Corrected 25 January 2019. See Erratum.

R ES E A RC H Corrected 4 February 2020. See full text.

CATALYSIS 90% conversion of all criteria pollutants at 150°C

(“The 150°C Challenge”) (2), a temperature which
is ~100°C lower than current state-of-the-art
Activation of surface lattice oxygen commercial automotive catalysts (11). In response
to this challenge, the ternary oxide (without pre-

in single-atom Pt/CeO2 for cious metals) CuCoCeOx was recently reported to

outperform PGM–based catalysts in CO oxidation
(12). However, its high-temperature hydrother-
low-temperature CO oxidation mal stability limits its commercial deployment.
In this study, we used Pt and ceria (CeO2),
Lei Nie,1* Donghai Mei,1* Haifeng Xiong,2* Bo Peng,1 Zhibo Ren,1,3
which are two of the key components of catalytic
converters in the market. Various efforts have
Xavier Isidro Pereira Hernandez,4 Andrew DeLaRiva,2 Meng Wang,1
been made to improve the dispersion of Pt to
Mark H. Engelhard,1 Libor Kovarik,1 Abhaya K. Datye,2† Yong Wang1,4†
maximize its use (13–15). We recently reported
that polyhedral CeO2 can anchor Pt as isolated
To improve fuel efficiency, advanced combustion engines are being designed to minimize
single atoms after thermal aging in air at 800°C
the amount of heat wasted in the exhaust. Hence, future generations of catalysts must
to yield an atomically dispersed and sinter-
perform at temperatures that are 100°C lower than current exhaust-treatment catalysts.
resistant catalyst (7). However, despite its high
Achieving low-temperature activity, while surviving the harsh conditions encountered at
dispersion and excellent thermal stability (5),
high engine loads, remains a formidable challenge. In this study, we demonstrate how
the low-temperature CO oxidation reactivity is
atomically dispersed ionic platinum (Pt2+) on ceria (CeO2), which is already thermally
limited, partly due to the inactive lattice oxygen
stable, can be activated via steam treatment (at 750°C) to simultaneously achieve the
and strong binding of CO molecules to Pt ions (6).
goals of low-temperature carbon monoxide (CO) oxidation activity while providing
The activity of ceria-supported catalysts can
outstanding hydrothermal stability. A new type of active site is created on CeO2 in the
be improved by treating the catalyst in a reduc-
vicinity of Pt2+, which provides the improved reactivity. These active sites are stable up to
ing atmosphere (16), specifically in H2. However,
800°C in oxidizing environments.
such a reducing treatment causes the formation
of Pt NPs (5, 9), which are subject to deactivation

A
dvanced combustion engines are being de- tal effects on CO oxidation by other pollutants, under oxidizing atmospheres (16). Surprisingly,
veloped to meet higher standards of fuel such as hydrocarbons and NOx present in the we discovered that hydrothermal aging at high
efficiency and lowered greenhouse gas emis- simulated vehicle exhaust, were observed—that temperature (e.g., 750°C) can activate the atom-
sions (1, 2), but their commercial potential is, T100 of CO conversion was achieved at 150°C ically dispersed Pt/CeO2 catalyst, leading to
is contingent on meeting emission stan- even under simulated exhaust conditions. The substantially improved low-temperature CO ox-
dards for the control of criteria pollutants (CO, improved low-temperature activity is attributed idation without any change in the atomic dis-
NOx, hydrocarbons, and particulate matter). The to the activation of surface lattice oxygen that is persion of Pt. Although steam treatment is widely
lower exhaust temperature of advanced engines bonded to H, forming hydroxyls on the CeO2 used to improve catalytic stability of zeolites, it
requires catalysts that are active at temperatures support in the vicinity of atomically dispersed is rarely applied to supported PGM catalysts
<150°C to meet future emission regulations (3). Pt. These results demonstrate the important role because sintering of the metal NPs and degra-
Single-atom heterogeneous catalysts have demon- of activation of the catalyst support for simulta- dation of metal-oxide supports can occur (17, 18),
strated excellent low-temperature reactivity (4) neously achieving high reactivity and durability, leading to reduced catalyst activity.
but do not meet the demands of high-temperature which remains a major challenge in the field of We now show that steam treatment facilitated
thermal and/or hydrothermal durability that are single-atom catalysis. the formation of active surface lattice oxygen near
needed during operation under high engine loads The oxidation of CO, a key reaction in au- atomically dispersed Pt and dramatically en-
and periodic regeneration of catalytic soot filters. tomotive emission abatement, has been exten- hanced catalytic performance. We designated
We show that the activation of atomically sively studied (5–9). In the current generation thermally aged and subsequently steam-treated
dispersed Pt2+ on CeO2 via high-temperature of emission-treatment catalysts, the reaction is (hydrothermally aged) catalysts as Pt/CeO2 and
(e.g., 750°C) treatment in steam simultaneously carried out over metallic nanoparticles (NPs) Pt/CeO2_S, respectively. Catalyst preparation de-
achieved the goals of low-temperature CO oxi- containing Pt, Pd, and Rh supported over alumi- tails are summarized elsewhere (fig. S1) (19). In
dation activity while providing thermal stability. num oxide with other oxide promoters. Zero- the Pt/CeO2 catalyst (Fig. 1A), Pt is atomically
Specifically, T100 (temperature required to reach valent atoms of platinum group metals (PGMs) dispersed, in agreement with our previous re-
100% conversion) of CO decreased from 320° to are mobile at high temperatures and agglomer- port (7). Interestingly, in the Pt/CeO2_S sample,
148°C, and there was no evident catalyst de- ate into larger particles, losing their catalytic no sintering of Pt occurred, and Pt remained
activation in consecutive CO oxidation light-off efficiency. To maintain this dispersion under atomically dispersed (Fig. 1B), even after harsh
measurements. In addition, cofeeding water working conditions, atoms must be anchored to steam treatment at the high temperature of
further enhanced CO oxidation, and no detrimen- the support by forming covalent bonds with ox- 750°C. The presence of Pt NPs should be readily
ygen atoms in the catalyst support. However, visible by scanning transmission electron micros-
1
achieving high catalytic activity with anchored copy (STEM) (fig. S2). No such NPs were found in
Institute for Integrated Catalysis and Environmental
Molecular Sciences Laboratory, Pacific Northwest National
metal ions remains a formidable challenge. Pt/CeO2 or Pt/CeO2_S, even by higher-resolution
Laboratory, Post Office Box 999, Richland, WA 99352, USA. A precious metal–based perovskite, LaFe0.95 STEM. No diffraction peaks of Pt were observed
2
Department of Chemical and Biological Engineering and Pd0.05O3, was developed by Tanaka and co-workers in x-ray diffraction patterns for both Pt/CeO2
Center for Micro-Engineered Materials, University of New (10) and termed the “intelligent” catalyst because and Pt/CeO2_S samples, further confirming the
Mexico, Albuquerque, NM 87131, USA. 3State Key Laboratory
of Chemical Resources Engineering, Beijing University of
of the ability of the precious metal to move in high dispersion of Pt (fig. S3). The x-ray absorp-
Chemical Technology, Beijing 100029, China. 4The Gene and and out of perovskite oxides by forming a solid tion near-edge structure spectra show that
Linda Voiland School of Chemical Engineering and solution or metallic NP, depending on the re- the Pt remained oxidized on both Pt/CeO2 and
Bioengineering, Washington State University, Pullman, WA dox conditions. In this manner, the sintering of Pt/CeO2_S samples and that there were no de-
99164, USA.
*These authors contributed equally to this work.
the precious metal is prevented, but its low- tectable Pt–Pt first- or second-shell interactions
†Corresponding author. Email: datye@[Link] (A.K.D.); temperature reactivity is limited. The U.S. De- in the extended x-ray absorption fine structure
[Link]@[Link] (Y.W.) partment of Energy has set the goal of achieving (EXAFS) results, verifying the atomic dispersion

Nie et al., Science 358, 1419–1423 (2017) 15 December 2017 1 of 5

 Corrected 25 January 2019. See Erratum.
R ES E A RC H | R E PO R T Corrected 4 February 2020. See full text.

of Pt (fig. S4). Moreover, the surface areas and temperature was lowered to ~60°C, and T100 de- as hydrocarbons and NOx, in the feed when the
pore volumes for Pt/CeO2 and Pt/CeO2_S were creased from 320° (Pt/CeO2) to 148°C (Pt/CeO2_S). CO oxidation performance of Pt/CeO2_S was
comparable to each other (table S1), suggesting Compared to other reported catalysts that have evaluated under simulated exhaust conditions
the existence of stable textural properties after potential commercial viability as well as current (fig. S8A). In addition, cofeeding water could
high-temperature steam treatment. Addition- commercial catalysts tested under similar condi- further enhance the low-temperature CO oxida-
ally, Pt remained in ionic form Pt2+ over both tions that have been subjected to 800°C treat- tion activity over Pt/CeO2_S (fig. S8B), as previ-
catalysts, as evidenced by x-ray photoelectron ment in air, Pt/CeO2_S is among the most active ously reported (13).
spectroscopy (XPS) (fig. S5). CO oxidation catalysts (table S2). Because the To provide mechanistic insights into the en-
It is generally accepted that the CO oxidation Pt/CeO2_S catalyst was pretreated under harsh hanced low-temperature CO oxidation reactiv-
over Pt/CeO2 follows a Mars–van Krevelen reac- hydrothermal conditions at 750°C, it is not sur- ity of Pt/CeO2 by steam treatment, adsorption
tion mechanism, (13, 20). Adsorbed CO on Pt re- prising that it also exhibits stable reactivity. There of CO over Pt sites was studied by diffuse-
acts with active lattice oxygen species provided is no noticeable deactivation during 310-hour reflectance infrared Fourier-transform spectros-
by CeO2, where no competitive adsorption be- time-on-stream testing with eight light-off cy- copy (DRIFTS) for both Pt/CeO2 and Pt/CeO2_S
tween CO and O2 is involved. The reaction rates cles, and 95% conversion of CO is maintained at catalysts (6). Under CO oxidation reaction con-
do not depend on the partial pressure of both 145°C for 310 hours (fig. S6). ditions at 180°C (CO oxidation steady state in
CO and O2, i.e., 0 th order (8, 21). The reaction For comparison, we also tested CoCuCeOx and Fig. 2, A and B), only ionic Pt2+ was present, as
mechanism and kinetics are valid over a wide 0.5% Pd/La-Al2O3, which are two other prom- evidenced by the bands at 2091 and 2103 cm–1,
range of reactant compositions (lean, stoichi- ising catalysts (table S2) (12, 22). After hydro- which are assigned to linearly adsorbed CO on
ometric, and rich conditions) (20). thermal aging under the same conditions as isolated ionic Pt2+ (6, 23). By combining the re-
To mimic lean-burn diesel engine exhaust, we the Pt/CeO2_S catalyst, their T100 increased to sults from STEM (Fig. 1, A and B), XPS (fig. S5),
used excess O2 in the reactant (CO/O2 = 1/25 in 350° and 190°C, respectively (Fig. 1D). To further DRIFTS, and EXAFS (fig. S4), we conclude that
molar ratio) (12). The CO oxidation light-off curves investigate the durability of Pt/CeO2_S especially atomic dispersion of Pt2+ was maintained on
were measured to evaluate catalyst performance. A at high temperatures, which is crucial for op- both Pt/CeO2_S and Pt/CeO2 and that steam
gas hourly space velocity of 200,000 ml gcat–1 hour–1 erations under high engine loads, light-off per- treatment did not affect the dispersion or valence
(gcat, grams of catalyst) was used to match stan- formance at temperatures up to 500° and 800°C (Pt2+) of platinum.
dard vehicle exhaust conditions. As shown in was tested (fig. S7). No evident deactivation was Over Pt/CeO2, the infrared (IR) band (2103 cm–1)
Fig.1C, Pt/CeO2 showed a high onset temper- found at 500°C (fig. S7A), and slight deactiva- did not change appreciably after CO flow was
ature of ~210°C. After steam treatment (hydro- tion was observed at 800°C after one cycle, but stopped at 180°C while O2 continued to flow
thermal aging) at 750°C, the Pt/CeO2_S exhibited stable performance was maintained thereafter (Fig. 2A). This result suggested that CO adsorp-
dramatically improved low-temperature reactiv- (fig. S7B). Furthermore, there is no detrimental tion on the ionic Pt site was very strong at 180°C,
ity, compared to that of Pt/CeO2, as the onset effect on CO oxidation by other pollutants, such as reported previously (6, 7), and it is consist-
ent with the lack of activity for Pt/CeO2 below
210°C (Fig. 1C). However, over Pt/CeO2_S, after
CO flow was discontinued for 15 min at 180°C
(with continuing O2 flow), the intensity of the
IR band at 2091 cm–1 decreased substantially (by
57%) (Fig. 2B) as opposed to a 7% reduction on
Pt/CeO2 (Fig. 2A), suggesting that the CO adsorbed
on single-ion Pt2+ was readily oxidized to CO2.
This observation agrees well with the low-
temperature CO oxidation reactivity shown in
Fig. 1C, i.e., Pt/CeO2_S became active at 60°C
and 100% conversion was achieved at 148°C. We
concluded that CO adsorbed on Pt2+ in the Pt/
CeO2_S sample was more reactive than that ad-
sorbed on Pt2+ in the Pt/CeO2 sample. Because
Pt on both samples Pt/CeO2_S and Pt/CeO2 ex-
hibited the same atomic dispersion and valence
(Pt2+), the difference in low-temperature reacti-
vity between Pt/CeO2_S and Pt/CeO2 could be
attributed to neighboring lattice oxygen, which is
part of the active site (6, 9, 24) and thus should
have a dramatic effect on the reactivity of the
ionic Pt sites.
Active lattice oxygen, usually associated with
the oxygen vacancies on the uppermost ceria
layers in vicinity of Pt sites, can be considered
to be part of the active sites for this reaction.
However, they are short-lived and are difficult to
observe under steady-state reaction conditions
because the reoxidation rate of oxygen vacan-
cies is at least one order of magnitude faster than
Fig. 1. Characterization and performance of Pt/CeO2 catalysts. Representative aberration- that of oxygen-vacancy generation (20, 25). Hence,
corrected–STEM images of (A) Pt/CeO2 and (B) Pt/CeO2_S. Single atoms of Pt are circled in the CO2 formation in time-resolved CO oxidation
images. d(111), CeO2(111) lattice spacing. (C and D) Catalytic CO oxidation light-off performance of experiments was used to semiquantitatively mea-
different catalysts. [O2] = 10% and [CO] = 0.4% balanced with argon at a gas hourly space velocity sure these short-lived active oxygen species at
of 200,000 ml gcat–1 hour–1. Temperature ramp, 2°C per min; pressure, 1 atm. 300°C. Compared to the Pt/CeO2 sample, steam

Nie et al., Science 358, 1419–1423 (2017) 15 December 2017 2 of 5

 Corrected 25 January 2019. See Erratum.
R ES E A RC H | R E PO R T Corrected 4 February 2020. See full text.

treatment roughly doubled the amount of active 2098cm-1

lattice oxygen in Pt/CeO2_S (Fig. 2C). 0.05
0.05
2096cm-1
ionic Pt
The oxygen species of the catalysts were fur- ionic Pt
ther characterized by H2 temperature-programmed
reduction (H2-TPR) analysis (Fig. 2D). The reduc-
tion of bulk oxygen on CeO2 took place at or
above 600°C, and the absence of reduction peak
below room temperature was confirmed by cry-
ogenic H2-TPR (5). Two major reduction peaks 2174cm-1
2174cm-1
Gas phase CO
were observed for the Pt/CeO2 sample: (i) reduc- Gas phase CO
tion of the surface lattice oxygen in the vicinity
of Pt (Pt–O–Ce bond), centered at 184°C; and
(ii) reduction of surface lattice oxygen on CeO2
distant from Pt, centered at 348°C (5, 24). Over
Pt/CeO2_S, an extra peak at 162°C was observed, He flow CO/He flow
which was likely caused by a new type of active 184°C
surface lattice oxygen generated during steam Pt-O-Ce
bond
treatment. It is possible that over Pt/CeO2_S, CO 162°C
adsorbed on Pt sites was readily oxidized by this activated
type of active surface lattice oxygen, as confirmed surface
lattice
by DRIFTS (Fig. 2B), but over Pt/CeO2, it was not oxygen
(Fig. 2A). Detailed quantitative analysis for H2- 348°C
TPR (fig. S9) suggests that some of the sur-
face oxygen on CeO2 near Pt was also reduced
by H2 at a temperature <200°C in addition to
the Pt–O–Ce bonds (and/or the activated surface
lattice oxygen).
It has been accepted that the CO oxidation re-
Fig. 2. Identification of Pt single atoms (Pt2+) and active surface lattice oxygen. CO adsorption
action over metallic Pt supported on nonreducible
DRIFTS for (A) Pt/CeO2 and (B) Pt/CeO2_S. After 30 min of CO oxidation (black lines), the CO
oxides (Al2O3, SiO2, etc.) follows a Langmuir-
flow was discontinued, and the recording of spectra continued for 15 min with continuing O2 flow
Hinshelwood mechanism. For example (26, 27),
(magenta lines). Temperature, 180°C; a.u., arbitrary units. (C) Time-resolved CO oxidation with
over Pt/Al2O3, CO has an inhibiting effect on Pt0
surface active lattice oxygen of Pt/CeO2 catalysts at 300°C. Conditions: 50 standard cubic centimeter
reactivity at low temperatures due to competitive
per minute (SCCM) of He from 0 to 50 s; 50 SCCM of 10% CO in He from 50 to 200 s. (D) H2-TPR
adsorption between CO and O2, with a rate in-
profiles of Pt/CeO2 catalysts.
versely proportional to the partial pressure of
CO and first-order proportional to O2. By contrast,
over Pt/CeO2 catalysts, a Mars–van Krevelen re-
action mechanism is followed by dissociative O2
adsorption and activation, preferentially occur-
ring on ceria (in the vicinity of Pt), and the com-
petitive adsorption between O2 and CO over the
metal sites is circumvented (8, 20, 21). Both Pt/CeO2
and Pt/CeO2_S have similar atomically dispersed
Pt in the form of Pt2+, so the active surface lattice
oxygen aforementioned should be responsible
for the differences in the low-temperature reac-
tivity of these two catalysts.
In the current study, the Pt/CeO2 sample
(aged in air at 800°C) did not show CO oxida-
tion activity at temperatures lower than 210°C
(Fig. 1C). It was reported that thermal aging at
800°C led to strong Pt–O–Ce bond formation (5),
which overstabilizes the surface lattice oxygen
and results in the lack of low-temperature CO
oxidation reactivity (24). However, the strong
Pt–O–Ce bond led to atomically dispersed Pt and
excellent thermal stability (without Pt sintering
or CeO2 structure collapse). For Pt/CeO2_S, the
Pt–O–Ce bond was retained even after harsh
steam treatment (i.e., Pt remained as atomically
dispersed), which was also evidenced by the
XPS and Raman spectra (figs. S5 and S10).
Thus, compared to Pt/CeO2, the improvement Fig. 3. Illustration of steam-treatment effects on the atomically dispersed Pt/CeO2 catalyst.
in low-temperature CO oxidation reactivity of (A) The active site created by the steam treatment, which is responsible for low-temperature CO
Pt/CeO2_S could be attributed to the effect of oxidation activity, is highlighted by dashed green circles. (B) Gibbs free energy (DG°) of dissociative
high-temperature steam treatment (H2O vapor), water adsorption on the atomically dispersed Pt/CeO2 surface. One oxygen vacancy was filled by water
whose role is complex. under steam-treatment conditions (PH2O = 0.1 atm).

Nie et al., Science 358, 1419–1423 (2017) 15 December 2017 3 of 5

 Corrected 25 January 2019. See Erratum.
R ES E A RC H | R E PO R T Corrected 4 February 2020. See full text.

formed over atomically dispersed Pt/CeO2 by co-

feeding water during CO oxidation (13) or water
dissociation over Pt/CeO2 (29–32). Cofeeding
water in the reactants can further enhance the
low-temperature CO oxidation activity over Pt/
CeO2_S (fig. S8B). However, such enhance-
ment disappeared when water in the feed was
discontinued, because of the instability of the OH
groups formed on the Ce under reaction condi-
tions (13). By contrast, here, the active Olattice[H]
generated via high-temperature steam treatment
is thermally much more stable (up to 767°C), and
below this temperature, it can be readily regen-
erated during CO oxidation reaction cycles with-
out the need to cofeed water. This difference is
the main reason that we observed no deactiva-
tion during light-off measurements up to 500°C
(fig. S7A), and only at 800°C did we see slight
deactivation of the catalyst (fig. S7B). This is
further confirmed by the fact that all Pt remains
as single atoms after the first cycle to 800°C, as
evidenced by aberration-corrected–STEM (fig.
S13). The stronger basicity of the Olattice[H] com-
pared to that of surface OH may also lead to the
optimal Lewis acid-base pairs that promote low-
temperature CO oxidation.
Water vapor is always present in vehicle ex-
haust, and thus, our catalyst would be inher-
ently stable under exhaust conditions because
Fig. 4. Proposed reaction mechanism for CO oxidation on isolated Pt on a CeO2(111) surface. it was synthesized via calcination at 800°C in
The inset shows the calculated energy profiles in kJ mol–1. The structures of intermediates air followed by steam treatment at 750°C. More
and transition states (TSs) of the key elementary steps are shown in the reaction cycle. The importantly, this enhanced CO oxidation is also
reaction cycle corresponds to the energy profile for Pt/CeO2_S (steam-treated Pt/CeO2), found to occur on other commercially available
which is shown by the blue line in the inset. The red line shows the energy profile for Pt/CeO2 ceria, for example, from Aldrich and Rhodia (figs.
(reaction cycle is shown in fig. S12). S14 and S15). High-temperature steam treatment
not only enhances CO oxidation under simu-
lated vehicle exhaust conditions (fig. S16A), but
To better understand the nature of this new type with an activation barrier of 24 kJ mol–1 [(Fig. 4, also improves the oxidation of other compo-
of active surface lattice oxygen generated by transition state 2 (TS2)]. Thereafter, the OO[H] nents of exhaust, such as saturated and unsatu-
high-temperature steam treatment (H2O vapor) species (Fig. 4, intermediate V) reacts with the rated hydrocarbons (propane and propylene) and
on atomically dispersed Pt/CeO2, density func- second adsorbed CO, generating another CO2 NOx (figs. S16, B and C, and S17). The enhanced
tional theory calculations and reaction kinetic molecule with a smaller activation barrier of reactivity is not the result of the formation of
analyses were conducted. Oxygen vacancies from 38 kJ mol–1 (Fig. 4, TS3). Finally, the atomically Pt NPs, but rather the activation of surface oxy-
the CeO2 bulk can be redistributed to the CeO2(111) dispersed Pt/CeO2_S surface is recovered after gen on the ceria support. This demonstration of
surface (Fig. 3A) as a result of exposure to water CO2 desorption, and the catalytic cycle over the hydrothermal stability, along with high reactiv-
at a high temperature of 380°C, as previously re- steam-treated catalyst surface (2Olattice[H]) is ity, makes it possible to bring single-atom catal-
ported (28). Under steam-treatment conditions, closed. The overall energy barrier of the entire ysis closer to industrial application.
H2O molecules can then fill out the oxygen vacancy reaction cycle is 52 kJ mol–1, which is in agree-
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