Articles

https://doi.org/10.1038/s41563-019-0349-9

Structural evolution of atomically dispersed Pt

catalysts dictates reactivity
Leo DeRita1,8, Joaquin Resasco1,8, Sheng Dai2,8, Alexey Boubnov3, Ho Viet Thang4,
Adam S. Hoffman   3, Insoo Ro   1, George W. Graham2,5, Simon R. Bare3, Gianfranco Pacchioni4,
Xiaoqing Pan2,6,7 and Phillip Christopher   1*

The use of oxide-supported isolated Pt-group metal atoms as catalytic active sites is of interest due to their unique reactivity
and efficient metal utilization. However, relationships between the structure of these active sites, their dynamic response
to environments and catalytic functionality have proved difficult to experimentally establish. Here, sinter-resistant cata-
lysts where Pt was deposited uniformly as isolated atoms in well-defined locations on anatase TiO2 nanoparticle supports
were used to develop such relationships. Through a combination of in situ atomic-resolution microscopy- and spectroscopy-
based characterization supported by first-principles calculations it was demonstrated that isolated Pt species can adopt a
range of local coordination environments and oxidation states, which evolve in response to varied environmental conditions.
The variation in local coordination showed a strong influence on the chemical reactivity and could be exploited to control
the catalytic performance.

T
he synthesis of oxide-supported Pt-group catalysts typically
produces metal particles with dimensions of a few nanome-
tres1. Recent work has shown that Pt-group species can coex-
ist as nanoparticles and single atoms2–4, and that careful synthetic
approaches can produce exclusively single atoms4–8. Interest in the
reactivity of supported isolated Pt atoms (Ptiso) and other rare met-
als stems from the maximized metal utilization efficiency, unique
reactivity or selectivity, connection to organometallic catalysis and
the potential for making well-defined active sites8–10. It has proved
challenging to characterize the intrinsic catalytic activity of these
dispersed active sites on oxide supports at a level that relates local
electronic and geometric structure to function. The difficulty arises
from their atomic dispersion, heterogeneity in the local coordina-
tion of active sites on most catalysts (that is, isolated species sit at
different sites on the support)11, dynamic changes in local coor-
dination under reactive environments12 and often the low load-
ing of metal that is required to achieve site isolation13. Exploring
the dynamic restructuring of supported metal catalysts has long
been of interest14–16, with recent experimental work analysing the
dynamic formation and fragmentation of supported ~1 nm metal
clusters under reactive environments17–19, but similar insights into
the dynamic behaviour of dispersed Pt-group species have been dif-
ficult to develop20.
In this work, using a sinter-resistant catalyst consisting of
Ptiso species uniformly deposited at a well-defined location on a
nanoparticle anatase TiO2 support, we demonstrate that environ-
mental conditions dictate the local coordination and charge state
of Ptiso species, which are related to chemical and catalytic reactiv-
ity. Insights into the evolution of local coordination and proper-
ties of Ptiso species in response to varying environmental conditions
were provided by in situ spectroscopy and microscopy correlated to
first-principles calculations.
Catalysts were synthesized via strong electrostatic adsorption21
(see Supplementary Fig. 1) to deposit [Pt(NH3)4]2+ complexes onto
5-nm-diameter anatase TiO2 nanocrystals at a weight loading of
~0.025%, which correlates to nominally ~0.5 Pt atoms per TiO2 par-
ticle22. Through controlled deposition of on average <1 Pt atom per
TiO2 particle, Pt cluster formation was mitigated by the energeti-
cally difficult transfer of Pt atoms between TiO2 particles, enabling
analysis of Ptiso species under conditions where they are mobile but
unable to form clusters. Before analysis, catalysts were calcined in
air at 450 °C to remove remaining ligands from synthesis.
To understand the influence of environmental conditions on
the local environment of Ptiso species, CO probe molecule Fourier
transform infrared (FTIR) spectroscopy was executed at −140 °C
following pretreatment of the catalyst in oxidative and reduc-
tive conditions. Figure 1a shows normalized FTIR spectra of CO
adsorbed at −140 °C on Ptiso/TiO2 following pretreatment via in situ
oxidation (300 °C in O2), mild reduction (250 °C in H2) or harsh
reduction (450 °C in H2). Different characteristics of adsorbed CO
were observed: (1) oxidation resulted in an adsorbed CO stretch-
ing frequency of 2,135 cm−1 with a full-width at half-maximum
(FWHM) of 13.5 cm−1, (2) mild reduction resulted in an adsorbed
CO stretching frequency of 2,112 cm−1 and a FWHM of 10.5 cm−1
and (3) harsh reduction resulted in two CO stretching frequencies
centred at 2,077 and 2,050 cm−1 with a FWHM of 28 and 36 cm−1,
respectively. These vibrational frequencies are generally consis-
tent with CO bound to (1, 2) cationic Pt22, and (3) near-neutral,
Ptδ+, sites23–26. The local coordination and oxidation state of the
Ptiso species can influence the vibrational frequency of CO. Thus,

1
Department of Chemical Engineering, University of California Santa Barbara, Santa Barbara, CA, USA. 2Department of Materials Science and Engineering,
University of California Irvine, Irvine, CA, USA. 3Stanford Synchrotron Radiation Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA,
USA. 4Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, Milano, Italy. 5Department of Materials Science and Engineering, University of
Michigan, Ann Arbor, MI, USA. 6Department of Physics and Astronomy, University of California Irvine, Irvine, CA, USA. 7Irvine Materials Research Institute
(IMRI), University of California Irvine, Irvine, CA, USA. 8These authors contributed equally: Leo DeRita, Joaquin Resasco, Sheng Dai.
*e-mail: pchristopher@ucsb.edu

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NaTure MaTerials Articles
a b c
1.2 450 °C reduction 1.2 450 °C reduction 450 °C reduction
250 °C reduction 250 °C reduction 250 °C reduction
300 °C oxidation 300 °C oxidation 10–4 300 °C oxidation
2,135 cm–1 2,112 cm–1 2,077 cm–1
1.0 1.0

Normalized absorbance
Normalized absorbance

Rate (mol s–1 gPt–1)

Ea = 48 kJ mol–1
0.8 0.8

0.6 0.6
2,050 cm–1 Ea = 78 kJ mol–1

0.4 10–5
0.4
13.5 10.5
28 cm–1
cm–1 cm–1 Ea = 72 kJ mol–1
0.2 0.2
36 cm–1

0.0 0.0
2,150 2,125 2,100 2,075 2,050 2,025 –100 –50 0 50 100 150 0.24 0.26 0.28 0.30
Wavenumber (cm–1) Temperature (°C) 1/RT (mol kJ–1)

Fig. 1 | Controlling chemical and catalytic reactivity of Ptiso via pretreatment. a, FTIR spectra of CO adsorbed at saturation coverage and −140 °C to
Ptiso/TiO2 following pretreatment via in situ oxidation (300 °C in 760 torr O2), mild reduction (250 °C in 760 torr H2) and harsh reduction (450 °C in
760 torr H2). The spectra are normalized to the maximum intensity of the CO stretch for each pretreatment condition. The band centre is listed above each
spectrum and the FWHM within. b, Normalized intensity of the CO stretch absorbance as a function of temperature during TPD experiments associated
with the three different catalyst pretreatments. c, Arrhenius plots showing the temperature dependence of the per-gram Pt rate (mol s−1 gPt−1) for CO
oxidation on each catalyst from 150 to 200 °C in a 200 sccm flow of 1% CO, 1% O2 and balance He at 760 torr. The apparent activation energy (Ea) is shown
for each pretreatment condition with error bars indicating standard error.

unambiguous determination of the Ptiso oxidation state on the been reported for small Pt clusters, substantiating the assertion that
basis of adsorbed CO stretching frequency alone is not possible27. Pt remained as isolated atoms throughout all pretreatments30. In the
Re-oxidation of the catalyst following harsh reduction and exposure case of oxidized Ptiso/TiO2, CO2 evolution was observed to occur
to CO showed the same sharp stretches and desorption below room simultaneously with CO desorption initiating at −110 °C, and thus
temperature observed for Ptiso exposed to oxidation conditions (see a CO adsorption energy was not estimated (Supplementary Figs. 4
Supplementary Fig. 2 for details), which is in contrast to PtxOy clus- and 5).
ters produced by oxidation of 1 nm Pt nanoparticles that bind CO To relate variations in Ptiso properties to catalytic reactiv-
strongly (desorption above 200 °C)22. This suggested retained exis- ity, CO oxidation was performed under strict kinetic control
tence of Ptiso species following harsh reduction. (Supplementary Fig. 6). This reaction has been extensively studied
The FWHM of adsorbed CO stretches after oxidation (13.5 cm−1) with atomically dispersed Pt catalysts due to the interest in decreas-
and mild reduction (10.5 cm−1) were narrower than reports of zeo- ing Pt loading in automotive exhaust applications31. Figure 1c shows
lite-supported Ptiso species, where well-defined anchoring sites are that the reactivities of Ptiso sites following oxidation and mild reduc-
present (15–25 cm−1)28, and Ptiso species on other oxide supports tion were similar, with apparent activation energies, Ea, in the range
(>25 cm−1 for Ptiso/CeO2, FeOx and so on)4–6. A comparable ~10 cm−1 of 70–80 kJ mol−1. By contrast, following harsh reduction, Ptiso sites
FWHM for the adsorbed CO stretch was reported for Ptiso species showed an increase in activity of two- to fivefold, depending on
at a well-defined location on a Cu2O model system in a surface sci- temperature, and a decrease in Ea to 48 kJ mol−1, close to the Ea for
ence study25, which provides evidence that following oxidation and small Pt clusters on TiO2 of 53 kJ mol−1 (ref. 22). CO and O2 partial-
mild reduction pretreatments the Ptiso species observed here were pressure-dependent measurements and microkinetic modelling
predominately located at a single adsorption site on the support11. suggested that CO oxidation proceeded by a Mars–van Krevelen
The similar FWHM of the CO stretch following both pretreatments mechanism with kinetically relevant O2 dissociation at the interface
suggests that Ptiso species did not move significantly between the of an oxygen vacancy in TiO2 and Ptiso for all pretreatment condi-
two pretreatments, and that a modification in local coordination tions (see Supplementary Figs. 7 and 8 and associated discussion).
or Pt oxidation state induced the change in adsorbed CO stretch The rate law is consistent with reports of metal clusters on reducible
frequency. By contrast, harsh reduction resulted in broadened CO oxide supports, where metal atoms at the interface with the support
stretches with FWHMs of 28 cm−1 and 36 cm−1, accompanied by a serve as the active site32. Ptiso/TiO2 catalysts exhibited comparable
decrease in vibrational frequency. This suggests that Ptiso species apparent activation barriers and turnover frequencies to the small-
were reduced to a near-neutral charge state, became mobile on the est Pt clusters on reducible oxides22, which have enhanced CO oxi-
TiO2 surface and adopted a range of coordination environments. dation activity per surface metal atom compared to small Pt clusters
Following CO adsorption at −140 °C, temperature-programmed supported on irreducible oxides33 and unsupported Pt34.
desorption (TPD) experiments were executed (Supplementary Fig. The results in Fig. 1 suggest that during oxidation and mild
3). The intensities of the CO stretches were normalized to saturation reduction pretreatments Ptiso species did not significantly move on
coverage (Fig. 1a), and are shown as a function of temperature in the TiO2 surface, but existed in distinct local coordination environ-
Fig. 1b. During the TPD measurement, the CO stretch frequency, ments when probed by CO at −140 °C. On the basis of the simi-
symmetry and FWHM were essentially constant for the oxidized larities in site location and steady-state catalytic reactivity, it is
and mildly reduced cases, providing evidence that Ptiso species were hypothesized Ptiso species pretreated by oxidation and mild reduc-
spatially separated and existed in a predominant local environment tion dynamically evolved to similar local coordination environ-
(Supplementary Fig. 3). CO adsorption energies estimated using ments under CO oxidation conditions. By contrast, harsh reduction
Redhead analysis29 on mildly and harshly reduced Ptiso/TiO2 were induced mobility and left Ptiso species in close-to-neutral states. It
84 kJ mol−1 and 115–145 kJ mol−1, respectively (see Supplementary is hypothesized that the near-neutral Pt charge state facilitated the
Fig. 3 and associated discussion30). The inferred CO binding energy rate-limiting O2 dissociation step in CO oxidation, as compared
for the harshly reduced case is significantly weaker than what has to the more cationic state of Ptiso species that existed following

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Articles
a b
300 °C, oxidation 250 °C reduction
1 nm
Fig. 2 | In situ AC-STEM characterization of Ptiso/TiO2. a–c, In situ AC-STEM images of Ptiso/TiO2 after 30 min at different annealing conditions: 300 °C,
760 torr of O2 for 30 min (a); 250 °C, 760 torr of 5% H2 (balanced with Ar) for 30 min (b); 450 °C, 760 torr of 5% H2 (balanced with Ar) for 30 min (c).
The yellow circles identify the same Pt single atom. A false-colouring scale was used in a–c to enhance contrast on the Pt atom. d, Intensity profile of a line
scan (along the yellow arrows) shown in a and c normalized to the identified Pt atom.
pre-oxidation and mild reduction (see discussion in Supplementary
Information, step 4 in mechanism).
In situ aberration-corrected scanning transmission electron
microscopy (AC-STEM) at atmospheric pressure was executed to
examine the mobility of Pt atoms on the TiO2 support and corrobo-
rate inferences from infrared measurements. An in situ AC-STEM
experiment was performed on Ptiso/TiO2 during sequential exposure
to 760 torr of O2 at 300 °C, 760 torr of 5% H2 at 250 °C and 760 torr
of 5% H2 at 450 °C. Small probe currents and minimal acquisition
times were used to minimize beam effects (see Supplementary
Information for discussion). Previous studies have demonstrated
the ability to conduct these measurements without artefacts from
electron beam effects or sample drift24,35,36.
Figure 2a shows a high-angle annular dark-field (HAADF)-
STEM image of one Ptiso species on TiO2 following 30 min of in
situ oxidation treatment. After 30 min of exposure to H2 at 250 °C,
this Pt atom remained at the same location on the TiO2 support
(Fig. 2b). Following 30 min of exposure to H2 at 450 °C, the Pt atom
moved 1.6 nm, demonstrating mobility imparted to the single Pt
atom without the formation of a Pt cluster. Line-scan intensity
analysis and in situ STEM experiments as a function of time were
used to substantiate the identification of Ptiso species and dem-
onstrate that the electron beam did not induce Pt motion (Fig.
2d and Supplementary Fig. 9). While exposure to H2 at 450 °C
induced mobility of the Pt atom, a relatively stable adsorption site
must have been reached to allow the atom to be imaged. Exposure
to H2 at 450 °C also induced minor structural changes in TiO2,
demonstrated by the loss of visible lattice fringes in Fig. 2c and
Supplementary Fig. 9. The direct imaging of induced Ptiso mobility
only during the harsh reduction pretreatment and the structural
modification of TiO2 are consistent with inferences made on the
basis of sample-averaged infrared measurements, substantiating
the hypothesis that Ptiso species adopted a range of local coordina-
tion environments following harsh reduction.
In situ X-ray absorption spectroscopy (XAS) experiments were
executed under pretreatment and reaction conditions to provide
complementary sample-averaged information regarding the evo-
lution of the Ptiso oxidation state and local coordination37. Figure
3a shows in situ Pt L3-edge X-ray absorption near-edge structure
(XANES) spectra for each state of the catalyst (see Supplementary
Information for experimental details). For the pretreated samples
(before CO oxidation), the white-line intensity decreased in the
order of oxidized  > mildly reduced >  harshly reduced, consis-
tent with the trends in oxidation state inferred from the infrared
748
NaTure MaTerials
c d
450 °C, reduction Pt
1.0
0.9 300 °C
0.8
Normalized intensity (a.u.)
oxidation
0.7
0.6
0.5
0.4
1.0 Pt
0.9
0.8 450 °C
0.7 reduction
0.6
0.5
0.4
0.3
0 0.5 1.0 1.5 2.0 2.5
Distance (nm)
measurements, although again we refrain from explicitly assign-
ing oxidation states based on the XANES alone (see Supplementary
Information for discussion). Extended X-ray absorption fine-
structure (EXAFS) spectra associated with these states of the cata-
lyst (shown in Fig. 3c and Supplementary Table 1) demonstrate:
lack of measurable Pt–Pt scattering for all pretreatments, consis-
tent with the assertion that Pt remained atomically dispersed in
all explored conditions; a decrease in the extent of Pt–O coordina-
tion comparing oxidizing to reducing conditions; and well-defined
Pt–O and Pt–Ti scattering paths for the pre-oxidized and mildly
reduced catalysts, indicating uniformity in the local coordination
of the Pt single atoms.
XANES and EXAFS measurements obtained under CO oxida-
tion reaction conditions showed that the Ptiso species evolved, with
the Pt in the oxidized and mildly reduced states approaching a sim-
ilar oxidation state and local coordination environment under CO
oxidation conditions (Fig. 3b,c). This rationalizes the similarity in
observed reactivity and is consistent with the similar location of the
Pt atom in both cases. Measurements under CO oxidation condi-
tions following harsh reduction showed that the nearly neutral Pt
state was maintained. This is consistent with the enhanced reac-
tivity in CO oxidation observed for this sample, as a more neutral
Pt atom would be expected to more effectively facilitate the rate-
limiting O2 dissociation step.
To develop structural models of the local coordination of Ptiso
species on TiO2, ex situ STEM images were collected along various
zone axes of the TiO2 support for Ptiso/TiO2 following 250 ˚C reduc-
tion in H2 (see Supplementary Information). Figure 4a presents a
HAADF-STEM image taken along the [021] zone axis of anatase
TiO2, where (100) and (012) planes are indexed in the atomic-reso-
lution image. Ti and O atomic columns are not overlapping in this
projection and from the Z-contrast the visible spots in Fig. 4a must
correspond to Ti atoms38. The brighter spots (highlighted by the
yellow circles), exhibited a higher Z-contrast than surrounding Ti
columns, corresponding to the existence of Pt single atoms22. The
intensity profile (Fig. 4b) taken along the lines indicated by the yel-
low arrows in Fig. 4a, and along the perpendicular direction across
the same Pt atom (Supplementary Fig. 11), demonstrates that this is
the case. Thus, following 250 °C reduction Pt atoms sat in place of,
or above the position of Ti columns (see also Supplementary Fig.
12). On the basis of the in situ STEM in Fig. 2, it is assumed that
Ptiso species must also sit in place of, or above, the position of Ti
columns following oxidation, and probably at a range of positions
on the TiO2 surface following harsh reduction.
Nature Materials | VOL 18 | JULY 2019 | 746–751 | www.nature.com/naturematerials
NaTure MaTerials
a b
2.0
450 °C reduction
250 °C reduction
300 °C oxidation
Normalized absorption
Normalized absorption
1.5
1.0
0.5
Pretreated
0.0
11,550 11,560 11,570 11,580 11,590
Energy (eV)
Fig. 3 | XAS of Ptiso/TiO2 catalysts. a, XANES spectra collected at 200 °C immediately following various pretreatments (shown using solid lines). b, XANES
spectra collected under CO oxidation reaction conditions (200 °C, 1% CO, 1% O2, balance He). Corresponding spectra following pretreatment are shown using
dotted lines to emphasize changes induced by exposure to reaction conditions. The arrows show the change induced by exposure to CO oxidation conditions.
c, EXAFS of catalysts after each pretreatment and under CO oxidation reaction conditions. The magnitude and imaginary portion of the Fourier transforms of
the EXAFS spectra are shown using solid and dotted lines, respectively. Fits are shown in magenta. See also Supplementary Fig. 10 for EXAFS spectra.
Density functional theory (DFT) calculations were per-
formed to identify stable Ptiso structures on the (101) terrace and
(145) stepped surfaces of anatase TiO2 (ref. 39), and to supplement
recently reported calculations (see Supplementary Figs. 13–16
and Supplementary Information for details30). Among the consid-
ered structures, (PtO2)ads species at the (101) anatase TiO2 terrace,
where the Pt atom is bound to two extra O atoms on the surface,
showed excellent agreement with observed characteristics for
mildly reduced Ptiso/TiO2 including the CO vibrational frequency
(2,112 cm−1 measured versus 2,121 cm−1 calculated) and CO adsorp-
tion energy (84 kJ mol−1 measured versus 103 kJ mol−1 calculated).
Good agreement was also found between characteristics of (PtO2)ads
at the (145) TiO2 step site and the experimental results, with calcu-
lated CO vibrational frequency and adsorption energy of 2,107 cm−1
and 50 kJ mol−1, respectively. The (PtO2)ads structures at either the
step or terrace site of TiO2 are consistent with STEM measurements,
showing Pt in line with Ti cation columns when observed along the
[021] axis (see Fig. 4c).
Calculations of CO adsorbing to Ptiso species replacing a six-
fold coordinated Ti (Ti6c) atom at the bottom of the (145) step
edge, or on the (101) terrace, showed barrierless CO2 formation,
which agreed with experimental observations for oxidized Ptiso/
TiO2 (Supplementary Figs. 4 and 5). This Ti6c-substituted Pt posi-
tion is vertically in line with (PtO2)ads along the <021> zone axis,
consistent with the lack of lateral motion observed for Ptiso spe-
cies between oxidation and mild reduction conditions via in situ
STEM. Finally, CO adsorbed to (PtOH)ads species on the TiO2 step
and terrace sites showed reasonable agreement with the measured
vibrational frequencies (2,068 cm−1, step, and 2,087 cm−1, terrace,
calculated, versus 2,050 and 2,077 cm−1, measured) and adsorp-
tion energies (184 kJ mol−1, step, and 210 kJ mol−1, terrace, versus
115–145 kJ mol−1, measured), given the known over-prediction of
CO binding energy in DFT calculations40. Observable changes to
the TiO2 support after harsh reduction indicate that this pretreat-
ment introduced surface defects, resulting in a variety of sites for
(PtOH)ads species to occupy.
The DFT-calculated structures described above (Pt at the Ti6c
site, (PtO2)ads and (PtOH)ads) were used to calculate Pt L3-edge
XANES spectra, which showed agreement in shape and white-line
intensity with the experimental measurements (Supplementary Fig.
17). Fitting of EXAFS data after pretreatment showed close agree-
ment in coordination numbers (CNs) and bond distances with the
DFT-predicted structures (Supplementary Tables 1 and 2, respec-
tively). In particular, oxidation resulted in Pt–O CNs of 6.0 ± 0.7
Nature Materials | VOL 18 | JULY 2019 | 746–751 | www.nature.com/naturematerials
Articles
c
2.0 12 450 °C reduction
450 °C reduction
250 °C reduction 250 °C reduction
300 °C oxidation 300 °C oxidation
Fourier transform EXAFS
9
1.5
(k2-weighted)
9
1.0 Reaction conditions
3
0.5
0
Reaction conditions Pretreated
0.0
11,550 11,560 11,570 11,580 11,590 0 1 2 3 4 5 6
Energy (eV) R (Å)
with a bond distance of 2.0 ± 0.1 Å, consistent with the calculated
structure of Pt sitting in an octahedral Ti site at the (145) step edge
(CN of 6, bond distance of 1.97–2.04 Å). Mild reduction decreased
the total first shell Pt–O coordination, with two distinct Pt–O bond
distances of 1.90 ± 0.05 (CN 1.2 ± 0.6) and 2.10 ± .05 (CN 1.7 ± 0.7).
This showed agreement with the calculated structure of (PtO2)ads
at the (145) step edge, with 1 Pt–O bond distance of 1.83 (CN 2)
and 1 Pt–O bond distance of 2.13 (CN 2). Agreement between fits
to experimental spectra and theory was also found beyond first-
shell fits. EXAFS fitting was not performed on spectra taken under
reaction conditions, due to uncertainty in description of a physical
model for these structures.
On the basis of the comparison of the experimental and cal-
culated characteristics of the different states of the Ptiso species, it
is proposed that oxidation of Ptiso/TiO2 resulted in Pt substituting
into the Ti6c position; mild reduction pulled Ptiso out of the lattice to
form (PtO2)ads species; and harsh reduction induced the formation
of (PtOH)ads species that were mobile and adsorbed to both step and
terrace sites on the support (Fig. 4d). Based on the better agreement
of the calculated and measured XANES and EXAFS characteristics
for the oxidized and mildly reduced Ptiso species at the TiO2 (145)
step edge, as compared to the (101) terrace, it is hypothesized that
Ptiso species were predominantly located at TiO2 step edges. The
proposed Ptiso structures have formal oxidation states of +4 for Pt
substituted at the Ti6c site, +2 for (PtO2)ads and +1 for (PtOH)ads.
These charge assignments are consistent with trends from XANES,
infrared and Bader charge analysis (see Supplementary Tables 2 and
3 and Supplementary Information for discussion). While Pt charge-
state estimations showed consistent trends, each method has unique
limitations in the ability to quantitatively describe charge states and
exact values are dependent on the method used41.
Future analysis aims to interrogate the mechanism of transfor-
mations between these various states of the Ptiso species and how
these states are modified by exposure to CO oxidation conditions.
We expect that these changes were driven not only by energetics
of the Pt cation, but also by structural transformations of reduc-
ible supports. For example, TiO2 surfaces are known to become
mobile following high-temperature reduction14. Future work will
investigate how these structural transformations depend on choice
of support. It is hypothesized that here the transition from (PtO2)ads
to (PtOH)ads occurs by release of the first O atom, forming H2O,
and hydroxylation of the second O atom during high-tempera-
ture reduction, consistent with observations of temperature-pro-
grammed reduction experiments (Supplementary Fig. 18).
749
Articles NaTure MaTerials

a b Pt + Ti

Normalized intensity (a.u)

1.0
3.77 Å
(100) 0.8

0.6 Ti Ti Ti Ti

0.4

0.2
2.95 Å
0.0
(012)
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Distance (nm)

1 nm
<021> zone axis <021> ZA

d (PtO2)ads Harsh reduction

Oxidation
(PtOH)ads,terrace

Mild
(PtOH)ads,step
reduction

PtTi6c

Fig. 4 | Structural models of Ptiso/TiO2. a, An ex situ AC-STEM image of Ptiso/TiO2 following reduction at 250 °C along the <021> zone axis of TiO2.
The yellow circles highlight the Pt single atoms. b, Normalized intensity profile taken along the line indicated by the yellow arrows in a (see Supplementary
Fig. 11 for additional line scans). c, DFT-calculated model of the Ptiso/TiO2 along the anatase TiO2 <021> zone axis (ZA) for the (PtO2)ads structure. It
is seen that the Pt is in line with Ti columns, consistent with the STEM image in a. d, Schematic showing the proposed dynamic evolution of Ptiso/TiO2
catalysts following oxidation, mild reduction and harsh reduction (shown left to right, respectively). Structures were derived from DFT calculations and are
consistent with experimental data. Ti, O, Pt and H atoms are blue, red, white and light-pink spheres, respectively.

Ptiso species can adopt a range of local coordination environ-
ments, which dynamically form in response to varied environmen-
tal conditions, analogous to the dynamic behaviour of metal ions
in zeolites42. This variation in local coordination showed a strong
influence on the chemical reactivity and catalytic performance for
systems where the Ptiso active site was adsorbed at well-defined loca-
tions on the support. This work demonstrates that to understand the
behaviour of atomically dispersed catalysts at the level of defining
structure–function relationships, it is not sufficient to merely show
that all metal species are atomically dispersed; a detailed character-
ization of the uniformity of the local coordination environment and
how this local coordination responds to environmental conditions
must be considered.
Online content
Any methods, additional references, Nature Research reporting
summaries, source data, extended data, supplementary informa-
tion, acknowledgements, peer review information; details of author
contributions and competing interests; and statements of data and
code availability are available at https://doi.org/10.1038/s41563-
019-0349-9.
Received: 7 January 2019; Accepted: 15 March 2019;
Published online: 22 April 2019
References
1. Campbell, C. T., Parker, S. C. & Starr, D. E. The effect of size-dependent
nanoparticle energetics on catalyst sintering. Science 298, 811–814 (2002).
2. Fu, Q., Saltsburg, H. & Flytzani-Stephanopoulos, M. Active nonmetallic
Au and Pt species on ceria-based water-gas shift catalysts. Science 301,
935–938 (2003).
3. Van’t Blik, H. F. J. et al. Structure of rhodium in an ultradispersed Rh/Al2O3
catalyst as studied by EXAFS and other techniques. J. Am. Chem. Soc. 107,
3139–3147 (1985).
4. Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx.
Nat. Chem. 3, 634–641 (2011).
5. Jones, J. et al. Thermally stable single-atom platinum-on-ceria catalysts via
atom trapping. Science 353, 150–154 (2016).
6. Ding, K. et al. Identification of active sites in CO oxidation and water-gas
shift over supported Pt catalysts. Science 350, 189–192 (2015).
7. 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. 126, 9050–9053 (2014).
8. Matsubu, J. C., Yang, V. N. & Christopher, P. Isolated metal active site
concentration and stability controls catalytic CO2 reduction selectivity.
J. Am. Chem. Soc. 137, 3076–3084 (2015).

750 Nature Materials | VOL 18 | JULY 2019 | 746–751 | www.nature.com/naturematerials

NaTure MaTerials
9. Flytzani-Stephanopoulos, M. & Gates, B. C. Atomically dispersed supported
metal catalysts. Annu. Rev. Chem. Biomol. Eng. 3, 545–574 (2012).
10. Bruix, A. et al. Maximum noble-metal efficiency in catalytic materials: atomically
dispersed surface platinum. Angew. Chem. Int. Ed. 53, 10525–10530 (2014).
11. Hoffman, A. S., Fang, C.-Y. & Gates, B. C. Homogeneity of surface sites in
supported single-site metal catalysts: assessment with band widths of metal
carbonyl infrared spectra. J. Phys. Chem. Lett. 7, 3854–3860 (2016).
12. Parkinson, G. S. et al. Carbon monoxide-induced adatom sintering in a
Pd–Fe3O4 model catalyst. Nat. Mater. 12, 724–728 (2013).
13. Hoffman, A. S. et al. Beating heterogeneity of single-site catalysts: MgO-
supported iridium complexes. ACS Catal. 8, 3489–3498 (2018).
14. Tauster, S. J., Fung, S. C. & Garten, R. L. Strong metal-support interactions.
Group 8 noble metals supported on titanium dioxide. J. Am. Chem. Soc. 100,
170–175 (1978).
15. Gänzler, A. M. et al. Tuning the structure of platinum particles on ceria
in situ for enhancing the catalytic performance of exhaust gas catalysts.
Angew. Chemie Int. Ed. 56, 13078–13082 (2017).
16. Zugic, B. et al. Dynamic restructuring drives catalytic activity on nanoporous
gold–silver alloy catalysts. Nat. Mater. 16, 558–564 (2016).
17. 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).
18. Moliner, M. et al. Reversible transformation of Pt nanoparticles into single
atoms inside high-silica chabazite zeolite. J. Am. Chem. Soc. 138,
15743–15750 (2016).
19. Wei, S. et al. Direct observation of noble metal nanoparticles transforming to
thermally stable single atoms. Nat. Nanotechnol. 13, 856–861 (2018).
20. Liu, L. & Corma, A. Metal catalysts for heterogeneous catalysis: from single
atoms to nanoclusters and nanoparticles. Chem. Rev. 118, 4981–5079 (2018).
21. Schreier, M. & Regalbuto, J. R. A fundamental study of Pt tetraammine
impregnation of silica: 1. The electrostatic nature of platinum adsorption.
J. Catal. 225, 190–202 (2004).
22. DeRita, L. et al. Catalyst architecture for stable single atom dispersion enables
site-specific spectroscopic and reactivity measurements of CO adsorbed to Pt
atoms, oxidized Pt clusters, and metallic Pt clusters on TiO2. J. Am. Chem.
Soc. 139, 14150–14165 (2017).
23. 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).
24. Avanesian, T. et al. Quantitative and atomic-scale view of CO-induced Pt
nanoparticle surface reconstruction at saturation coverage via DFT
calculations coupled with in situ TEM and IR. J. Am. Chem. Soc. 139,
4551–4558 (2017).
25. Therrien, A. J. et al. An atomic-scale view of single-site Pt catalysis for
low-temperature CO oxidation. Nat. Catal. 1, 192–198 (2018).
26. Ivanova, E., Mihaylov, M., Thibault-Starzyk, F., Daturi, M. & Hadjiivanov, K.
FTIR spectroscopy study of CO and NO adsorption and co-adsorption on Pt/
TiO2. J. Mol. Catal. A 274, 179–184 (2007).
27. Aleksandrov, H. A., Neyman, K. M., Hadjiivanov, K. I. & Vayssilov, G. N. Can
the state of platinum species be unambiguously determined by the stretching
frequency of an adsorbed CO probe molecule? Phys. Chem. Chem. Phys. 18,
22108–22121 (2016).
28. Zholobenko, V. L., Lei, G.-D., Carvill, B. T., Lerner, B. A. & Sachtler, W. M.
H. Identification of isolated Pt atoms in H-mordenite. J. Chem. Soc. Faraday
Trans. 90, 233–238 (1994).
29. Redhead, P. A. Thermal desorption of gases. Vacuum 12, 203–211 (1962).
30. Thang, H. V., Pacchioni, G., DeRita, L. & Christopher, P. Nature of stable
single atom Pt catalysts dispersed on anatase TiO2. J. Catal. 367,
104–114 (2018).
31. Freund, H.-J., Meijer, G., Scheffler, M., Schlögl, R. & Wolf, M. CO oxidation
as a prototypical reaction for heterogeneous processes. Angew. Chem. Int. Ed.
50, 10064–10094 (2011).
32. Bunluesin, T., Cordatos, H. & Gorte, R. J. Study of CO oxidation kinetics on
Rh/ceria. J. Catal. 157, 222–226 (1995).
33. Allian, A. D. et al. Chemisorption of CO and mechanism of CO oxidation on
supported platinum nanoclusters. J. Am. Chem. Soc. 133, 4498–4517 (2011).
Nature Materials | VOL 18 | JULY 2019 | 746–751 | www.nature.com/naturematerials
Articles
34. Berlowitz, P. J., Peden, C. H. F. & Goodman, D. W. Kinetics of carbon
monoxide oxidation on single-crystal palladium, platinum, and iridium.
J. Phys. Chem. 92, 5213–5221 (1988).
35. Dai, S. et al. In situ atomic-scale observation of oxygen-driven core–shell
formation in Pt3Co nanoparticles. Nat. Commun. 8, 204 (2017).
36. Matsubu, J. C. et al. Adsorbate-mediated strong metal–support interactions in
oxide-supported Rh catalysts. Nat. Chem. 9, 120–127 (2017).
37. Resasco, J., Dai, S., Graham, G., Pan, X. & Christopher, P. Combining in-situ
transmission electron microscopy and infrared spectroscopy for
understanding dynamic and atomic-scale features of supported metal
catalysts. J. Phys. Chem. C 122, 25143–25157 (2018).
38. Crewe, A. V., Wall, J. & Langmore, J. Visibility of single atoms. Science 168,
1338–1340 (1970).
39. Diebold, U., Ruzycki, N., Herman, G. S. & Selloni, A. One step towards
bridging the materials gap: surface studies of TiO2 anatase. Catal. Today 85,
93–100 (2003).
40. Schimka, L. et al. Accurate surface and adsorption energies from many-body
perturbation theory. Nat. Mater. 9, 741–744 (2010).
41. Walsh, A., Sokol, A. A., Buckeridge, J., Scanlon, D. O. & Catlow, C. R. A.
Oxidation states and ionicity. Nat. Mater. 17, 958–964 (2018).
42. Paolucci, C. et al. Dynamic multinuclear sites formed by mobilized copper
ions in NOx selective catalytic reduction. Science 357, 898–903 (2017).
Acknowledgements
We acknowledge S. Hanukovich for his assistance with the microkinetic modelling
in Supplementary Fig. 8 and the TPR experiment in Supplementary Fig. 18. P.C.
acknowledges funding from National Science Foundation (NSF) CAREER grant number
CBET-1823189. The UCSB MRL Shared Experimental Facilities are acknowledged for
use of the inductively coupled plasma–optical emission spectrometry equipment and
are supported by the MRSEC Program of the NSF under award no. DMR 1720256;
a member of the NSF-funded Materials Research Facilities Network (www.mrfn.
org). The work of H.V.T. and G.P. was supported by the Italian MIUR through the
PRIN Project 2015K7FZLH SMARTNESS. Use of the Stanford Synchrotron Radiation
Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department
of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-
AC02-76SF00515. Co-ACCESS is supported by the US Department of Energy, Office
of Science, Office of Basic Energy Sciences. TEM experiments was conducted using the
facilities in the Irvine Materials Research Institute at the University of California-Irvine.
The work at UC Irvine was supported by the National Science Foundation through the
grant number DMR-1506535.
Author contributions
L.D. developed the catalyst synthesis; L.D. and J.R. performed infrared characterization
and catalytic measurements; S.D. performed and analysed TEM measurements
with supervision by X.P. and G.W.G.; L.D., A.S.H., A.B. and I.R. performed the XAS
supervised by S.R.B.; A.B. performed the XAFS analysis; H.V.T. performed the DFT
calculations supervised by G.P.; I.R. performed the inductively coupled plasma–optical
emission spectrometry measurements. All authors analysed and interpreted the results
and contributed to the preparation of the manuscript. P.C. conceived the project and
oversaw all portions.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/
s41563-019-0349-9.
Reprints and permissions information is available at www.nature.com/reprints.
Correspondence and requests for materials should be addressed to P.C.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in
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751
Articles
Methods
Catalyst preparation. The synthesis of Ptiso catalysts on TiO2 has been
reported previously22. Briefly, a pH-adjusted solution (12.2) containing
tetraammineplatinum(II) nitrate was slowly injected into a solution containing
TiO2 (anatase, 5 nm diameter, 290 m2 g−1, US Research Nanomaterials). After
drying, the catalyst was calcined in a tube furnace at 450 °C for 4 h in flowing air
after ramping up the temperature at a rate of 10 °C min−1.
Infrared spectroscopy. FTIR experiments were carried out in a diffuse reflectance
reaction chamber (Harrick Scientific) equipped with ZnSe windows, mounted
inside a Praying Mantis diffuse reflectance adapter (Harrick Scientific), and
coupled to a Thermo Scientific Nicolet iS10 FTIR spectrometer with a liquid-
nitrogen-cooled HgCdTe (MCT-A) detector. During measurements, the FTIR and
Praying Mantis diffuse reflection accessory were purged with dry N2.
Electron microscopy. AC-STEM was performed on a JEOL Grand ARM300CF
microscope equipped with two spherical aberration correctors, operated at 200 kV.
HAADF-STEM images were recorded using a convergence semi-angle of 22 mrad,
and inner- and outer- collection angles of 83 and 165 mrad, respectively. To
minimize beam irradiation, a small beam current (<10 pA) was used for imaging,
while the acquisition time was always controlled to be less than 12 s for each frame.
In situ STEM experiments were performed in a Protochips Atmosphere gas cell
system, which allows for dynamic observation of nanomaterials heated under
atmospheric pressure inside a transmission electron microscope.
XAS measurements. XAS spectra were collected at beamline 9-3 at the Stanford
Synchrotron Radiation Lightsource at the SLAC National Laboratory. In the
experiments, 16 mg of 0.025 wt% Pt/TiO2 was diluted in mesoporous silica (MCM-41)
and loaded into a flow-through quartz tube, with an outer diameter of 3.0 mm and an
inner diameter of 2.8 mm, held at a 45° angle relative to the X-ray beam43. Fluorescence
XAS measurements were collected using a Canberra 100-element Ge detector
orthogonal (90°) to the beam path with 4 layers of Al foil to filter Ti fluorescence lines,
as well as lead shielding to minimize contributions from scattering of beamline optics.
A Pt foil reference was scanned simultaneously for energy calibration.
The raw data were processed using the Athena interface of the Demeter
software package44. The spectra were energy-calibrated, merged and normalized.
The EXAFS was extracted in k-space and Fourier-transformation was conducted
on the k2-weighted EXAFS function (k = 3.0–12.0 Å−1) to amplify the oscillations at
high k-values. Phase shifts and amplitudes for relevant back-scattering paths were
calculated using FEFF6.
Kinetic control and reactivity experimental details. After pretreatment and 12 h
exposure at 200 °C in a feed of 1% CO, 1% O2 and 98% He, temperature-dependent
measurements were taken between 150 °C and 200 °C, for 2 h at each temperature.
Catalyst dilution studies showed that differences in activity between the catalysts
are of kinetic origins, rather than a result of mass and heat transport limitations.
Partial-pressure-dependent measurements were executed at 200 °C.
DFT computational methods. Spin-polarized periodic DFT calculations were
performed using the Vienna Ab initio Simulation Package45. The Perdew–Burke–
Ernzerhof generalized gradient approximation was used46. The self-interaction
NaTure MaTerials
error inherent in DFT calculations was partly corrected using the DFT + U
approach where the Hubbard’s U parameter was empirically set to 3 eV47. The
projector augmented wave48,49 method was used and the valence electrons explicitly
treated were: Ti(3s2, 3p6, 3d2, 4s2), Pt (5p6, 5d9, 6s1), O (2s2, 2p4), C (2s2, 2p2) and
H (1s1). We used a plane-wave basis set with a cutoff energy of 400 eV and the
calculation was performed at the gamma point. The optimized structures were
considered converged when the ionic forces were <0.01 eV Å−1.
We adopted the models of (3 × 1) and (2 × 1) supercell slabs including five
atomic layers for the anatase TiO2 (101) or the stepped TiO2 (145) surfaces,
respectively. A vacuum of more than 15 Å was used to avoid the interaction
between slabs50. The TiO2 (101) surface terminates with two types of Ti cation,
five-fold coordinated Ti (Ti5c) and six-fold coordinated Ti (Ti6c), and two
types of O anion, two-fold coordinated O sites (O2c) and three-fold coordinated
O sites (O3c).
CO adsorption energies were calculated as the difference between isolated
species and the adsorption complexes. The CO frequencies were computed within
the harmonic approximation, in which CO and its first neighbouring atoms were
considered in the calculation. In the gas phase, the CO bond length (1.144 Å) and
stretching frequency (2,125 cm−1) were obtained at the Perdew–Burke–Ernzerhof
level. A scaling factor α = 2,143/2,125 = 1.0085 was applied to all frequencies to
take into account the difference with respect to the experimental CO frequency in
the gas phase (2,143 cm−1).
Data availability
All the data reported in this paper are available from the corresponding author
upon request.
References
43. Hoffman, A. S., Singh, J. A., Bent, S. F. & Bare, S. R. In situ observation of
phase changes of a silica-supported cobalt catalyst for the Fischer–Tropsch
process by the development of a synchrotron-compatible in situ/operando
powder X-ray diffraction cell. J. Synchrotron Radiat. 25, 1673–1682 (2018).
44. Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis
for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12,
537–541 (2005).
45. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations
for metals and semiconductors using a plane-wave basis set. Comput. Mater.
Sci. 6, 15–50 (1996).
46. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation
made simple. Phys. Rev. Lett. 78, 1396–1399 (1997).
47. Chen, H.-Y. T. Y. T., Tosoni, S. & Pacchioni, G. Adsorption of ruthenium
atoms and clusters on anatase TiO2 and tetragonal ZrO2 (101) surfaces: a
comparative DFT study. J. Phys. Chem. C 119, 10856–10868 (2015).
48. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50,
17953–17979 (1994).
49. Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector
augmented-wave method. Phys. Rev. B 59, 1758 (1999).
50. Chen, H.-Y. T., Tosoni, S. & Pacchioni, G. A. DFT study of the acid–base
properties of anatase TiO2 and tetragonal ZrO2 by adsorption of CO and CO2
probe molecules. Surf. Sci. 652, 163–171 (2016).
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