ARTICLE

https://doi.org/10.1038/s41467-022-30291-x OPEN

Photo-thermo semi-hydrogenation of acetylene

on Pd1/TiO2 single-atom catalyst
Yalin Guo1,2,7, Yike Huang 1,2,7, Bin Zeng2,3, Bing Han1,2, Mohcin AKRI1, Ming Shi2,3, Yue Zhao3, Qinghe Li1,
Yang Su1, Lin Li1, Qike Jiang4, Yi-Tao Cui5, Lei Li6, Rengui Li 3 ✉, Botao Qiao 1 ✉ & Tao Zhang 1
1234567890():,;

Semi-hydrogenation of acetylene in excess ethylene is a key industrial process for ethylene

purification. Supported Pd catalysts have attracted most attention due to their superior
intrinsic activity but often suffer from low selectivity. Pd single-atom catalysts (SACs) are
promising to significantly improve the selectivity, but the activity needs to be improved and
the feasible preparation of Pd SACs remains a grand challenge. Here, we report a simple
strategy to construct Pd1/TiO2 SACs by selectively encapsulating the co-existed small
amount of Pd nanoclusters/nanoparticles based on their different strong metal-support
interaction (SMSI) occurrence conditions. In addition, photo-thermo catalysis has been
applied to this process where a much-improved catalytic activity was obtained. Detailed
characterization combined with DFT calculation suggests that photo-induced electrons
transferred from TiO2 to the adjacent Pd atoms facilitate the activation of acetylene.
This work offers an opportunity to develop highly stable Pd SACs for efficient catalytic
semi-hydrogenation process.

1 CASKey Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
2 University
of Chinese Academy of Sciences, Beijing, China. 3 State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of
Chemical Physics, Chinese Academy of Sciences, Dalian, China. 4 Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian, China. 5 SANKA High Technology Co. Ltd. 90-1, Tatsuno, Hyogo, Japan. 6 Synchrotron Radiation Research Center, Hyogo Science
and Technology Association, Hyogo, Japan. 7These authors contributed equally: Yalin Guo, Yike Huang. ✉email: [email protected]; [email protected]

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E
thylene, one of the basic building blocks to produce plastic such as hydrogenation, oxidation, CO2 reduction, Fischer-
and key chemicals, is predominantly manufactured from Tropsch synthesis, water–gas shift reaction45–52. Despite of
steam cracking of hydrocarbons thus usually concomitant these great progress, whether photo-thermocatalysis is possible to
with small amount of co-produced acetylene. The co-existed acet- boost semi-hydrogenation of acetylene still remains inconclusive.
ylene can severely poison the downstream catalyst for ethylene Few studies related to photocatalysis of selective hydrogenation
transformation, thereby has to be diminished to an acceptable level for nitrobenzene53, benzaldehyde54, and alkynyl group55–59 were
(often <5 ppm)1,2. Diverse methods have been developed to reported, but the related works for photo-thermocatalytic acet-
eliminate the acetylene impurity among which the electrocatalysis ylene semi-hydrogenation are limited. Swearer et al. firstly
has been proven a green chemistry approach3,4. For example, Shi used Pd NPs and aluminum nanocrystals (AlNC) to construct
et al. reported a room-temperature electrochemical reduction a heterometallic antenna-reactor complexes photocatalyst
strategy of acetylene over a layered double hydroxide (LDH)- for semi-hydrogenation of acetylene but with a low product
derived Cu catalyst, which manifested high catalytic performance yield60. The other one is working at relatively high temperature
but suffers from unaddressed issues for large-scale applications, by converting photo into heat rather than an integration of
such as the low cell energy efficiency3. On the other hand, ther- photo-thermo catalysis process at lower temperature28.
mocatalytic semi-hydrogenation of acetylene into ethylene seems Herein, we report a simple yet general strategy to improve
more efficient, and has been extensively applied in industry for the selectivity of TiO2 supported Pd catalysts prepared by a
decades. Among various catalysts explored, supported Pd catalysts variety of methods via selectively encapsulating the co-existed
have attracted most attention on account of their superior intrinsic small amount of Pd nanoclusters/nanoparticles (NPs) due to
activity. Unfortunately, the low selectivity, especially at the full their different SMSI occurrence temperatures. In addition, on
conversion of acetylene, has long been a serious concern. Several account of the superior photocatalysis of TiO2 support, a much-
strategies based on the “active site isolation” concept, such as improved catalytic activity was obtained by integrating photo-
selective poisoning/covering special Pd sites (Lindlar catalysts5) or thermo catalysis and a dramatically decreased working tem-
forming Pd-M alloy/intermetallic compounds (industrially used perature of as low as 70 °C was realized. Detailed studies reveal
Ag-Pd/Al2O3 catalysts)6–11 to weaken the adsorption of ethylene that photo-induced electrons transferred from TiO2 to
have been frequently used to improve the selectivity12–21, which the adjacent Pd atoms facilitate the activation of acetylene and
are, nevertheless, often at the cost of activity loss due to the pre- thus benefit the photo-thermo catalytic semi-hydrogenation
sence of substantial inaccessible Pd sites. reaction.
Single-atom catalysts (SACs) have attracted rapid growing
interests as a new frontier in heterogeneous catalysis field22,23. In
SACs, isolated metal atoms are spatially separated and uniformly Results
distributed on the surface of the support, perfectly meeting the Synthesis and structural characterization of Pd/TiO2. The
“active-site isolation” concept while simultaneously maximizing Pd/TiO2 catalyst was firstly synthesized by ball milling based on
the metal utilization efficiency. Hence, SACs have been regarded the so called “precursor-dilution” strategy61–64 to obtain better
as an ideal candidate for semi-hydrogenation of alkyne and have dispersion but we will propose later that much more practical
shown promising catalytic performance24–29. Unfortunately, methods such as strong electrostatic adsorption (SEA) and even
SACs are generally less effective for H2 activation, giving rise to a impregnation methods also work well. The obtained Pd/TiO2 was
depressed hydrogenation activity30. Moreover, to maintain the reduced at 200 °C and 600 °C, denoted as Pd/TiO2-200H, and
isolated dispersion and good stability of SACs, a very low metal Pd/TiO2-600H, respectively. For comparison, the Pd/TiO2-600H
loading is often used. This is particularly true for Pd-based catalyst was re-oxidized by 10 vol% O2 at 300 °C, denoted as
SACs31. All these render the semi-hydrogenation of acetylene on Pd/TiO2-600H-O300. In addition, pure rutile supported catalysts
Pd SACs working currently at elevated temperatures. Therefore, were also prepared and tested in similar procedures.
to meet industrial application, it is necessary to develop stable and The BET specific surface area was measured to be about
efficient Pd SACs meanwhile lowering the working temperature. 70 m2 g−1 by N2 physical adsorption–desorption process, and the
Strong metal–support interaction (SMSI), a topic being incorporation of Pd did not change the surface area much,
extensively studied for more than 40 years in heterogeneous Supplementary Fig. 1. As shown in Supplementary Fig. 2, the
catalysis area32,33, has sparked renewed interests due to their X-ray diffraction (XRD) spectrum of the synthesized TiO2
potential in modifying catalyst performance, and especially in support displays typical patterns of both anatase and rutile,
stabilizing catalysts34–40. Recently, we found that isolated Pt suggesting a mixture structure. After loading of Pd, and even after
atoms supported on TiO2 can manifest classical SMSI34 but at a reduction at different temperatures and re-oxidation, there is no
much higher reduction temperature. A feature of this finding obvious structure change of the TiO2 support as evidenced by the
is that the co-existed nanoparticles (NPs) can be selectively similar diffraction patterns of various catalysts to that of TiO2
encapsulated while single atoms keep exposed through reduction support. In addition, no any diffraction pattern associated
at suitable temperatures. This finding might be extended to TiO2 with Pd species is observed, suggesting either the Pd is highly
supported other metal catalysts thus providing a new strategy to dispersed or the Pd loading is too low to be detected. The high
construct stable SACs. On the other hand, Photo-thermo catalysis dispersion of Pd was further examined by aberration-corrected
is an emerging sub-discipline that involves the integration of scanning transmission electron microscopy (AC-STEM). High-
thermo- and photocatalytic processes, which is distinct from the magnification high-angle annular dark-field (HAADF) STEM
traditional thermo-catalysis because photogenerated carriers can images reveal the presence of relatively high density of Pd single
directly transfer into the orbitals of adsorbed molecules to pro- atoms on all catalysts, Fig. 1a–d. Meanwhile some other HAADF-
mote their desorption, dissociation, or activation thus trigger the STEM images indicate the presence of small portion of Pd NPs,
chemical reaction, giving rise to a totally different reaction Supplementary Fig. 3. It stressed the great difficulty in fabricating
pathway41–44. Recent pioneering studies have demonstrated that “absolute” Pd SACs (presence of only isolated single atoms
the coupling of thermo- and photocatalytic processes overcomes without any clusters/NPs) even with such an effective ball-milling
the low activity in photocatalysis and high reaction barrier in method61–64. To our knowledge, so far the Pd SACs with
thermocatalysis, thus offering a promising strategy to promote relatively high metal loading on non-carbon supports have been
the activity and/or selectivity for various meaningful reactions, rarely reported65–67.

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Fig. 1 Structural characterization of Pd/TiO2 serial catalysts. a–d AC-HAADF-STEM images of a Pd/TiO2, b Pd/TiO2-200H, c Pd/TiO2-600H, and d Pd/
TiO2-600H-O300; Pd single atoms are highlighted in yellow circles. e, f DRIFT spectra of CO adsorption on Pd/TiO2-200H, Pd/TiO2-600H, and Pd/TiO2-
600H-O300 e at CO saturation adsorption and f upon He purging for 2.5 min at room temperature. g XANES spectra of different Pt/TiO2 catalysts at Pd
K-edge absorption edge.

Very recently, we discovered that Pt single atoms on TiO2 can TiOx nature was confirmed by electron energy loss spectroscopy
manifest classical SMSI upon reduction but at a much higher (EELS), Fig. 2b. After calcination at 300 °C, all CO adsorption on
reduction temperature compared with Pt NPs. The most mean- Pd NPs appears again, suggesting the encapsulation is reversible,
ingful feature of this discovery is that the NP active sites can be another typical characteristic of SMSI. The retreated cover layer
selectively encapsulated upon reduction at certain temperatures, was revealed by both BF-STEM image and EELS spectra, Fig. 2c, d.
therefore the catalytic performance can be finely tuned34–40. We Significantly, the still co-existence of single Pd atoms and Pd NPs
believe this scenario is general and may be extended to TiO2 illustrates that no aggregation happened during the reversible
supported Pd catalysts to distinctly refine their catalytic perfor- encapsulation process as shown in Fig. 1 and Supplementary
mance and we will prove this in the following. Fig. 3. This set of characterization unambiguously indicates that
Diffuse reflectance infrared Fourier transform (DRIFT) spectra the co-presented small amount of Pd NPs can be selectively
of CO adsorption were first employed to study the SMSI state of encapsulated by TiOx layer upon reduction at 600 °C.
our Pd/TiO2 sample and the results are presented in Fig. 1e, f and The electronic properties of Pd species with different
Supplementary Fig. 4. For CO saturation adsorption on Pd/TiO2- treatments were studied by X-ray absorption near-edge structure
200H, Fig. 1e, two peaks centered at 2106 and 2091 cm−1 and a (XANES) spectroscopy with Pd foil and PdO as reference
broad band existed in the range of 1840–1990 cm−1 were observed samples. As shown in Fig. 1g, XANES spectra display that the
in addition to the two gas phase CO bands. The former two are Pd K-edge absorption edge for Pd/TiO2, Pd/TiO2-200H, and Pd/
ascribed to linear CO adsorption on Pd single atoms and Pd TiO2-600H all located between that of Pd foil and PdO, indicating
NPs68, respectively, while the latter band is ascribed to the bridged the existence of positively charged Pd species. Additionally, the
and/or three-hollowed CO adsorption on Pd NPs. The linear CO spectrum of Pd/TiO2-600H is closer to that of Pd foil, suggesting
adsorption on Pd single atoms (2106 cm−1) can be further verified a lower chemical state with deeper reduction. The positive
by the weaker adsorption (i.e., faster desorption upon He purge) chemical state was contributed by Pd single atoms. Since the fact
and no frequency shift with CO coverage, which is in contrast to a that under SMSI state Pd NPs often existed as metallic or even
stronger CO adsorption and a frequency shift with CO coverage negatively charged state69, the slightly positive chemical state of
change on Pd NPs (from 2091 to 2082 cm−1), Fig. 1f and Pd suggests that the proportion of Pd NPs in the catalyst is very
Supplementary Fig. 4. The DRIFT characterization indicated the low. The valence state of Pd species on Pd/TiO2-600H was further
co-presence of Pd single atoms and Pd NPs, in consistent with the examined by X-ray photoelectron spectroscopy (XPS), Supple-
AC-STEM characterization results. After reduction at 600 °C, both mentary Fig. 5. It shows a mixture of Pd0 and Pdδ+, consistent
linear and bridged CO adsorption on Pd NPs disappeared well with the XANES result and further verifying the high valence
completely, Fig. 1e, suggesting the Pd NPs were encapsulated by of Pd single atoms.
reduced TiOx layer, a typical characteristic of SMSI. On the
contrary, CO adsorption on Pd single atoms remains almost
unchanged, suggesting the occurrence of SMSI on Pd atoms is Catalytic performance evaluation. Above results exhibited that
harder than that on Pd NPs. The encapsulation of Pd NPs was the small amount of co-existed Pd clusters/NPs on TiO2 sup-
further examined by AC-STEM, Fig. 2. The encapsulation layer ported Pd SACs can be selectively encapsulated meanwhile Pd
can be clearly observed in bright field (BF) image, Fig. 2a, and the single atoms were kept exposed thanks to their different SMSI

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Fig. 2 Structural characterization of Pd/TiO2 serial catalysts. a BF-STEM and HAADF-STEM images of Pd/TiO2-600H. b EELS spectra of Pd/TiO2-600H.
c BF-STEM and HAADF-STEM images of Pd/TiO2-600H-O300. d EELS spectra of Pd/TiO2-600H-O300.

occurrence temperatures. This feature is highly valuable in (Supplementary Figs. 7, 8). The stability is also very good; for
manipulating the catalytic performance. We testified this in semi- example, Pd/TiO2-SEA catalyst tested at 120 °C and 150 °C
hydrogenation of acetylene which is very sensitive to the isolation displays negligible selectivity change after 30 h, Supplementary
nature of the active sites. As shown in Fig. 3a, Pd/TiO2-200H Fig. 8. Additionally, a similar scenario happened on rutile
exhibited a high catalytic activity and the conversion of acetylene supported Pd catalysts, which show that the ethylene selectivity
reached 100% at 120 °C at a high weight hourly space velocity after reduction at a higher temperature 700 °C is much improved
(WHSV = 120,000 mL h−1 gcat−1). However, the selectivity of compared with that reduced at 200 °C, Supplementary Fig. 9. A
ethylene is as low as −300% due to the over hydrogenation of slightly higher reduction temperature of 700 °C was adopted
acetylene and hydrogenation of ethylene raw materials, Fig. 3b. It because rutile is slightly harder to form SMSI34,71. This result
further decreased to −500% with reaction temperature increase. suggests that the crystal phase of the support has limited influence
Remarkably, Pd/TiO2-600H exhibits a much-improved ethylene on the catalytic performance of SACs, in contrast to that on Pd
selectivity (from −500% to 40%) without any activity compro- nanocatalysts72,73.
mise in a wide reaction temperature window of 100−200 °C. In
addition, in a 40 h long-term test at 120 °C, the selectivity only
slightly decreased from 65 to 50% in the initial 30 h and kept Photo-thermo catalysis of semi-hydrogenation of acetylene.
almost unchanged thereafter, suggesting a good catalyst dur- Above results show that we have developed a general strategy to
ability, Fig. 3c. HAADF-STEM images of the used catalyst did not manipulate the catalytic performance, i.e., significantly improving
reveal detectable sintering of Pd single atoms/NPs, Supplemen- the selectivity of acetylene semi-hydrogenation. However, the
tary Fig. 6, in consistent well with the good catalyst durability. dissociation of H2 usually goes to a heterolytic pathway on SACs,
Above results demonstrated the application of Pd/TiO2 overcoming a higher barrier than that on the NPs with homolytic
catalysts in selective hydrogenation reaction by controlling the dissociation29. Lacking cooperation from neighboring metal
SMSI. Since the catalyst was prepared by a high-energy ball- atoms and losing metallic property, may decrease the ability of
milling process and the phthalocyanine precursors are costly, the single metal atoms to dissociate H2, leading to a lower intrinsic
process is less feasible for practical application. To verify activity for SACs. Recently, photo-thermo catalysis, i.e., inte-
the universality of this strategy, we prepared 0.15 wt% Pd/TiO2 grating photo- and thermo-catalysis to boost catalytic perfor-
catalysts by SEA70 (Pd/TiO2-SEA) and incipient wet- mance at more mild reaction condition, has attracted growing
impregnation (Pd/TiO2-IWI) methods, which are more simple attention45. However, little attention has been paid on the photo-
and practically applicable. Same scenario was observed on both thermo catalysis of acetylene semi-hydrogenation so far28,60. Here
catalysts that the selectivity after reduction at a high temperature we verified that photo-thermo catalysis could be a promising way
(650 °C) was much improved compared with those reduced at for semi-hydrogenation of acetylene. A continuous flow fixed-bed
200 °C, with only a little activity decrease on both catalysts reactor, as illustrated in Supplementary Fig. 10, was used for the

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Fig. 3 Catalytic performance of Pd/TiO2 serial catalysts. Acetylene conversion a and ethylene selectivity b as a function of temperature for acetylene
semi-hydrogenation over Pd/TiO2-200H and Pd/TiO2-600H. c Durability test on Pd/TiO2-600H at 120 °C for 40 h. Reaction conditions: 1 vol% C2H2,
10 vol% H2, 20 vol% C2H4 balanced with He; WHSV = 120,000 mL h−1 gcat−1.

photo-thermo catalytic semi-hydrogenation of acetylene. It turns increase the reactor temperature by 10 °C below 100 °C. As a result,
out that the introduction of light irradiation can indeed boost the a 10 °C-correction was used when performing photo-thermo
conversion of acetylene in semi-hydrogenation reaction remark- catalysis. It should be emphasized that upon light irradiation a
ably (from 20 to 80%) with a decreased ethylene selectivity, Fig. 4 very sharp response rather than a gradual increased process was
and Supplementary Fig. 11, indicating that the photogenerated observed, Fig. 4, demonstrating this is a photo-thermo catalysis
charges may involve in the reaction process. The decreased process by integration of photo- and thermo-catalysis45. To further
selectivity upon irradiation might stem from the increased acet- investigate the effect of light irradiation on semi-hydrogenation of
ylene conversion as the ethylene selectivity is usually acetylene- acetylene, the wavelength-dependence experiment was conducted
conversion-dependent1. After an initial evaluation stage (first under different wavelength ranges (full spectrum, λ > 420 nm and
cycle), the activity increased significantly from 30 to 80% upon λ > 480 nm). As shown in Fig. 4b, when the catalyst was irradiated
irradiation with an increased WHSV of 180,000 mL h−1 gcat−1, only by visible light (λ > 420 nm), the increasement of acetylene
then the conversion and selectivity maintain stable (see second conversion was significantly reduced compared with the full-
cycle) which can be verified by tests with more cycles, Supple- spectrum case in Fig. 4a, which indicates that the photoexcitation
mentary Fig. 12. The almost unchanged ethylene selectivity after of TiO2 is critical in semi-hydrogenation of acetylene. Noted that a
second cycle further confirms the above conjecture that ethylene slight improvement is still present when the visible light irradiated,
selectivity decrease is mainly related to the acetylene conversion, owing to the weak light absorption at the band edges of TiO2.
although influences from irradiation induced other changes, such Further, a 480 nm cutoff filter was introduced for comparison,
as chemical and/or SMSI74 state of Pd species, cannot be com- which can remove the possibility of the photoexcitation of TiO2. As
pletely excluded. expected, no improvement can be seen under light condition
To identify whether the improvement was induced by the (λ > 480 nm) compared with the dark case, Fig. 4c. Above results
thermal effect or not, we carefully measured the temperature under imply that the improvement in semi-hydrogenation of acetylene is
the light irradiation. As shown in Supplementary Fig. 10, the significantly attributed to the photoexcitation of TiO2, manifesting
potential heat effect was minimized by using a water bath equipped that the photogenerated charges involve and contribute to the
with circulating water. It is suggested that the light can still semi-hydrogenation reaction. A control experiment using Al2O3 as

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Fig. 4 Catalytic performance of photo-thermo catalysis over Pd/TiO2-600H, Pd/Al2O3 and XPS characterization. a–c Acetylene conversion over the
catalyst of 0.15 wt% Pd/TiO2-600H at 70 °C in the dark and 60 °C upon a full-spectrum light irradiation, power density: 167 mW cm−2, b visible light
(λ > 420 nm), power density: 141 mW cm−2 and c λ > 480 nm, power density: 127 mW cm−2. Reaction conditions: 1 vol% C2H2, 10 vol% H2, 20 vol% C2H4
balanced with He; WHSV = 180,000 mL h−1 gcat−1. d Acetylene conversion over the catalyst of 0.036 wt% Pd/Al2O3 at 70 °C in the dark and 60 °C upon
full-spectrum light irradiation with the similar reaction conditions. e Arrhenius plots for acetylene hydrogenation over the Pd/TiO2-600H upon light
irradiation or in the dark under the gas mixture of 1 vol% C2H2, 20 vol%H2, 20 vol% C2H4 balanced with He. f Pd 3d XPS spectra of Pd/TiO2-200H after
light irradiation by Xe lamp as well as the catalyst in dark.

a catalyst support to replace of TiO2, which suggests no irradiation was conducted at WHSV = 360,000 mL h−1 gcat−1,
enhancements in conversion and selectivity were observed, Fig. 4d Supplementary Fig. 13. The acetylene activity is boosted with the
and Supplementary Fig. 11d, further verifying the superiority of increased power density from 133 to 270 mW cm−2 accompanied
photo-thermo catalysis on the Pd/TiO2 catalyst. Additionally, by an opposite trend in ethylene selectivity. Moreover, kinetic
an intensity-dependent experiment upon a full-spectrum light measurement suggests that the apparent activation energy in

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suppress electron–hole recombination and accept the photo-

generated electrons via Schottky-junction. XPS measurement
reveals clearly that after light irradiation the binding energy (B.E.)
of Pd 3d5/2 shifted from 335.1 eV of Pd0 (metallic state) to
334.7 eV, Fig. 4f, indicating that photogenerated electrons in the
conduction band of TiO2 transferred to the adjacent Pd species to
increase their electron density. It was proposed that electron-rich
Pd is more effective for unsaturated hydrocarbons activation75,76
and/or hydrogen activation29. To verify the possible facilitated
hydrogen activation process, H2-D2 isotope exchange reaction
was firstly performed on Pd/TiO2-600H to evaluate H2 dissocia-
tion ability upon light irradiation or not, Supplementary Fig. 14.
The formation of HD could be observed immediately after D2
pulse and its formation rate was almost the same under both
cases. This excludes the improvement of H2 dissociation by
photo-thermo catalysis, implying that the main reason should be
the improvement of acetylene activation.

Simulation and calculation. To verify our hypothesis that pho-

togenerated carriers generated via excitation light facilitate the
activation of acetylene, first-principle simulations were performed
on a Pd1/TiO2 model catalyst. Note that in real catalyst, structures
of reactive sites are not uniformed, and in our case, the support is
a mixture of anatase and rutile. Detailed comparison between
structures obtained from simulation and experiments are shown
in the following Supplementary Table 2. Therefore, three kinds of
widely reported structures were used to simulate the model cat-
alyst (two for anatase, one for rutile, denoted as Pd/TiO2-a101-1,
Pd/TiO2-a101-2 and Pd/TiO2-r110, respectively, Supplementary
Fig. 15)77–79. For each model, three kinds of adsorbed structures
were considered, i.e., adsorbed H2 (H2*), adsorbed C2H2 (C2H2*),
and C2H2*-dissociated hydrogen (C2H2*-2H*), based on the
classical addition-elimination mechanism44, Supplementary
Fig. 16. Projected density of states (PDOS) analysis was per-
formed on wavefunctions of adsorbed structure as shown in
Fig. 5. Compared with the other two kinds of structures, in H2-
adsorbed structures, unoccupied states projected onto H element
distribute at higher energy than those projected onto C element.
This may imply it is harder to activate H–H bond than C–C
bond, which is in agreement with the experiment results.
According to PDOS, it is also shown that there are half-occupied
states belong to C2H2 molecule in all C2H2-adsorbed structures
but not in C2H2-2H-adsorbed structures. The half-occupied states
mainly localized on C2H2 imply strong electron-donation effect
of Pd single atom. In these cases, C–C bond is spontaneously
activated. More DOS of adsorbed structures, especially about
ethylene are provided in Supplementary Figs. 17–26.
To further study the effect of photo-induced activation of
Fig. 5 Projected density of states (PDOS) of ground states of nine chemical bonds, in principle, classical excitation methods such as
adsorbed structures on catalysts. a Pd/TiO2-a101-1. b Pd/TiO2-a101-2. Time Dependent Density Field Perturbation Theory (TDDFPT),
c Pd/TiO2-r110. Density of states that projected onto different kinds of Complete Active Space Self Consistent Field (CASSCF) or multi-
atoms are drawn with different color: C: pink, H: red, Pd: blue, Total DOS: configurational method should be used. However, for periodic
black. Fermi level has been shifted to 0 eV and marked by orange system which contains hundreds of atoms (in our cases more
dashed line. than 150 atoms at most), it is less possible to calculate excitation
states directly in a wide or even normal excitation energy range
photo-thermo catalysis is lower than that in thermal catalysis (22.9 like isolated molecular system because numbers of states need to
vs. 33.3 kJ mol−1), Fig. 4e, implying that a different reaction be calculated which increase exponentially respect to upper
pathway under light irradiation compared with the traditional boundary of excitation energy chosen to consider, Supplementary
thermal catalysis. Significantly, comparing with the previously Fig. 27. Fortunately, in our case, it is demonstrated that there
reported catalysts, the Pd/TiO2-600H is among the best and must be electrons excited in charge-transfer type ways from
outperforms most Pd-based catalysts for semi-hydrogenation of orbitals localized to support or its relative part, to orbitals
acetylene including both NPs and SACs, Supplementary Table 1. localized to absorbate, H2 and/or C2H2. To simulate charge-
Further study was performed to reveal the underlying reason of transfer type excitation and obtain approximated wavefunctions
the improved performance by photo-thermo catalysis process. of excited states, calculations based on Constraint Density
In general, metals supported on semiconductor can serve to Functional Theory (CDFT) were performed.

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Table 1 Bond orders of states and energy differences between charge-transfer states and their corresponding ground states in
wavelength units.

Structure Method B.O. λ/nm Activation or not

Pd/TiO2-a101-1-C2H2* DFT (ground state) 2.24 – –
CDFT Method 1 2.18a 348.61a Yesa
CDFT Method 2 2.25 487.22
Pd/TiO2-a101-1-C2H2*-2H* DFT (ground state) 2.22 – –
CDFT Method 1 2.25 884.29
CDFT Method 2 2.16a 500.58a Yesa
Pd/TiO2-a101-1-H2* DFT (ground state) 0.65 – –
CDFT Method 1 0.63c 321.88c Negligiblec
CDFT Method 2 0.70/0.74b 886.71/286.78b Nob
Pd/TiO2-a101-2-C2H2* DFT (ground state) 2.22 – –
CDFT Method 1 2.24 414.84
CDFT Method 2 2.25 546.59
Pd/TiO2-a101-2-C2H2*-2H* DFT (ground state) 2.29 – –
CDFT Method 1 2.31 1420.39
CDFT Method 2 2.24a 541.86a Yesa
Pd/TiO2-a101-2-H2* DFT (ground state) 0.68 – –
CDFT Method 1 0.67c 315.75c Negligiblec
CDFT Method 2 0.74/0.76b 594.23/285.80b Nob
Pd/TiO2-r110-C2H2* DFT (ground state) 2.22 – –
CDFT Method 1 2.21a 479.17a Yesa
CDFT Method 2 2.26 563.57
Pd/TiO2-r110-C2H2*-2H* DFT (ground state) 2.29 – –
CDFT Method 1 2.32/2.25a 3272.00/661.10a Yesa
CDFT Method 2 2.35/2.15a 863.89/337.65a Yesa
Pd/TiO2-r110-H2* DFT (ground state) 0.60 – –
CDFT Method 1 0.61 381.44
CDFT Method 2 0.66/0.69b 699.54/241.22b Nob

Excitation wavelengths of 18 possible modes on 9 structures are obtained by performing further CDFT by increasing number of electrons transferred, for more details, see the Supplementary Methods,
Supplementary Fig. 29 and Supplementary Figs. 32–34. TiO2-a101: anatase (101), TiO2-r110: rutile (110). For more detailed structural information, see the Supplementary Figs. 15, 16. Although there are
modes showing activation of unsaturated C–C chemical bond with wavelength larger than 480 nm, which may have negligible contribution to the activity improvement upon irradiation light in our case.
aModes showing decrease in B.O. and their wavelengths are larger than 320 nm are marked as “yes”.
bModes showing increase in B.O. and wavelengths shorter than 320 nm are marked as “no”.
cModes showing small decrease in B.O. but wavelengths close to 320 nm are marked as “negligible”.

CDFT is the method that extends energy functional by adding Then electrons start to fill orbitals with higher energy which
more variational terms (constraints), then optimizes extended contains anti-bonding orbitals of adsorbate, so bond order shows
energy functional as an outer loop of regular self-consistent-field rapid decrease. However, in real excitation process, there is no
calculation. Works on excitation properties with help of CDFT need or it is not compulsory to fill energy-lower orbitals first, so
have been widely reported and discussed in depth80,81. Those energy required for excitations which have activation effect on
constraints are always constructed manually with reasonable chemical bonds will only be smaller but not larger, i.e.,
consideration. In our case, the number of electrons transferred wavelength will only be longer but not shorter. In our CDFT
was considered and tuned in two ways (from TiO2 to Pd- simulated system, it turned out that C–C activation indeed exists
adsorbate composite (Method 1) or from catalyst (Pd/TiO2) to in Pd/TiO2-a101-1-C2H2*-2H*, Pd/TiO2-a101-2-C2H2*-2H*,
adsorbate (Method 2), see Computational details). The more Pd/TiO2-r110-C2H2* and Pd/TiO2-r110-C2H2*-2H* models at
electrons transfer to anti-bonding orbitals of adsorbate to activate least, H–H activation does not exist in all our models which
chemical bonds (H–H or C–C), the higher excitation energy (the shows consistency with ground state PDOS, and in good
shorter wavelength of light used to excite electron) will be needed, agreement with our experiments again. There are some excitation
Supplementary Fig. 28. Therefore, possibility of charge-transfer modes left uncertain in Table 1, but it is already enough to
type excitation caused activation of chemical bonds can be summarize that light irradiation can improve the reactivity of
estimated by judging if corresponding wavelength can locate in acetylene semi-hydrogenation by facilitating acetylene activation.
the catalyst absorption wavelength range. Wavefunctions of A possible mechanism as well as the reaction process is proposed
charge-transferred states were optimized with PBE0-TC-LRC in Supplementary Fig. 30, described as following: (1) Irradiation
hybrid functional, based on that of ground state also with ground leads to band-gap excitation of TiO2 support, generating
state optimized geometry, then energy differences between those electron–hole pairs, (2) H2 dissociation goes to a heterolytic
of two kinds of states were calculated and treated as approxima- pathway on isolated Pd sites and TiO2 (at the Pd–O interface), (3)
tions of vertical excitation energies. Mayer bond orders (B.O.) C2H2 molecules adsorb on isolated Pd sites and then photo-
were calculated as scalar descriptors to estimate impacts of charge generated electrons transfer to isolated Pd sites, facilitating the
transfer on chemical bonds activation listed in Table 182. activation of adsorbed C2H2, and (4) H species react with the
As shown in Supplementary Fig. 28, when increasing number activated C2H2 on Pd single atoms to form Pd-C2H4 species,
of electrons transferred, at first, electrons will fill orbitals with followed by C2H4 desorption. According to this mechanism, there
lower energy which contain components of bonding orbitals of should not be net charge accumulation. However, this seems in
adsorbate (significant in PDOS of C2H2-adsorbed structures contrast to the XPS characterization where net charge accumula-
shown in Fig. 5), so there will be small increase in bond order. tion occurs upon irradiation. It is conjectured that without the

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NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-022-30291-x ARTICLE

presence of reactants, a certain degree of net charge accumulation He gas at 200 °C and 650 °C for 0.5 h, denoted as Pd/TiO2-IWI-200H and Pd/
occurs because Pd atoms can accept some electrons from TiO2, TiO2-IWI-650H, respectively.
resulting in a difficulty in electron–hole recombination. However,
Strong electrostatic adsorption (SEA). As previously described70, 25 mL of deionized
under reaction condition electrons can be consumed by reactants, water was mixed with 75 mL of NH4OH to dissolve 1 g TiO2 support. Separately,
inhibiting the continuous net charge accumulation. This can be 40 μL of Pd(NO3)2 · 4NH3 was added to 25 mL of NH4OH to stir and disperse. The
verified by the stability of a 0.1 wt% Pd/TiO2-NP-200H catalyst 25 mL Pd(NO3)2 · 4NH3 solution was injected dropwise into the support solution
(to avoid any plausible effect of light on the SMSI state). It can be over 2 h by a constant flow pump stirring constantly. After precursor addition, the
seen that after an evaluation in the initial few hours in dark stirring solution was heated to 70 °C until completely dried. The dried catalyst was
calcined in a muffle furnace at 450 °C in air for 4 h (denoted as Pd/TiO2-SEA). Pd
condition, the catalytic performance is quite stable upon light loading of Pd/TiO2-SEA determined was 0.149 wt%. It was followed by reducing
irradiation, excluding the continuous net charge accumulation under 10 vol% H2/He gas at 200 °C and 650 °C for 0.5 h, denoted as Pd/TiO2-SEA-
(which may arouse activity change), Supplementary Fig. 31. 200H and Pd/TiO2-SEA-650H, respectively.

Sol–gel method. 0.1 wt% Pd/TiO2 NP catalyst was synthesized by sol–gel method.
Discussion Typically, 0.835 mL of PVA solution (2 mg mL−1) and 1 mL of Na2PdCl4 solution
In summary, we employed a simple yet general method to dra- (2 mg mL−1) were added to 10 mL aqueous solution at room temperature under
matically improve the selectivity of Pd/TiO2 catalysts in semi- vigorous stirring. After 30 min, 1.4 mL of 2 mg mL−1 NaBH4 solution was rapidly
hydrogenation of acetylene via selectively encapsulating the co- injected into the solution which turn to dark immediately, indicating the formation
of Pd colloid. 2 g of support TiO2 dispersed in 50 mL aqueous solution was then
existed small amount of Pd clusters/NPs to construct Pd1/TiO2 added and the mixture was continuously stirred for 12 h. The solid was collected
SACs according to their different SMSI occurrence conditions. by filtration, washed with deionized water, dried at 60 °C overnight, and then
Moreover, the photo-thermo catalysis was applied to this process calcined at 400 °C for 5 h under air. The obtained sample was then reduced in
and a much-improved catalytic activity was obtained: Upon H2/He (10 vol% H2/He, 30 ml · min−1) at 200 °C for 0.5 h prior to the hydro-
genation reaction, denoted as Pd/TiO2 NP-200H.
photo-thermo catalysis condition the semi-hydrogenation of
acetylene can be realized at temperature as low as 70 °C. Detailed
studies combined with DFT calculation revealed that photo- Characterizations
induced electrons transferred from TiO2 to the adjacent Pd spe- BET. Brunauer–Emmett–Teller (BET) surface area of TiO2 as well as the supported
cies facilitate the activation of acetylene thus benefiting the catalsyts was measured by N2 adsorption at 77 K using a Micromeritics ASAP 2010
reaction process. This work offers a promising strategy to apparatus. The samples were degassed at 100 °C for 1 h and 300 °C for 4 h before
nitrogen adsorption.
manipulate the catalytic performance of acetylene semi-hydro-
genation, and may also open up a window for photo-thermo UV–Vis spectra. UV–Vis spectra were collected by a UV/Vis/NIR spectro-
catalytic selective hydrogenation reaction. photometer (Perkin-Elmer, Lambda 950) with Peltier-controlled PbS detector. The
data interval is 0.2 nm and UV/Vis bandwidth is 2 nm.
Methods
Materials and chemicals. Palladium phthalocyanine (PdPc, 98%) was purchased ICP-AES/OES. The actual Pd loadings of all catalysts were determined by induc-
from 3A Materials, Titanyl phthalocyanine (TiOPc, purified by sublimation) was tively coupled plasma atomic emission spectroscopy (ICP-AES) on an IRIS
purchased from Tokyo Chemical Industry (TCI), and ethanol (99.7%) was pur- Intrepid II XSP instrument (Thermo Electron Corporation) or inductively coupled
chased from Sinopharm Chemical Reagent Co. Ltd. Ammonia (25 wt %) and plasma Optical Emission Spectrometer (ICP-OES) on ICPS-8100 instrument
Polyvinyl alcohol (PVA, Mw = 10,000, 80% hydrolyzed) were purchased from (Shimadzu Co., Ltd.).
Aladdin. Titanium (IV) oxide (mixture phases (99.7%) and rutile (AR)) and
sodium borohydride (NaBH4, 98%) were purchased from Alfa Aesar. Tetra- XRD. Powder XRD was performed at a PANalytical X’Pert PRO X-ray dif-
amminepalladium (II) nitrate solution (Pd(NO3)2 · 4NH3, 10 wt% in H2O) and fractometer using Cu-Kα radiation (λ = 0.15432 nm), operating at 40 kV
Sodium tetrachloropalladate (II) (Na2PdCl4, Pd 30%) were purchased from Sigma- and 40 mA.
Aldrich. All reagents were used without further purification. Deionized water was
obtained from a Millipore Autopure system. HAADF-STEM, AC-HAADF-STEM, and EELS. The high-angle annular dark-field
scanning transmission electron microscopy (HAADF-STEM) images were obtained
Catalyst preparation on JEOL JEM-2100F operated at 200 kV. The aberration-corrected high-angle
Ball milling. All in situ milling experiments were performed in Planetary Ball Mill annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM)
of RETSCH PM100 with a ZrO2 capsule (V = 50 ml) and ZrO2 milling balls images and the electron energy loss spectroscopy (EELS) were obtained on JEOL
(15 × 5 mm and 15 × 3 mm), and the milling speed was 400 rpm during the whole JEM-ARM200F operated at 200 kV equipped with a Gatan Quantum 965 image filter
process. For the preparation of support TiO2, TiOPc (4 g) was filled in the chamber system. The chemical compositions of the covering layer of Pd NPs were char-
firstly by a brief ball-milling process for 20 min, then 10 mL ethanol was added for acterized by directly putting electron beam at the Pd NPs in a STEM mode. Before
another 12 h grinding. The mixture was subsequently filtered and dried at 60 °C measurements, the samples were ultrasonically dispersed in ethanol, and then a drop
overnight, and the obtained material was calcined at 600 °C for 2 h in air of the solution was put onto the carbon film supported by a copper grid.
atmosphere.
For the preparation of Pd/TiO2, phthalocyanine (Pc) precursors containing DRIFTS. In situ diffuse reflectance infrared Fourier transform spectra (DRIFTS)
metal centers for Pd and Ti, i.e., PdPc (5 mg) and TiOPc (4 g) were mixed with a were acquired with a VERTEX 70 V infrared spectrometer equipped with a mer-
low weight ratio of 1: 800 (i.e., “precursor-dilution” strategy) firstly by a brief ball- cury cadmium telluride (MCT) detector and operated at a resolution of 4 cm–1
milling process for 20 min, then 10 mL ethanol was added to the chamber for using 32 scans. Before CO adsorption, all catalysts except Pd/TiO2-fresh were
another 12 h grinding. The mixture was filtered and dried at 60 °C overnight. After reduced at corresponding temperatures with 10 vol% H2/He and purged with pure
this process, PdPc was dispersed in the bulk TiOPc. After calcination at 600 °C for He for 30 min at the same temperature before being cooled. After cooled to room
2 h in air, the two precursor salts were converted to PdOx and TiO2, respectively, temperature, the background spectrum was recorded and then 2 vol% CO/He was
and Pd species was anchored on the support TiO2 in the form of single atoms introduced into the reaction cell, and the spectra were collected until the state
together with small amount of Pd NPs. The synthesized catalyst was denoted as Pd/ steady. Subsequently, pure He was introduced again to desorb the gas phase CO,
TiO2. It was followed by reducing under 10 vol% H2/He gas at 200 °C, 600 °C for and the spectra were also recorded.
0.5 h, denoted as Pd/TiO2-200H and Pd/TiO2-600H, respectively. The Pd/TiO2-
600H catalyst was re-oxidized under 10 vol% O2/He at 300 °C for 0.5 h, denoted as XANES. The X-ray absorption spectroscopy study was performed at the BL08B2*
Pd/TiO2-600H-O300. of SPring-8 (8 GeV, 100 mA), Japan, in which, the X-ray beam was mono-
chromatized with water-cooled Si (111) double-crystal monochromator and
Incipient wet impregnation. 0.15 wt% Pd/TiO2 catalyst was synthesized by incipient focused with two Rh coated focusing mirrors with the beam size of 2.0 mm in the
wet impregnation of 1 g TiO2 (mixture phases or rutile) with 1.5 mL 1 mg mL−1 horizontal direction and 0.5 mm in the vertical direction around sample position,
solution of sodium tetrachloropalladate (II) and 3.5 mL H2O. Prior to impregna- to obtain X-ray adsorption fine structure (XAFS) spectra both in near and extended
tion, the support was pre-reduced at 250 °C for 1 h (20 vol% H2/Ar, 50 mL min−1). edge.1 Pd foil and PdO samples were used as references. The catalysts and standard
After impregnation, the sample was dried at 60 °C and then calcined in a muffle samples were measured with fluorescence and transmission mode, respectively.
furnace at 450 °C for 4 h (denoted as Pd/TiO2-IWI). Pd loading of Pd/TiO2-IWI The spectra were analyzed and fitted using an analysis program Demeter.2 Before
determined by ICP was 0.146 wt%. It was followed by reducing under 10 vol% H2/ measurement, the Pd/TiO2 sample was reduced under 10 vol% H2/He at 200 and

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ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-022-30291-x

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styrene on titania supported platinum photocatalyst under 385 nm The authors thank Prof. Can Li at Dalian Institute of Chemical Physics for his valuable
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60. Swearer, D. F. et al. Heterometallic antenna-reactor complexes for B.Q. and T.Z. conceived and supervised the project. Y.G. carried out the catalyst
photocatalysis. PNAS 113, 8916–8920 (2016). synthesis, catalytic performance test, stability evaluation, and conducted some

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characterizations. Y.H. conducted the simulation and calculation. B.H., M.A., Q.L., and Reprints and permission information is available at http://www.nature.com/reprints
Li.Li. helped to analyze the data. Y.S. and Q.J. carried out the STEM and EELS char-
acterizations. Y.T.C. and Le.Li. carried out the XAS measurements and analysis. B.Z., Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in
M.S., and Y.Z. performed some photocatalytic experiments and helped on the discussion published maps and institutional affiliations.
of mechanism. R.L. guided and supervised the experiments of photo-thermo catalysis and
wrote the corresponding section. Y.G. and B.Q. wrote the paper. All authors contributed
to project discussions and modified the paper. Open Access This article is licensed under a Creative Commons
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