 7880.

S.T., Z.W and W.G. contributed equally.

(22) Chen, X.; Zhang, J.; Fu, X.; Antonietti, M.; Wang, X. J. Am. Chem. Soc. 2009, 131, 11658.

Notes The authors declare no competing financial interests.

(23) Wang, X.; Chen, X.; Thomas, A.; Fu, X.; Antonietti, M. Adv. Mater. 2009, 21, 1609.

ACKNOWLEDGMENT

(24) Di, T.; Zhu, B.; Cheng, B.; Yu, J.; Xu, J. J. Catal. 2017, 352, 532.

This work was supported by China Ministry of Science and Technology under Contract of 2016YFA (0202801), and the National Natural Science Foundation of China (21471089, 21671117, 21521091, 21390393, 21590792, 91645203, U1463202).

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Temperature-Controlled Selectivity of Hydrogenation and

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