Letter reSeArCH
5.
Chinchen, G. C., Denny, P. J., Jennings, J. R., Spencer, M. S. & Waugh, K. C.
Synthesis of methanol. Part 1. Catalysts and kinetics. Appl. Catal. 36, 1–65
25. Belokoneva, E. L., Gubina, Y. K. & Forsyth, J. B. The charge density distribution
3 3 2 2
and antiferromagnetic properties of azurite Cu [CO ] (OH) . Phys. Chem.
Miner. 28, 498–507 (2001).
(1988).
6
.
.
Rhodes, C., Hutchings, G. J. & Ward, A. M. Water-gas shift reaction: finding the
mechanistic boundary. Catal. Today 23, 43–58 (1995).
Short, G. D., Chinchen, G. C. & Williamson, J. G. Synthesis of methanol; finely
divided oxides of zinc, aluminum, magnesium; with metallic copper. US patent
26. Perchiazzi, N. & Merlino, S. The malachite-rosasite group: crystal structures of
glaukosphaerite and pokrovskite. Eur. J. Mineral. 18, 787–792 (2006).
2
27. Belin, S. et al. CuAu/SiO catalysts for the selective oxidation of propene to
7
acrolein: the impact of catalyst preparation variables on material structure and
catalytic performance. Catal. Sci. Technol. 3, 2944–2957 (2013).
4,788,175 (1988).
8
.
.
Behrens, M. et al. The active site of methanol synthesis over Cu/ZnO/Al
industrial catalysts. Science 336, 893–897 (2012).
Baltes, C., Vukojevic, S. & Schueth, F. Correlations between synthesis, precursor,
and catalyst structure and activity of a large set of CuO/ZnO/Al O catalysts for
2 3
methanol synthesis. J. Catal. 258, 334–344 (2008).
2
O
3
28. Chinchen, G. C., Waugh, K. C. & Whan, D. A. The activity and state of the copper
surface in methanol synthesis catalysts. Appl. Catal. 25, 101–107 (1986).
29. Behrens, M. et al. The potential of microstructural optimization in metal/oxide
catalysts: higher intrinsic activity of copper by partial embedding of copper
nanoparticles. Chem. Cat. Chem. 2, 816–818 (2010).
9
1
1
1
0. Bems, B. et al. Relations between synthesis and microstructural properties of
copper/zinc hydroxycarbonates. Chemistry 9, 2039–2052 (2003).
1. Pollard, A. M. et al. Georgeite and azurite as precursors in the preparation of
coprecipitated copper/zinc oxide catalysts. Appl. Catal. A 85, 1–11 (1992).
2. Prieto, G., de Jong, K. P. & de Jongh, P. E. Towards ‘greener’ catalyst
Acknowledgements We thank C. Brookes, L. Van de Water, H. Stanness and
C. Ramson for technical assistance. We thank Johnson Matthey and the
Engineering and Physical Sciences Research Council (EPSRC) for funding
though a CASE award, and acknowledge funding from the UK Technology
Strategy Board and the EPSRC and UK Catalysis Hub (grants EP/K014714/1,
EP/K014714/1, EP/K014668/1, EP/K014706/1, EP/H000925/1 and
EP/I019693/1). We used the B18 beamline at the Diamond Light Source
(allocation number SP8071) with the help of D. Gianolio and G. Cibin; and we
used the I15 beamline, which contributed to the PDF results. This research
used the resources of the Advanced Photon Source (APS)—a US Department
of Energy (DOE) Office of Science User Facility, operated for the DOE Office of
Science by Argonne National Laboratory under contract DE-AC02-06CH11357;
we thank K. Chapman for collecting PDF data at beamline 11-ID-B, APS. C.J.K
acknowledges funding from the National Science Foundation Major Research
Instrumentation program (GR#MRI/DMR-1040229). M.J.R. is a Royal Society
Research Professor. We thank the A.P. Møller and Chastine Mc-Kinney Møller
Foundation for contributing to the establishment of the Center for Electron
2 3
manufacture: reduction of wastewater from the preparation of Cu/ZnO/Al O
methanol synthesis catalysts. Catal. Today 215, 142–151 (2013).
1
3. Tang, Z.-R. et al. New nanocrystalline Cu/MnO
supercritical antisolvent precipitation. ChemCatChem 1, 247–251
2009).
x
catalysts prepared from
(
14. Reverchon, E. Supercritical antisolvent precipitation of micro- and nano-
particles. J. Supercrit. Fluids 15, 1–21 (1999).
1
1
5. Rogers, A. P. A review of the amorphous minerals. J. Geol. 25, 515–541 (1917).
6. Pollard, A. M., Thomas, R. G., Williams, P. A., Just, J. & Bridge, P. J. The synthesis
and composition of georgeite and its reactions to form other secondary
copper(II) carbonates. Mineral. Mag. 55, 163–166 (1991).
1
1
1
2
7. Behrens, M. et al. Performance improvement of nanocatalysts by promoter-
induced defects in the support material: methanol synthesis over Cu/ZnO:Al.
J. Am. Chem. Soc. 135, 6061–6068 (2013).
8. Campbell, J. S. Influences of catalyst formulation and poisoning on the activity
and die-off of low temperature shift catalysts. Ind. Eng. Chem. Process Des. Dev.
9, 588–595 (1970).
9. Schur, M. et al. Continuous coprecipitation of catalysts in a micromixer:
nanostructured Cu/ZnO composite for the synthesis of methanol. Angew.
Chem. Int. Edn 42, 3815–3817 (2003).
0. Rothe, J., Hormes, J., Bonnemann, H., Brijoux, W. & Siepen, K. In situ X-ray
absorption spectroscopy investigation during the formation of colloidal copper.
J. Am. Chem. Soc. 120, 6019–6023 (1998).
Author Contributions S.A.K., J.K.B., S.H.T., M.S.S., G.J.K., C.W.P., M.J.R., C.J.K.
and G.J.H. designed the experiments. S.A.K. and P.J.S. prepared samples for
TGA/EGA analysis and IR spectroscopy; S.A.K., P.J.S. and J.H.C. carried out the
catalysis evaluation and determination of copper surface area; S.A.K., P.J.S. and
P.A.C. carried out the XRD analysis; P.A.C. carried out the PDF analysis; P.P.W.,
S.A.K. and P.J.S. carried out the XAFS and interpretation; L.L. and C.J.K. carried
out the TEM and interpretation; E.M.F., J.B.W., C.J.K. and S.A.K. carried out
the ETEM and interpretation; D.J.M., P.J.S. and S.A.K. carried out the XPS and
interpretation. S.A.K., C.J.K., J.B.W., G.J.K., M.J.R. and G.J.H. wrote and edited the
manuscript. G.J.H. directed the research.
2
2
2
1. Klokishner, S. et al. Cation ordering in natural and synthetic (Cu1-xZn
x 2 3 2
) CO (OH)
and (Cu1-xZn (CO (OH) . J. Phys. Chem. A 115, 9954–9968 (2011).
)
x 5
)
3 2
6
2. Behrens, M. & Girgsdies, F. Structural effects of Cu/Zn substitution in the
malachite-rosasite System. Z. Anorg. Allg. Chem. 636, 919–927 (2010).
3. Michel, F. M. et al. Short- to medium-range atomic order and crystallite size of
the initial FeS precipitate from pair distribution function analysis. Chem. Mater.
1
7, 6246–6255 (2005).
4. Harding, M. M., Kariuki, B. M., Cernik, R. & Cressey, G. The structure of
aurichalcite, (CuZn) (OH) (CO determined from a microcrystal. Acta
Crystallogr. B 50, 673–676 (1994).
2
5
6
3 2
)
0
0 M o n t h 2 0 1 6 | V o L 0 0 0 | n A t U R E | 5
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