In situ observation of oscillatory redox dynamics of copper.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
16 07 2020
16 07 2020
Historique:
received:
13
03
2020
accepted:
23
06
2020
entrez:
18
7
2020
pubmed:
18
7
2020
medline:
18
7
2020
Statut:
epublish
Résumé
How a catalyst behaves microscopically under reaction conditions, and what kinds of active sites transiently exist on its surface, is still very much a mystery to the scientific community. Here we present an in situ study on the red-ox behaviour of copper in the model reaction of hydrogen oxidation. Direct imaging combined with on-line mass spectroscopy shows that activity emerges near a phase boundary, where complex spatio-temporal dynamics are induced by the competing action of simultaneously present oxidizing and reducing agents. Using a combination of in situ imaging with in situ X-ray absorption spectroscopy and scanning photoemission microscopy, we reveal the relation between chemical and morphological dynamics and demonstrate that a static picture of active sites is insufficient to describe catalytic function of redox-active metal catalysts. The observed oscillatory redox dynamics provide a unique insight on phase-cooperation and a convenient and general mechanism for constant re-generation of transient active sites.
Identifiants
pubmed: 32678088
doi: 10.1038/s41467-020-17346-7
pii: 10.1038/s41467-020-17346-7
pmc: PMC7366672
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
3554Références
Tao, F. et al. Break-up of stepped platinum catalyst surfaces by high CO coverage. Science 327, 850–853 (2010).
pubmed: 20150498
Tamaru, K. Dynamic in-situ studies of catalytic reactions. Appl. Catal. A Gen. 113, 125–130 (1994).
Somorjai, G. A. & Vanhove, M. A. Adsorbate-induced restructuring of surfaces. Prog. Surf. Sci. 30, 201–231 (1989).
Besenbacher, F. et al. Dynamics of adsorbate-induced restructuring and reaction between adsorbates on Cu and Ni surfaces studied by scanning-tunneling-microscopy. J. Vac. Sci. Technol. A 11, 1637–1639 (1993).
Xu, F. et al. Redox-mediated reconstruction of copper during carbon monoxide oxidation. J. Phys. Chem. C 118, 15902–15909 (2014).
Bluhm, H. et al. Methanol oxidation on a copper catalyst investigated using in situ X-ray photoelectron spectroscopy. J. Phys. Chem. B 108, 14340–14347 (2004).
Greiner, M. T. et al. The oxidation of copper catalysts during ethylene epoxidation. Phys. Chem. Chem. Phys. 17, 25073–25089 (2015).
pubmed: 26345450
Greiner, M. T. et al. Phase coexistence of multiple copper oxides on AgCu catalysts during ethylene epoxidation. ACS Catal. 8, 2286–2295 (2018).
Hendriksen, B. L. M. et al. The role of steps in surface catalysis and reaction oscillations. Nat. Chem. 2, 730–734 (2010).
pubmed: 20729891
Wang, Y. & Wöll, C. Chemical reactions on metal oxide surfaces investigated by vibrational spectroscopy. Surf. Sci. 603, 1589–1599 (2009).
Wachs, I. E., Jehng, J.-M. & Ueda, W. Determination of the chemical nature of active surface sites present on bulk mixed metal oxide catalysts. J. Phys. Chem. B 109, 2275–2284 (2005).
pubmed: 16851220
Eren, B., Heine, C., Bluhm, H., Somorjai, G. A. & Salmeron, M. Catalyst chemical state during CO oxidation reaction on Cu(111) studied with ambient-pressure X-ray photoelectron spectroscopy and near edge X-ray adsorption fine structure spectroscopy. J. Am. Chem. Soc. 137, 11186–11190 (2015).
pubmed: 26275662
Vendelbo, S. B. et al. Visualization of oscillatory behaviour of Pt nanoparticles catalysing CO oxidation. Nat. Mater. 13, 884–890 (2014).
pubmed: 25038730
Hendriksen, B.L.M. & Frenken, J.W.M. CO oxidation on Pt(110): scanning tunneling microscopy inside a high-pressure flow reactor. Phys. Rev. Lett. 89, 046101 (2002).
van Spronsen, M. A., Frenken, J. W. M. & Groot, I. M. N. Observing the oxidation of platinum. Nat. Commun. 8, 429 (2017).
pubmed: 28874734
pmcid: 5585323
Ammon, C. et al. Dissociation and oxidation of methanol on Cu(110). Surf. Sci. 507, 845–850 (2002).
Pradhan, S., Reddy, A. S., Devi, R. N. & Chilukuri, S. Copper-based catalysts for water gas shift reaction: influence of support on their catalytic activity. Catal. Today 141, 72–76 (2009).
Mistry, H. et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat. Commun. 7, 12123 (2016).
Lunkenbein, T., Schumann, J., Behrens, M., Schlogl, R. & Willinger, M. G. Formation of a ZnO overlayer in industrial Cu/ZnO/Al
Schmidtw, R. D. & Martinez, M. Growth and microstructural control of single-crystal cuprous-oxide Cu
DeNardis, D., Rosales-Yeomans, D., Borucki, L. & Philipossian, A. Studying the effect of temperature on the copper oxidation process using hydrogen peroxide for use in multi-step chemical mechanical planarization models. Thin Solid Films 518, 3903–3909 (2010).
Wan, Y. et al. Corrosion behavior of copper at elevated temperature. Int. J. Electrochem Sci. 7, 7902–7914 (2012).
Stampfl, C., Soon, A., Piccinin, S., Shi, H.Q. & Zhang, H. Bridging the temperature and pressure gaps: close-packed transition metal surfaces in an oxygen environment. J. Phys. Condens. Matter, 184021 20 (2008).
Werner, H., Herein, D., Schulz, G., Wild, U. & Schlögl, R. Reaction pathways in methanol oxidation: kinetic oscillations in the copper/oxygen system. Catal. Lett. 49, 109–119 (1997).
Amariglio, A., Benali, O. & Amariglio, H. Oscillating oxidation of propene on copper oxides. J. Catal. 118, 164–174 (1989).
Yang, J. C. & Zhou, G. W. In situ ultra-high vacuum transmission electron microscopy studies of the transient oxidation stage of Cu and Cu alloy thin films. Micron 43, 1195–1210 (2012).
pubmed: 22537718
Gattinoni, C. & Michaelides, A. Atomistic details of oxide surfaces and surface oxidation: the example of copper and its oxides. Surf. Sci. Rep. 70, 424–447 (2015).
Zhou, G. W. & Yang, J. C. Initial oxidation kinetics of Cu(100), (110), and (111) thin films investigated by in situ ultra-high-vacuum transmission electron microscopy. J. Mater. Res. 20, 1684–1694 (2005).
Kim, J. Y., Rodriguez, J. A., Hanson, J. C., Frenkel, A. I. & Lee, P. L. Reduction of CuO and Cu
pubmed: 12940754
Wang, X. Q., Hanson, J. C., Frenkel, A. I., Kim, J. Y. & Rodriguez, J. A. Time-resolved studies for the mechanism of reduction of copper oxides with carbon monoxide: complex behavior of lattice oxygen and the formation of suboxides. J. Phys. Chem. B 108, 13667–13673 (2004).
Yang, F., Choi, Y. M., Liu, P., Hrbek, J. & Rodriguez, J. A. Autocatalytic reduction of a Cu
Chen, X. B. et al. In situ atomic-scale observation of inhomogeneous oxide reduction. Chem. Commun. 54, 7342–7345 (2018).
Cabrera, N. & Mott, N. F. Theory of the oxidation of metals. Rep. Prog. Phys. 12, 163–184 (1948).
Lampimaki, M., Lahtonen, K., Hirsimaki, M. & Valden, M. Nanoscale oxidation of Cu(100): oxide morphology and surface reactivity. J. Chem. Phys. 126, 034703 (2007).
Yang, J. C., Bharadwaj, M. D., Zhou, G. W. & Tropia, L. Surface kinetics of copper oxidation investigated by in situ ultra-high vacuum transmission electron microscopy. Microsc. Microanal. 7, 486–493 (2001).
pubmed: 12597793
Yang, J. C., Evan, D. & Tropia, L. From nucleation to coalescence of Cu
Milne, R. H. & Howie, A. Electron-microscopy of copper oxidation. Philos. Mag. A 49, 665–682 (1984).
Zou, L. F., Li, J., Zakharov, D., Stach, E. A. & Zhou, G. W. In situ atomic-scale imaging of the metal/oxide interfacial transformation. Nat. Commun. 8, 307 (2017).
LaGrow, A. P., Ward, M. R., Lloyd, D. C., Gai, P. L. & Boyes, E. D. Visualizing the Cu/Cu
pubmed: 27936677
Zhou, G. W. & Yang, J. C. In situ UHV-TEM investigation of the kinetics of initial stages of oxidation on the roughened Cu(110) surface. Surf. Sci. 559, 100–110 (2004).
Zhou, G. W. & Yang, J. C. Initial oxidation kinetics of copper (110) film investigated by in situ UHV-TEM. Surf. Sci. 531, 359–367 (2003).
Kolmakovl, A., Gregoratti, L., Kiskinova, M. & Gunther, S. Recent approaches for bridging the pressure gap in photoelectron microspectroscopy. Top. Catal. 59, 448–468 (2016).
Sezen, H., Al-Hada, M., Amati, M. & Gregoratti, L. In situ chemical and morphological characterization of copper under near ambient reduction and oxidation conditions. Surf. Interface Anal. https://doi.org/10.1002/sia.6276 (2017).
Ho, J. H. & Vook, R. W. (111) Cu2O growth modes on (111)Cu surfaces. J. Cryst. Growth 44, 561–569 (1978).
Legrand-Bonnyns, E. & Ponslet, A. Pre-oxidation structures at 650 °C on Cu(100), (210) and (841) surfaces studied by rheed and microscopy. Surf. Sci. 53, 675–688 (1975).
Vollmer, S., Birkner, A., Lukas, S., Witte, G. & Woll, C. Nanopatterning of copper (111) vicinal surfaces by oxygen-induced mesoscopic faceting. Appl Phys. Lett. 76, 2686–2688 (2000).
Wu, D., Liu, Q., Li, J., Sadowski, J. T. & Zhou, G. Visualizing reversible two-dimensional phase transitions in oxygen chemisorbed layers. J. Phys. Chem. C 122, 28233–28244 (2018).
Reinecke, N., Reiter, S., Vetter, S. & Taglauer, E. Steps, facets and nanostructures: investigations of Cu(11n) surfaces. Appl. Phys. A 75, 1–10 (2002).
Coulman, D., Wintterlin, J., Barth, J. V., Ertl, G. & Behm, R. J. An Stm investigation of the Cu(110)-C(6x2)O system. Surf. Sci. 240, 151–162 (1990).
Jensen, F., Besenbacher, F. & Stensgaard, I. Two new oxygen induced reconstructions on Cu(111). Surf. Sci. 269, 400–404 (1992).
Lian, X., Xiao, P. H., Liu, R. L. & Henkelman, G. Calculations of oxygen adsorption-induced surface reconstruction and oxide formation on Cu(100). Chem. Mater. 29, 1472–1484 (2017).
Lahtonen, K., Hirsimaki, M., Lampimaki, M. & Valden, M. Oxygen adsorption-induced nanostructures and island formation on Cu{100}: Bridging the gap between the formation of surface confined oxygen chemisorption layer and oxide formation. J. Chem. Phys. 129, 124703 (2008).
Zhu, Q., Zou, L. F., Zhou, G. W., Saidi, W. A. & Yang, J. C. Early and transient stages of Cu oxidation: atomistic insights from theoretical simulations and in situ experiments. Surf. Sci. 652, 98–113 (2016).
Li, L., Liu, Q. Q., Li, J., Saidi, W. A. & Zhou, G. W. Kinetic barriers of the phase transition in the oxygen chemisorbed Cu(110)-(2 x 1)-O as a function of oxygen coverage. J. Phys. Chem. C 118, 20858–20866 (2014).
Duan, X., Warschkow, O., Soon, A., Delley, B. & Stampfl, C. Density functional study of oxygen on Cu(100) and Cu(110) surfaces. Phys. Rev. B 81, 075430 (2010).
Wang, J., Li, C., Zhu, Y., Boscoboinik, J. A. & Zhou, G. Insight into the phase transformation pathways of copper oxidation: from oxygen chemisorption on the clean surface to multilayer bulk oxide growth. J. Phys. Chem. C 122, 26519–26527 (2018).
Qin, H., Chen, X., Li, J., Sutter, P. & Zhou, G. Atomic-step-induced local nonequilibrium effects on surface oxidation. J. Phys. Chem. C 121, 22846–22853 (2017).
Li, C., Zhang, P., Wang, J., Boscoboinik, J. A. & Zhou, G. Tuning the deoxygenation of bulk-dissolved oxygen in copper. J. Phys. Chem. C 122, 8254–8261 (2018).
Greiner, M. T., Jones, T. E., Klyushin, A., Knop-Gericke, A. & Schlogl, R. Ethylene epoxidation at the phase transition of copper oxides. J. Am. Chem. Soc. 139, 11825–11832 (2017).
pubmed: 28753282
Gao, D., Arán-Ais, R. M., Jeon, H. S. & Roldan Cuenya, B. Rational catalyst and electrolyte design for CO
Velasco-Vélez, J.-J. et al. The role of the copper oxidation state in the electrocatalytic reduction of CO
Bottcher, A., Krenzer, B., Conrad, H. & Niehus, H. Mesoscopic-scale pattern formation induced by oxidation of Ru(0001). Surf. Sci. 466, L811–L820 (2000).
Michaelides, A., Bocquet, M. L., Sautet, P., Alavi, A. & King, D. A. Structures and thermodynamic phase transitions for oxygen and silver oxide phases on Ag{111}. Chem. Phys. Lett. 367, 344–350 (2003).
Li, W.-X., Stampfl, C. & Scheffler, M. Why is a noble metal catalytically active? The role of the O-Ag interaction in the function of silver as an oxidation catalyst. Phys. Rev. Lett. 90, 256102 (2003).
pubmed: 12857148
Reuter, K. & Scheffler, M. Composition and structure of the RuO2(110) surface in an O
Donald, A. M. The use of environmental scanning electron microscopy for imaging wet and insulating materials. Nat. Mater. 2, 511–516 (2003).
pubmed: 12894259