Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation

Nature Communications - Tập 8 Số 1
Zailei Zhang1, Yihan Zhu2, Hiroyuki Asakura3, Bin Zhang1, Jiaguang Zhang1, Maoxiang Zhou4, Yu Han2, Tsunehiro Tanaka3, Aiqin Wang4, Tao Zhang4, Ning Yan1
1Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117585, Singapore
2Physical Sciences and Engineering Division, Advanced Membranes and Porous Materials Center, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia
3Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
4State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Tóm tắt

AbstractSingle-atom metal catalysts offer a promising way to utilize precious noble metal elements more effectively, provided that they are catalytically active and sufficiently stable. Herein, we report a synthetic strategy for Pt single-atom catalysts with outstanding stability in several reactions under demanding conditions. The Pt atoms are firmly anchored in the internal surface of mesoporous Al2O3, likely stabilized by coordinatively unsaturated pentahedral Al3+ centres. The catalyst keeps its structural integrity and excellent performance for the selective hydrogenation of 1,3-butadiene after exposure to a reductive atmosphere at 200 °C for 24 h. Compared to commercial Pt nanoparticle catalyst on Al2O3 and control samples, this system exhibits significantly enhanced stability and performance for n-hexane hydro-reforming at 550 °C for 48 h, although agglomeration of Pt single-atoms into clusters is observed after reaction. In CO oxidation, the Pt single-atom identity was fully maintained after 60 cycles between 100 and 400 °C over a one-month period.

Từ khóa


Tài liệu tham khảo

Hunt, A. J., Matharu, A. S., King, A. H. & Clark, J. H. The importance of elemental sustainability and critical element recovery. Green Chem. 17, 1949–1950 (2015).

Forecast of Platinum Supply & Demand in 2015 (Johnson Matthey, 2015).

Yang, X. F. et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Acc. Chem. Res. 46, 1740–1748 (2013).

Thomas, J. M. Catalysis: tens of thousands of atoms replaced by one. Nature 525, 325–326 (2015).

Flytzani-Stephanopoulos, M. & Gates, B. C. Atomically dispersed supported metal catalysts. Annu. Rev. Chem. Biomol. Eng. 3, 545–574 (2012).

Liu, J. Catalysis by supported single metal atoms. ACS Catal. 7, 34–59 (2017).

Flytzani-Stephanopoulos, M. Gold atoms stabilized on various supports catalyze the water-gas shift reaction. Acc. Chem. Res. 47, 783–792 (2014).

Cargnello, M. et al. Control of metal nanocrystal size reveals metal-support interface role for ceria catalysts. Science 341, 771–773 (2013).

Dvorak, F. et al. Creating single-atom Pt-ceria catalysts by surface step decoration. Nat. Commun. 7, 10801 (2016).

Gates, B. C. Supported metal clusters: synthesis, structure, and catalysis. Chem. Rev. 95, 511–522 (1995).

Willinger, M. G. et al. A case of strong metal-support interactions: combining advanced microscopy and model systems to elucidate the atomic structure of interfaces. Angew. Chem. Int. Ed. 53, 5998–6001 (2014).

Bruix, A. et al. Maximum noble-metal efficiency in catalytic materials: atomically dispersed surface platinum. Angew. Chem. Int. Ed. 53, 10525–10530 (2014).

Huang, W. et al. Low-temperature transformation of methane to methanol on Pd1O4 single sites anchored on the internal surface of microporous silicate. Angew. Chem. Int. Ed. 55, 13441–13445 (2016).

Kyriakou, G. et al. Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations. Science 335, 1209–1212 (2012).

Liu, P. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 352, 797–801 (2016).

Li, Y. K. et al. Thermal methane conversion to syngas mediated by Rh1-doped aluminum oxide cluster cations RhAl3O4 . J. Am. Chem. Soc. 138, 12854–12860 (2016).

Peterson, E. J. et al. Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina. Nat. Commun. 5, 4885 (2014).

Shi, Y. et al. Single-atom catalysis in mesoporous photovoltaics: the principle of utility maximization. Adv. Mater. 26, 8147–8153 (2014).

Vile, G. et al. A stable single-site palladium catalyst for hydrogenations. Angew. Chem. Int. Ed. 54, 11265–11269 (2015).

Wang, Y. G., Mei, D., Glezakou, V. A., Li, J. & Rousseau, R. Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles. Nat. Commun. 6, 6511 (2015).

Zhang, S. et al. Catalysis on singly dispersed bimetallic sites. Nat. Commun. 6, 7938 (2015).

Liu, J. et al. Tackling CO poisoning with single-atom alloy catalysts. J. Am. Chem. Soc. 138, 6396–6399 (2016).

Yang, S., Kim, J., Tak, Y. J., Soon, A. & Lee, H. Single-atom catalyst of platinum supported on titanium nitride for selective electrochemical reactions. Angew. Chem. Int. Ed. 55, 2058–2062 (2016).

Li, X. et al. Single-atom Pt as Co-catalyst for enhanced photocatalytic H2 evolution. Adv. Mater. 28, 2427–2431 (2016).

Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx . Nat. Chem. 3, 634–641 (2011).

Kistler, J. D. et al. A single-site platinum CO oxidation catalyst in zeolite KLTL: microscopic and spectroscopic determination of the locations of the platinum atoms. Angew. Chem. Int. Ed. 53, 8904–8907 (2014).

Choi, C. H. et al. Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst. Nat. Commun. 7, 10922 (2016).

Huang, Z. et al. Catalytically active single-atom sites fabricated from silver particles. Angew. Chem. Int. Ed. 51, 4198–4203 (2012).

Davis, R. J. & Derouane, E. G. A non-porous supported-platinum catalyst for aromatization of n-hexane. Nature 349, 313–315 (1991).

Joo, S. H. et al. Thermally stable Pt/mesoporous silica core-shell nanocatalysts for high-temperature reactions. Nat. Mater. 8, 126–131 (2009).

Jones, J. et al. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping. Science 353, 150–154 (2016).

Liu, L. et al. Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nat. Mater. 16, 132–138 (2017).

Lucci, F. R. et al. Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit. Nat. Commun. 6, 8550 (2015).

Yuan, Q. et al. Facile synthesis for ordered mesoporous gamma-aluminas with high thermal stability. J. Am. Chem. Soc. 130, 3465–3472 (2008).

Kwak, J. H. et al. Coordinatively unsaturated Al3+ centers as binding sites for active catalyst phases of platinum on gamma-Al2O3 . Science 325, 1670–1673 (2009).

Zhang, B. et al. Stabilizing a platinum1 single-atom catalyst on supported phosphomolybdic acid without compromising hydrogenation activity. Angew. Chem. Int. Ed. 55, 8319–8323 (2016).

Li, Y. H. et al. Unidirectional suppression of hydrogen oxidation on oxidized platinum clusters. Nat. Commun. 4, 2500 (2013).

Hall, M. D., Foran, G. J., Zhang, M., Beale, P. J. & Hambley, T. W. XANES determination of the platinum oxidation state distribution in cancer cells treated with platinum(IV) anticancer agents. J. Am. Chem. Soc. 125, 7524–7525 (2003).

Ding, K. et al. Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts. Science 350, 189–192 (2015).

Borchert, H. et al. Ligand-capped Pt nanocrystals as oxide-supported catalysts: FTIR spectroscopic investigations of the adsorption and oxidation of CO. Angew. Chem. Int. Ed. 46, 2923–2926 (2007).

Kale, M. J. & Christopher, P. Utilizing quantitative in situ FTIR spectroscopy to identify well-coordinated Pt atoms as the active site for CO oxidation on Al2O3-supported Pt catalysts. ACS Catal. 6, 5599–5609 (2016).

Kwak, J. H. et al. Role of pentacoordinated Al3+ ions in the high temperature phase transformation of γ-Al2O3 . J. Phys. Chem. C 112, 9486–9492 (2008).

Wei, H. et al. FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes. Nat. Commun. 5, 5634 (2014).

Schrader, I., Warneke, J., Backenkohler, J. & Kunz, S. Functionalization of platinum nanoparticles with L-proline: simultaneous enhancements of catalytic activity and selectivity. J. Am. Chem. Soc. 137, 905–912 (2015).

Morin, C., Simon, D. & Sautet, P. Intermediates in the hydrogenation of benzene to cyclohexene on Pt(111) and Pd(111): a comparison from DFT calculations. Surf. Sci. 600, 1339–1350 (2006).

Chen, C.-S., Chen, H.-W. & Cheng, W.-H. Study of selective hydrogenation of acetophenone on Pt/SiO2 . Appl. Catal. A-Gen. 248, 117–128 (2003).

Chen, M., Maeda, N., Baiker, A. & Huang, J. Molecular insight into Pt-catalyzed chemoselective hydrogenation of an aromatic ketone by in situ modulation–excitation IR spectroscopy. ACS Catal. 2, 2007–2013 (2012).

Musselwhite, N., Na, K., Alayoglu, S. & Somorjai, G. A. The pathway to total isomer selectivity: n-hexane conversion (reforming) on platinum nanoparticles supported on aluminum modified mesoporous silica (MCF-17). J. Am. Chem. Soc. 136, 16661–16665 (2014).

An, K., Alayoglu, S., Musselwhite, N., Na, K. & Somorjai, G. A. Designed catalysts from Pt nanoparticles supported on macroporous oxides for selective isomerization of n-hexane. J. Am. Chem. Soc. 136, 6830–6833 (2014).

Moses-DeBusk, M. et al. CO oxidation on supported single Pt atoms: experimental and ab initio density functional studies of CO interaction with Pt atom on theta-Al2O3(010) surface. J. Am. Chem. Soc. 135, 12634–12645 (2013).

Baker, L. R. et al. Furfuraldehyde hydrogenation on titanium oxide-supported platinum nanoparticles studied by sum frequency generation vibrational spectroscopy: acid-base catalysis explains the molecular origin of strong metal-support interactions. J. Am. Chem. Soc. 134, 14208–14216 (2012).

Tang, H. et al. Strong metal-support interactions between gold nanoparticles and nonoxides. J. Am. Chem. Soc. 138, 56–59 (2016).

Thông tin
Thông tin xuất bản

Nature Communications

Tập 8 Số 1

Thông tin tác giả