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Rational Design of Catalysts Using Quantum Chemical Calculations and Elucidation of Their Working Mechanism

峯 真也 大阪府立大学 DOI:info:doi/10.24729/00016959

2020.07.07

概要

This thesis consists of 6 chapters including chapter 1 as the overall introduction regarding to present research objectives, and chapter 2–6 are summarized as follows:

Chapter 2
This chapter describes the precise control of the optical properties of organic linkers within MOF photocatalysts for hydrogen production as well as the elucidation of their electronic state and activity prediction. In this study, we first synthesized two kinds of MOFs (Ti-MOF-NH2 and Zr- MOF-NH2) composed of a visible light responsive organic linker (2-aminoterephthalic acid :2-ATA) and inorganic metal clusters (Ti oxide cluster and Zr oxide cluster) and applied them for the hydrogen generation reaction from an aqueous solution of triethanolamine (TEOA) as a sacrificial reagent. As a result, of these two catalysts, only Ti-MOF-NH2 efficiently catalyzes the hydrogen evolution reaction under visible light irradiation in the wavelength range of 420 nm to 550 nm. The results of first-principles calculations on Ti-MOF-NH2 suggested that the LUMO level of 2-ATA is located at the energetically higher position than that of Ti oxide clusters. This energy difference enables the efficient electron transfer from photoexcited 2-ATA to Ti oxide clusters, that is a charge separation, leading to increase the reaction rate. On the other hand, the results of first-principles calculations on Zr-MOF-NH2 suggested that the LUMO level of 2-ATA is located at the energetically lower position than that of Ti oxide clusters. This shows that the photoexcitation process of Zr-MOF-NH2 are essentially localized on the 2-ATA without achieving the charge separation, thus leading to the fast charge recombination of photoformed charges to give a negligible reaction rate. Furthermore, quantum chemical calculations show that the LUMO level of Ti oxide clusters shifted to energetically higher position than that of bulk titanium oxide due to the quantum size effect. This LUMO level shift of Ti oxide clusters increases the reduction ability of photoformed electron, enabling an efficient hydrogen evolution reaction even without depositing the Pt nano particles as cocatalysts on Ti-MOF- NH2.

Chapter 3
In Chapter 3 describes the electronic state elucidation and activity prediction of MOF photocatalysts for oxygen generation reaction where the visible light excitation of metal oxide cluster plays a crucial role. Band structure elucidations of bulk metal oxides by first-principles calculation predicted that MOF (Fe-MOF) having Fe oxide cluster can have narrow energy gap and sufficiently deep HOMO level to oxidize water. This results suggest that Fe-MOF can act as an effective visible light responsive photocatalyst for oxygen generation reaction so that we have synthesized Fe-MOF- bpdc which is composed of 4,4 '-biphenyldicarboxylic acid (dpdc) and an Fe oxide cluster. It was found that Fe-MOF-bpdc shows activity for the oxygen evolution reaction from the sacrificial aqueous solution under visible light irradiation. Then, we have investigated the combination of Fe- MOF-bpdc with cobalt oxide (CoOx), an excellent oxygen generation co-catalyst, to enhance the reaction activity. As expected, the oxygen generation activity was improved about twice at the maximum when 2 wt% of CoOx as metal was supported. On the other hand, the rate of the 2- propanol oxidation reaction, which is a two-electron oxidation reaction, was hardly affected by the loading of CoOx. Therefore, it was clarified that CoOx acts as a hole trapping site on the Fe oxide cluster and shows a high co-catalytic ability especially for the oxidation reactions which requires large numbers of holes such as for the oxidation reaction of water.

Chapter 4
This chapter describes the development of a visible light responsive tantalum oxynitride (TaON) thin film photocatalyst using magnetron sputtering method and the band structure elucidation by DFT calculations. Nitrogen atoms doped in the transition metal oxide form bands at positions higher than the valence band level composed of the 2p orbitals of oxygen, and contribute to the narrowing of the band gap. In this study, we investigated the formation of tantalum-based photocatalysts by reactive sputtering using tantalum metal as a target material in the presence of oxygen and nitrogen. As a result, a thin film photocatalyst consisting of TaON phase was successfully synthesized by controlling the target-substrate distance and sputtering pressure appropriately under high substrate temperature condition (1073 K). As a result of the photoelectrochemical measurement, it was clarified that this thin film catalyst functions as a photoelectrode which promotes the oxidation reaction of water under the irradiation of visible light over 450 nm. It was also found that the photoelectrochemical properties of the TaON thin-film catalyst can be significantly improved by heating the catalyst in an ammonia atmosphere in order to increase the crystallinity and optimize the donor concentration. Then, the band structure of TaON was analyzed by first-principles calculations, and it was clarified that the TaON thin film has a narrow band gap suitable for visible light absorption and a sufficiently high conduction band level capable of hydrogen generation. Therefore, TaON thin film was supported by iridium oxide nanocolloid known as an efficient co-catalyst to reduce the hydrogen evolution overpotential and applied it to the hydrogen evolution reaction from methanol aqueous solution under visible light irradiation (λ > 450 nm). As a result, continuous hydrogen generation was confirmed and it was clarified that this catalyst effectively acts as a visible light responsive hydrogen generation photocatalyst.

Chapter 5
In Chapter 5, we describe the rapid synthesis and catalysis of functional spherical silica particles prepared using tannic acid as well as the results of first-principles calculations to elucidate the chemical role of tannic acid for the formation of silica particles. The tannic acid (TTA) obtained for natural products shows a unique adsorption behavior due to the phenolic hydroxyl groups contained with high density in its molecular structure. In this study, the rapid synthesis of silica particles was investigated aiming at promoting the condensation reaction of 3- aminopropyltrimethoxysilane (APTMS) based on the interaction between the amino group of APTMS and TA. As a result, it was found that the gelation easily proceeded just only by mixing APTMS with TA in an aqueous solvent at room temperature, and uniform spherical silica particles with a particle size of several hundred nanometers were synthesized. Usually, the trifunctional alkoxysilane alone did not cause gelation spontaneously under the basic conditions in the typical Stöber process. However, in the presence of TA, the gelation process of APTMS was completed in a few minutes to give spherical silica particles in good yield. Detailed investigations of synthesis conditions and first-principles calculations revealed that this high reactivity was due to the effective interaction of the deprotonated phenol group of TA with the protonated amino group of APTMS. By firing the spherical silica particles thus obtained, porous silica having micro-sized pores can be synthesized, and on the other hand, it has been found that the non-fired sample functions as an iron ion adsorbent based on a strong interaction between the contained TA and iron ions (Fe3 +), and also acts as a heterogeneous catalyst for the deacetalization reaction. Furthermore, the spherical silica particle synthesis method using TA was found to be applicable to other trifunctional alkoxysilanes having alkylamino and alkylthiol groups.

Chapter 6
In this chapter, the results and conclusions of the various investigations covered in this thesis have been summarized.

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参考文献

1. M. Choi, K. Na, J. Kim, Y. Sakamoto, O. Terasaki and R. Ryoo, Nature, 2009, 461, 246.

2. M. Waki, Y. Maegawa, K. Hara, Y. Goto, S. Shirai, Y. Yamada, N. Mizoshita, T. Tani, W. J. Chun, S. Muratsugu, M. Tada, A. Fukuoka and S. Inagaki, J. Am. Chem. Soc., 2014, 136, 4003.

3. N. R. Shiju, A. H. Alberts, S. Khalid, D. R. Brown and G. Rothenberg, Angew. Chemie-Int. Ed., 2011, 50, 9615.

4. A. Fukuoka, N. Higashimoto, Y. Sakamoto, M. Sasaki, N. Sugimoto, S. Inagaki, Y. Fukushima and M. Ichikawa, Catal. Today, 2001, 66, 23.

5. M. Chiesa, V. Meynen, S. Van Doorslaer, P. Cool and E. F. Vansant, J. Am. Chem. Soc., 2006, 128, 8955.

6. A. Corma, H. Garcia and F. X. Liabres i Xamena, Chem. Rev., 2010, 110, 4606.

7. A. Corma, Chem. Rev., 1997, 97, 2373.

8. N. M. Muresan, J. Willkomm, D. Mersch, Y. Vaynzof and E. Reisner, Angew. Chemie-Int. Ed., 2012, 51, 12749.

9. S. Inagaki, S. Guan, Y. Fukushima, T. Ohsuna and O. Terasaki, J. Am. Chem. Soc., 1999, 121, 9611.

10. A. Leyva-Pérez, P. García and A. Corma, Angew. Chemie-Int. Ed., 2014, 53, 8687.

11. J. Aleman, A. V. Chadwick, J. He, M. Hess, K. Horie, R. G. Jones, P. Kratochvil, I. Meisel, I. Mita and G. Moad, Pure Appl. Chem., 2007, 79, 1801.

12. G. Kickelbick, Hybrid Mater., 2014, 1, 39.

13. O. M. Yaghi, M. O'Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi and J. Kim, Nature, 2003, 423, 705.

14. S. Kitagawa, R. Kitaura and S. Noro, Angew. Chemie-Int. Ed., 2004, 43, 2334.

15. G. Férey, Chem. Soc. Rev., 2008, 37, 191.

16. M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe and O. M. Yaghi, Science, 2002, 295, 469.

17. N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O’Keeffe and O. M. Yaghi, Science, 2003, 300, 1127.

18. X. Zhao, B. Xiao, A. J. Fletcher, K. Thomas, D. Bradshaw and M. J. Rosseinsky, Science, 2004, 306, 1012.

19. S. Shimomura, M. Higuchi, R. Matsuda, K. Yoneda, Y. Hijikata, Y. Kubota, Y. Mita, J. Kim, M. Takata and S. Kitagawa, Nat. Chem., 2010, 2, 633.

20. W. Lu, Z. Wei, Z.-Y. Gu, T.-F. Liu, J. Park, J. Park, J. Tian, M. Zhang, Q. Zhang, T. Gentle Iii, M. Bosch and H.-C. Zhou, Chem. Soc. Rev., 2014, 43, 5561.

21. R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R. V. Belosludov, T. C. Kobayashi, H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe and Y. Mita, Nature, 2005, 436, 238.

22. T. Rodenas, I. Luz, G. Prieto, B. Seoane, H. Miro, A. Corma, F. Kapteijn, F. X. Llabrés, J. Gascon, F. X. Llabrés i Xamena and J. Gascon, Nat. Mater., 2014, 14, 48.

23. P. Horcajada, T. Chalati, C. Serre, B. Gillet, C. Sebrie, T. Baati, J. F. Eubank, D. Heurtaux, P. Clayette, C. Kreuz, J.-S. Chang, Y. K. Hwang, V. Marsaud, P.-N. Bories, L. Cynober, S. Gil, G. Férey, P. Couvreur and R. Gref, Nat. Mater., 2010, 9, 172.

24. R. Ricco, L. Malfatti, M. Takahashi, A. J. Hill and P. Falcaro, J. Mater. Chem. A, 2013, 1, 13033.

25. C.-Y. Sun, X.-L. Wang, X. Zhang, C. Qin, P. Li, Z.-M. Su, D.-X. Zhu, G.-G. Shan, K.-Z. Shao, H. Wu and J. Li, Nat. Commun., 2013, 4, 2717.

26. J. D. Evans, C. J. Sumby and C. J. Doonan, Chem. Soc. Rev., 2014, 43, 5933.

27. J. R. Li, J. Sculley and H. C. Zhou, Chem. Rev., 2012, 112, 869.

28. S. Horike, M. Dinca, K. Tamaki and J. R. Long, J. Am. Chem. Soc., 2008, 130, 5854.

29. J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and J. T. Hupp, Chem. Soc. Rev., 2009, 38, 1450.

30. F. Song, C. Wang, J. M. Falkowski, L. Ma and W. Lin, J. Am. Chem. Soc., 2010, 132, 15390.

31. M. Yoon, R. Srirambalaji and K. Kim, Chem. Rev., 2012, 112, 1196.

32. P. Deria, J. E. Mondloch, O. Karagiaridi, W. Bury, J. T. Hupp and O. K. Farha, Chem. Soc. Rev., 2014, 41.

33. C. A. Kent, D. Liu, L. Ma, J. M. Papanikolas, T. J. Meyer and W. Lin, J. Am. Chem. Soc., 2011, 133, 12940.

34. J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang and C.-Y. Su, Chem. Soc. Rev., 2014, 43, 6011.

35. D. Bradshaw, S. El-Hankari and L. Lupica-Spagnolo, Chem. Soc. Rev., 2014, 43, 5431.

36. Y. He, B. Li, M. O’Keeffe and B. Chen, Chem. Soc. Rev., 2014, 43, 5618.

37. Q.-L. Zhu and Q. Xu, Chem. Soc. Rev., 2014, 43, 5648.

38. Z. Zhang, W.-Y. Gao, L. Wojtas, S. Ma, M. Eddaoudi and M. J. Zaworotko, Angew. Chemie- Int. Ed., 2012, 51, 9330.

39. Y. Chen, V. Lykourinou, C. Vetromile, T. Hoang, L.-J. Ming, R. W. Larsen and S. Ma, J. Am. Chem. Soc., 2012, 134, 13188.

40. Z. Guo, C. Xiao, R. V. Maligal-Ganesh, L. Zhou, T. W. Goh, X. Li, D. Tesfagaber, A. Thiel and W. Huang, ACS Catal., 2014, 4, 1340.

41. G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surblé and I. Margiolaki, Science, 2005, 309, 2040.

42. Y. Liu and Z. Tang, Adv. Mater., 2013, 25, 5819.

43. M. Zhao, K. Deng, L. He, Y. Liu, G. Li, H. Zhao and Z. Tang, J. Am. Chem. Soc., 2014, 136, 1738.

44. X.-H. Liu, J.-G. Ma, Z. Niu, G.-M. Yang and P. Cheng, Angew. Chemie Int. Ed., 2015, 54, 988.

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