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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Silver/hydroxyapatite foam as a highly selective catalyst for

acetaldehyde production via ethanol oxidation
Jing Xu a, , Xin-Chao Xu a , Xue-Jing Yang a , Yi-Fan Han a,b
a
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
b
Research Center of Heterogeneous Catalysis and Engineering Sciences, School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou
450001, China

a r t i c l e i n f o a b s t r a c t

Article history: In this study, highly dispersed sliver (Ag) nanoparticles supported on a hydroxyapatite showed a sur-
Received 19 October 2015 prisingly high activity (1.38 s1 in turnover frequency (TOF)), selectivity (100%) and durability (100 h)
Received in revised form 18 February 2016 for the oxidative dehydrogenation of ethanol to acetaldehyde. The structure of Ag nanoparticles is char-
Accepted 2 March 2016
acterized using transmission electron microscopy (TEM), X-Ray Diffraction (XRD), in-situ and ex-situ
Available online xxx
X-ray photoelectron spectroscopy (XPS) and temperature-programmed surface reaction (TPSR). Den-
sity Functional Theory (DFT) calculations on Ag(1 1 1) were performed to understand the mechanism of
Keywords:
catalytic reactions at a molecular level. The calculation results revealed that the barrier for the forma-
Ethanol
Acetaldehyde
tion of acetaldehyde is 38.6 kJ/mol, and 126.4 kJ/mol for CO2 formation, thus leading to high selectivity
Silver to acetaldehyde. By combination of DFT calculation and experimental work, it can be concluded that
Hydroxyapatite ethanol oxidation predominantly took place on the terrace surface although step surface are more active.
Oxidation This study provides a methodology to develop completely selective practical catalysts especially for the
utilization of biomass.
2016 Elsevier B.V. All rights reserved.

1. Introduction commercialized by passing alcohol vapors and preheated air over

Selective oxidation/dehydrogenation of ethyl alcohols to alde-
hydes, ketones and carboxylic acids is both technically and
fundamentally important, and found to be an essential reaction in
the utilization of biomass [13]. Bioethanol has been regarded as a
key building block in future biorenery industry. The transforma-
tion of bioethanol to value-added chemicals has attracted growing
concerns in the last decades [47].
Acetaldehyde is an important intermediate for the production
of chemical commodities such as acetic acid, acetic anhydride,
hydrocyanic acid, ethyl acetate, alkylamines and pyridines [8].
Commercial processes for acetaldehyde production include the oxi-
dation or dehydrogenation of ethanol, the addition of water to
acetylene, the partial oxidation of hydrocarbons and the direct
oxidation of ethylene. The last route, also named as the Wacker
process, is the primary method for industrial production [8].
With the ever-growing of the world output of bioethanol, the
production of acetaldehyde via alcohol oxidation has been gradu-
ally considered a feasible process. Indeed, a gas-phase process was
Corresponding author.
E-mail address: xujing@ecust.edu.cn (J. Xu).
silver (Ag) catalysts at 753 K, with a conversion of 7482% and a
selectivity of ca. 80% [9]. However, the high cost of Ag catalysts
(Ag powder or inorganic Ag compounds) became the major draw-
back of this process [10,11]; Ag nanocatalysts may be a promising
alternative. However, owing to the poor thermal conductivity of Ag,
highly dispersed Ag particles are easily sintered and aggregated at
elevated temperatures, which usually leads to a remarkable cat-
alyst deactivation. In addition, acetic acid, as a byproduct, even
with a trace amount in the reaction system, can erode the reac-
tor seriously at high reaction temperatures, thus leading to the
rise of the operational cost. Platinum group elements, IB and IIB
group elements have also been studied for this reaction; however,
either the selectivity or activity of those catalytic reactions doesnt
meet the industrial demands [12,13]. Therefore, the development
of novel catalysts for this process is highly desired in bioren-
ery industry. Aldehydes production with a complete selectivity
from oxidation/dehydrogenation of alcohols is both technically and
fundamentally challenging. In general, for the sustainable devel-
opment of economics, the complete selectivity reaction is a main
mission in catalysis eld in the future.
For the fundamental aspects, the studies of oxidative dehydro-
genation of ethanol over Ag catalysts have rarely been reported
so far [1416]. Wachs and Madix [17,18] have proposed a

http://dx.doi.org/10.1016/j.cattod.2016.03.001
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Fig 1. (a,b) TEM images and (c) XRD patterns of HAp.

Fig. 2. Morphology of Ag nanoparticles over the fresh (a and c) and spent (b and d) (0.5 wt%)/HAp catalyst by TEM.

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100
1000 cps 30 (a)
Ag 3d5/2

Selectivity to acetaldehyde (%)

95

Conversion of ethanol (%)

Ag 3d3/2 25
90
A
Intensity (cps)

20
85

15 80

10 75
B
70
5
65
0
C
60
450 500 550 600 650
Temperature (K)
364 368 372 376 380
Binding Energy (eV) 100
100
90
Fig. 3. XPS Ag 3d spectra recorded from the reduced (A), fresh (B) and spent (C) (b)

Selectivity to acetaldehyde (%)

catalyst. Reduction conditions in reaction cell: 573 K for 30 min, H2 ow: 20 ml/min. 80

Conversion of ethanol (%)

80
70
mechanism for the oxidation of methanol on a single crys-
60
tal Ag(1 1 0), which consists of several reaction steps: (1) 60
methoxy formation through the activation of O H bond by 50
adsorbed atomic oxygen (2CH3 OH(g) + O* 2CH3 O* + H2 O*) at 40 40
180 K, (2) C H bond scission to form formaldehyde and hydrogen 30
(CH3 O* CH2 O* + H*), (3) recombination with a surface hydro-
gen atom (H*) to form methanol (CH3 O* + H* CH3 OH*), and (4) 20 20
reaction with adsorbed formaldehyde to yield methyl formate 10
and hydrogen via the adsorbed H2 COOCH3 intermediate. In the 0 0
presence of excess oxygen, formaldehyde is further oxidized to for- 10 20 30 40 50 60 70 80 90 100
mate, which subsequently decomposes to CO2 and H2 O with the Time-on-stream (h)
assistance of surface oxygen (O*). In addition, a similar reaction
mechanism of oxidation of methanol was found on both Ag(1 1 1)
and Ag(1 1 0), with exception of the absence of methyl formate (c)
product on Ag(1 1 1) [19].
Following a similar way, ethanol on Ag(1 1 0) [18] is rst oxi-
dized to surface ethoxy and water upon adsorption at 180 K, and
ethoxy subsequently decomposes into acetaldehyde and hydrogen.
The recombination of surface hydrogen (H*) with ethoxy to form
ethanol is also observed.
In this study, a hydroxyapatite foam (HAp) is employed as the
support, which has proved good ability to disperse Au, Ru nanopar-
ticles [20]. Pure HAp powder also showed high activity in the
oxidation of formaldehyde at room temperature [21]. A highly dis-
persed Ag/Hydroxyapatite catalyst was prepared for the oxidation
of ethanol for the rst time, showing unexpected high selectiv-
ity to acetaldehyde, and the kinetics was measured as well. The
structure of Ag nanoparticles was characterized using transmission
electron microscopy (TEM), in-situ and ex-situ X-ray photoelectron
spectroscopy (XPS) and temperature-programmed surface reaction
Fig. 4. (a) Ethanol oxidation in the temperature range 453653 K; (b) ethanol oxi-
(TPSR). Besides, in order to get deep insight into the mechanism of
dation at 523 K for 100 h; (c) Arrhenius plot of the reaction rate (Ln(r) vs 1/T for this
this reaction, especially, the elucidation for the ultra high selectiv- reaction). Catalyst: Ag (0.5 wt%)/HAp, feed gas: 8.0 kPa ethanol, 2.0 kPa O2 , GHSV:
ity (ca. 100%) toward acetaldehyde, density functional theory (DFT) 36,000 h1 . Carbon balance was 99.9%.
calculations of ethanol oxidation on Ag were carried out as well.

2. Methods several times prior to overnight drying at 373 K. A ceramic foam of

2.1. Preparation of catalyst
HAp precursor was prepared by the addition of 3.6 g Ca(NO3 )2
(99.0%, Merck) and 1.2 g (NH4 )2 HPO4 (99.0% purity, Aldrich) in
the presence of 34 ml NH4 OH and 145 ml H2 O as described else-
where [20,21]. Briey, the mixture was magnetically stirred and
heated to 363 K for 90 min then 373 K for 120 min. The precipitated
HAp precursor was separated using vacuum ltration and washed
HAp was prepared by stirring 1.0 g of methyl cellulose (Alfa Aesar)
in 45 ml of deionized water with a stainless steel blade agitator at
20,000 rpm for 5 min. A mixture of 5.0 ml H2 O with 0.512 g HAp
was added into polymer solution and stirred for 10 min. The prod-
uct was calcined with a ramp rate of 0.7 K min1 to 523 K, holding
30 min then increased to 923 K with a ramp rate of 3.3 K min1 and
held at this temperature for 300 min.
Ag element was introduced to the system as Ag (0.5 wt%) sup-
ported on HAp powder (200 mesh). The catalyst was prepared by

Please cite this article in press as: J. Xu, et al., Silver/hydroxyapatite foam as a highly selective catalyst for acetaldehyde production via
ethanol oxidation, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.03.001
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Fig. 5. TPSR spectra of the oxidation of ethanol to acetaldehyde: the fresh catalyst as
prepared was rst saturated with oxygen and then adsorbed ethanol. The ramping
rate was 10 K/min in an Ar ow of 20 ml/min.
an incipient wetness method using an aqueous solution of AgNO3 .
The precursors were dried in an oven at 393 K overnight.
2.2. Activity measurements
Ethanol oxidation was carried out in a vertical xed bed micro
reactor (quartz reactor with 20 cm long and 0.4 cm in diameter)
under atmospheric pressure. In a typical experiment, the catalyst
is packed between two layers of quartz wool in the reactor. Ahead
of the experiment, Ag/HAp was heated in an air ow of 20 ml/min at
673 K for 30 min followed by a reduction in a H2 ow (20 ml/min)
at 573 K for 30 min. The reaction temperature was monitored by
a thermocouple with its tip located at the catalyst bed and con-
nected by a PID-type temperature indicator-controller. Catalytic
tests were performed with a mixture of ethanol (8.0 kPa) and air,
introduced by bubbling an ethanol solution at 298 K. The gaseous
products were analyzed by online gas chromatography (Agilent
6890) equipped with a ame ionization detector (FID) using HP-
5 capillary column, and a thermal conductivity detector, using a
Hayesep D column; a methanizer was equipped for the detection
of CO and CO2 . It is noted that HAp is almost inert in the reaction
below 623 K.
Absolute mass-specic reaction rates (Eq. (1)) were calculated
for the average concentration of each component,ci , at the in- and
outlet of the reactor. The carbon balance is ca. 99%:
cEthanol,in XEthanol Vgas
r Ethanol = [mol s1 gAg 1 ]
mAg
where mAg : mass of Ag in the reactor bed, V : total molar ow rate,
XEthanol : conversion of ethanol, cEthanol : concentration of ethanol in
gas mixture, equal to pi /p0 , pi : partial pressure of reactants, p0 :
total pressure in the system.
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Sequentially, the reaction turnover rate (rTOF , s1 ) was obtained
by Eq. (2)
rEthanol MAg 1
rTOF = [s ] (2)
DAg
where MAg : atomic weight of Ag, DAg : dispersion of Ag atoms
exposure to reactants evaluated on the basis of the model of semi-
hemispheric ball, about 17.9% dispersion of Ag was calculated
according to an average size of 4.5 nm for the fresh catalyst and
10.5% for the spent catalyst, an average dispersion of 14.0% was
used for calculation.
Additionally, the kinetic study was performed and the conver-
sion of ethanol was kept below 10% by diluting the catalyst with
SiO2 , which is inert to ethanol oxidation under current conditions.
Evaluation of the Weisz criterion showed the absence of mass trans-
port related problems [22].
2.3. Characterization
2.3.1. Surface area (BET)
Specic surface area and nitrogen adsorption-desorption were
determined using an ASAP 2020 surface area and porosity analyzer
(Micromeritics) via the Brunauer-Emmett-Teller (BET) method. A
gaseous mixture of nitrogen and helium was allowed to ow
through the analyzer at a constant rate of 30 ml/min. Nitrogen gas
was used to calibrate the analyzer and also used as the adsorbate
at liquid nitrogen temperature. The samples were thoroughly out-
gassed for 5 h at 423 K, prior to exposure to the adsorbent gas. The
surface area of pure HAp is 8.1 m2 /g and became 7.5 m2 /g after
loading Ag.
2.3.2. TEM
The catalyst powders were lightly ground, ultrasonically dis-
persed in ethanol, and several drops of the suspension loaded on
holey carbon lms supported by copper grids. Bright-eld images
were collected at 200 KeV using a JEOL 2010 microscope tted with
an ultra-high resolution pole piece.
2.3.3. XRD
XRD patterns were recorded using a RigakuD/max 2550 diffrac-
tometer, with accelerating voltage 40 kV, and detector current
100 mA. Cu-K radiation was used for continuous scanning with a
step-size of 0.02 over a 2 h range of 10 80 with a scan speed of
4 /min.
2.3.4. XPS
Ex-situ XPS analysis was performed on a VG ESCALAB 250 spec-
trometer, using Al-K radiation (1486.6 eV, pass energy 20.0 eV).
The base pressure of the instrument is 1 109 Torr. In-situ
XPS for Ag/HAp catalyst (treated in a H2 ow at 573 K with a
ow rate of 20 ml/min for 30 min in a reaction cell) was per-
formed on the another VG ESCALAB spectrometer, using Al-K
radiation (1486.6 eV, pass energy 50.0 eV) at a base pressure of
2 108 Torr. The background contribution B (E) (obtained by the
Shirley method) caused by inelastic process was subtracted, while
the curve-tting was performed with Gaussian-Lorentzian prole
by a standard software. The binding energies (BEs) over supported
catalysts were calibrated using C1s peak at 285.0 eV. The instru-
ment was also calibrated by using Au wire. XPS spectra were
recorded at = 90 of X-ray sources.
(1)
2.3.5. TPSR
The TPSR experiments were performed using a micro x-
bed reactor, which was connected with a GC-QMS (HPR-20,
Hiden Analytical Ltd.); masses (m/e: 18(H2 O), 25(C2 H2 ), 27(C2 H4 ),
29(CH3 CHO), 31(C2 H5 OH), 32(O2 ), 44(CO2 ), 60(CH3 COOH)) were
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J. Xu et al. / Catalysis Today xxx (2016) xxxxxx
monitored. After pretreatment, the catalyst was cooled down
to room temperature in an Ar ow, and then purged with O2
(20 ml/min) for 2 h followed by Ar (50 ml/min) for 5 min to expel
residual oxygen in the system. Then, the adsorption of ethanol was
carried out in a ow of 8.0 kPa ethanol and Ar (20 ml/min) followed
by Ar purge (50 ml/min) for 5 min to expel residual ethanol. The
TPSR experiment was carried out in a mixture of Ar ow with a
rate of 50 ml/min and a ramping rate of 20 K/min. The temperature
was ramped from 298 to 700 K at a rate of 20 K/min.
2.4. Computational methods
Binding energies, reaction energies and activation energies
were calculated using periodic spin-polarized density functional
theory (DFT) with the Perdew-Wang 91 [23] functional. The
interaction between ionic cores and electrons was described by
the projector-augmented wave (PAW) method [24,25], and the
exchange-correlation energy was calculated within the generalized
gradient approximation (GGA). The Kohn-Sham equations were
solved using a plane-wave basis set with a kinetic energy cutoff
of 400 eV.
A p(2 2) unit cell was used for Ag(1 1 1). For some steps that
p(2 2) is not enough to exclude the interaction between each unit
cell, a larger unit cell p(3 3) was used. For the DFT calculations,
only the topmost layer was allowed to relax and the remaining
layers were xed at their bulk positions.
The calculated optimized lattice constant for bulk Ag was 4.15 ,
which is in good agreement with the experimental value of 4.08
[26]. An interslab spacing of 10 was found to be sufcient to avoid
interactions between repeated slabs. A 3 3 1 Monkhorst-Pack
k-point grid was used to sample the surface Brillouin zone. With
these settings, binding energies were found to be converged within
3 kJ/mol with respect to slab thickness, interslab spacing and k-
point sampling.
The binding energies, Eb , were calculated as Eq. (3)
Eb = EX/Ag Eclean EX (3)
where EX/Ag , EX and Eclean are the total energies of the optimized
adsorbate-Ag(1 1 1) system, gas phase species X, and the clean
Ag(1 1 1) surface, respectively.
The climbing-image nudged elastic band (CI-NEB) method, was
used to obtain an initial guess for the transition state. Five interme-
diate states were used in our calculations and forces are minimized
to 0.05 eV/ with the quasi-Newton algorithm. The CI-NEB inter-
mediate structure with the highest energy was taken as an initial
guess and further optimized to the transition state structure. Vibra-
tional frequencies were calculated to conrm the nature of the
transition state.
3. Results and discussion
3.1. Catalyst structure and performance
HAp, as the support, adopts the ideal composition
Ca10 (PO4 )6 (OH)2 and possesses a zeolite-like frame that is
thermally stable (>1000 K). The obtained sample contains both
acid and base sites, and OH-enriched channels [27]. TEM images
(Fig. 1a and b) showed that pure HAp (50 nm in diameter) is well
crystallized, as also veried by XRD (Fig. 1c).
The fresh and spent Ag/HAp catalysts were determined by TEM.
An average Ag particle size of 4.5 0.5 nm was estimated for the
fresh catalyst (Fig. 2a and c) and increased mildly to 6.0 1.0 nm
after reaction (Fig. 2b and d). In particular, the images of lattice
fringe in Fig. 2c and d shows interplanar distances of 0.234 nm
in fresh and spent catalysts, which indicates Ag (1 1 1) is the pre-
dominant phase in Ag crystallines for both samples. However, XRD
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5
patterns of Ag nanoparticles were not detected due to the low con-
centration of Ag.
Using the surface-sensitive analytical technique XPS we found
that binding energies of 368.4 and 374.4 eV for Ag 3d5/2 and Ag
3d3/2, respectively, are in agreement with metallic Ag. To further
investigate the chemical state of Ag, Auger spectra was also col-
lected in in-situ XPS measurement. However, no Ag Auger signals
were obtained because the Ag concentration (0.5 wt%) is very low.
With the combination of TEM and XPS techniques, the surface Ag
atoms in Ag/HAp catalysts proved to be existed mainly in the form
of metallic state (Fig. 2c and d, Fig. 3). Nevertheless, the existence of
a small amount of oxide Ag atoms cannot be excluded completely.
In addition, the decrease in atomic ratios of Ag/Ca and Ag/P
(Table 1) after reaction indicated that a moderate aggregation of
Ag particles might occur, while the surface structure of HAp was
nearly intact as an identical Ca/P measured for both catalysts.
The conversion of ethanol increased with the rise of temper-
ature (Fig. 4a), the reaction started at 423 K and reached to a
conversion of ca. 18% at 550 K, while the selectivity to acetalde-
hyde was ca. 100%. With continuously raising the temperature, the
selectivity decreased steadily by the production of CO2 through
the complete oxidation. Moreover, the catalyst showed excel-
lent stability, with almost no change in activity and selectivity
after time-on-stream 100 h (Fig. 4b) at 523 K. The Arrhenius plot
of the reaction rate yielded an apparent activation energy (Ea )
of 35.9 2.5 kJ/mol (Fig. 4c), and the turnover rate (TOF) was
1.38 s1 at 523 K. In comparison with the rate for a bulk Ag catalyst
(1.38 104 mol s1 g Ag 1 ) (Table 2), the reactivity over Ag/HAp
(1.78 103 mol s1 g Ag 1 ) was improved by almost one order
of magnitude under similar reaction conditions. Clearly, Ag/HAp
exhibited superior activity, selectivity and stability towards the
oxidation of ethanol to acetaldehyde under mild conditions.
3.2. Mechanistic study
3.2.1. TPSR of ethanol oxidation
Ca2+ inside HAp channels can be potentially exchanged with
other metal ions including Ag ions during preparation process.
However, the analytic results by inductively coupled plasma mass
spectrometry (ICP-MS) and XPS (Table 1) demonstrated that there
was almost no change in the Ca concentration in HAp framework
after loading Ag, which is supposed to locate mainly at the external
surface of pores.
Several mechanisms have been proposed for selective oxida-
tion of alcohols over bulk silver catalysts [10,17,28]. Up to now, the
pathways for this reaction over Ag catalysts are still under debate.
A well-accepted point is that the oxygen-free silver surface is inac-
tive to alcohols dehydrogenation. An electron transfer may occur
between adsorbed oxygen molecules (O2ad ) and Ag atoms to form
O2ad , leading to a decrease in the bond order from 2 (O2ad ) to 1.5
(O2ad ) by lling an electron into 2p * orbital, while O2ad is then
cleaved into two active atomic oxygen. Ethanol is adsorbed on the
Ag surface by forming alkoxy groups while -H is extracted by the
pre-adsorbed oxygen species and the -H of alkoxy is eliminated
[10,18,29]. This assertion was partially evidenced by a TPSR prole
(Fig. 5), which revealed the formation of acetaldehyde at 423 K, in
agreement with the experiment in Fig. 4a. Desorption of oxygen
(440 K) and ethanol (480 K) was observed simultaneously, while
there was no signal for the formation of acetic acid. It is noted that
there was no such a reaction in an O2 -free atmosphere.
3.2.2. DFT calculations on the Ag(1 1 1) surface
To further account for the surprisingly high selectivity observed
for supported Ag nanoparticles, DFT investigation was carried out
to quantitatively outline the complete reaction mechanism with
all elementary reaction steps on Ag(1 1 1). The energetics for all the
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Table 1
XPS and ICP-MS analysis of Ag/HAp catalysts.

Samples B.E. of Ag3d (eV) Ag/Ca Ag/P Ca/P Ag/Ca/Pb

3d5/2 3d3/2

HAp / / / 1.42 0/1.64/1

Ag(0.5 wt%)/HAp (Reduced) 368.4 374.4 4.3% 6.2% 1.41 /
Ag(0.5 wt%)/HAp (Fresh) 368.4 374.4 4.8% 6.4% 1.42 0.079/1.65/1
FMHWa (2.1) (2.1)
Ag(0.5 wt%)/HAp (Spent) 368.6 374.7 4.2% 6.0% 1.42 /
FMHW (2.4) (2.4)
a
FMHW: full maximum at half width.
b
from ICP-MS.

Table 2
Comparison of the mass-specic and TOF rates for oxidative dehydration of ethanol to acetaldehyde over Ag catalysts.

Catalysts Ag loading Feed gas Temperature Mass-specic TOF (s1 ) Selectivity to Ref.
amount (wt%) (K) rate acetaldehyde (%)
(mol s1 g Ag 1 )

Ag-hollandite 9.7% pC2 H5 OH : 5.0 kPa, 523 2.30 104 / 70 11

(Ag0.7 Mn8 O16 ) pO2 :8.0 kPa
Bulk pure 593 1.38 104 / 85 28
electrolytic
silver
Ag/HAp 0.5 pC2 H5 OH : 8.0 kPa, 523 1.78 103 1.38 100 This
pO2 :2.0 kPa study

Fig. 6. Potential energy diagram of preferred pathways for ethanol oxidation towards acetaldehyde on Ag(1 1 1). The O and OH involved are omitted for clarity.

elementary steps has been summarized in Table 3. The plausible
potential energy diagram for the most preferred pathway of ethanol
oxidation is depicted in Fig. 6. The key step for this reaction is the
adsorption of ethanol and consequent reactions. Three mechanisms
are postulated for ethanol adsorption: (a) an oxygen-assisted disso-
ciative adsorption, (b) a hydroxyl-assisted dissociative adsorption,
and (c) direct dehydrogenation without any assistance.
Generally, ethanol molecules are rst weakly adsorbed on
Ag(1 1 1), and then dissociate to form ethoxy (CH3 CH2 O) and
hydroxyl species with a barrier of 7.7 kJ/mol through an oxygen-
assisted dehydrogenation mechanism. It indicates that ethanol can
readily dissociate in the presence of chemisorbed oxygen atom.
The formation of acetaldehyde by abstracting a hydrogen atom
from ethoxy with an assistance of chemisorbed oxygen is highly
exothermic and gives a reaction barrier of 38.6 kJ/mol. Therefore,
the oxygen-assisted dehydrogenation mechanism is preferred for
this reaction. The reaction barrier is in good agreement with our
measured apparent Ea of 35.9 2.5 kJ/mol (Fig. 4c). Acetaldehyde
found to be weakly adsorbed on the Ag(1 1 1) surface with a binding
energy of 8.7 kJ/mol, which indicates that acetaldehyde is facile
for desorption from the surface. Our DFT results are well supported
by the production of acetaldehyde in the presence of chemisorbed
oxygen at 423523 K (Fig. 5).

Please cite this article in press as: J. Xu, et al., Silver/hydroxyapatite foam as a highly selective catalyst for acetaldehyde production via
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Table 3
Activation barriers (Ea ), reaction energies (H) from DFT calculations for elementary reaction steps on Ag(111).

No. Reaction Ea /(kJ/mol) H/(kJ/mol)

1 CH3 CH2 OH* + O* CH3 CH2 O* + OH* 7.7 13.5

CH3 CH2 OH* + OH* CH3 CH2 O* + H2 O* 64.6 34.7
CH3 CH2 OH* + * CH3 CH2 O* + H* / 154.3

2 CH3 CH2 OH* + O* CH2 CH2 OH* + OH* 33.8 16.4

CH3 CH2 OH* + OH* CH2 CH2 OH* + H2 O* / 83.0
CH3 CH2 OH* + * CH2 CH2 OH* + H* / 193.9

3 CH3 CH2 OH* + O* CH3 CHOH* + OH* 74.3 1.9

CH3 CH2 OH* + OH* CH3 CHOH* + H2 O* / 100.3
CH3 CH2 OH* + * CH3 CHOH* + H* / 192.0

4 CH3 CH2 O* + O* CH3 CHO* + OH* 38.6 212.3

CH3 CH2 O* + OH* CH3 CHO* + H2 O* 62.7 73.3
CH3 CH2 O* + * CH3 CHO* + H* 46.3 2.9

5 CH3 CH2 O* + O* CH2 CH2 O* + OH* 95.5 5.8

CH3 CH2 O* + OH* CH2 CH2 O* + H2 O* / 62.7
CH3 CH2 O* + * CH2 CH2 O* + H* / 139.9

6 CH3 CHO* + O* CH3 CO* + OH* 67.5 41.5

CH3 CHO* + * CH3 CO* + H* / 120.6
CH3 CHO* + OH* CH3 CO* + H2 O* 102.3 29.9

7 CH3 CHO* + O* CH2 CHO* + OH* 49.2 21.2

CH3 CHO* + OH* CH2 CHO* + H2 O* 31.8 11.6
CH3 CHO* + * CH2 CHO* + H* / 128.3

8 CH2 CHO* + O* CH2 CO* + OH* 29.9 33.8

CH2 CHO* + OH* CH2 CO* + H2 O* 59.8 26.1
CH2 CHO* + * CH2 CO* + H* / 63.7

9 CH2 CHO* + O* CHCHO* + OH* 61.8 19.3

CH2 CHO* + OH* CHCHO* + H2 O* 54.0 47.3
CH2 CHO* + * CHCHO* + H* / 165.0

10 CH2 CO* + O* CHCO* + OH* 33.8 26.1

CH2 CO* + OH* CHCO* + H2 O* 101.3 17.4
CH2 CO* + O* CH2 COO* 6.8 115.8

11 CHCO* + O* CCO* + OH* 21.2 30.9

CHCO* + OH* CCO* + H2 O* 16.4 28.0
CHCO* + O* CHCOO* + * 15.4 93.6

12 CCO* + O* CCOO* + * 21.2 100.3

13 CH3 CO* + * CH3 * + CO* 173.7 106.1

CH2 CO* + * CH2 * + CO* / 228.7
CHCO* + * CH* + CO* / 225.8

14 CH2 COO* + * CH2 * + CO2 * 155.3 38.6

CHCOO* + * CH* + CO2 * 137.0 9.7
CCOO* + * C* + CO2 * 126.4 13.5

As long as acetaldehyde formed on the surface, it may be
dehydrogenated continuously via oxygen-assisted dehydrogena-
tion mechanism. Prior to the formation of CCOO intermediates,
all elementary reactions are exothermic and the maximum barrier
is 49.2 kJ/mol (Fig. 6). The only endothermic step is the dissocia-
tion of CCOO to form CO2 with a reaction energy of 33.8 kJ/mol.
Moreover, CCOO is the thermodynamic sink along the reaction
path and can be the precursor of CO2 . The breaking of C C bond
of CCOO gives an activation barrier of 126.4 kJ/mol. Such a high
barrier implies that CO2 formation can be beset with very slow
kinetics associated with the difculty in the C C bond scission. Con-
sequently, there is almost no CO2 detected at temperatures below
523 K.
The potential energy diagram for acetaldehyde formation on
Ag(1 1 1) (Fig. 6) indicates that surface oxygen atoms play an
essential role in the reaction. Our DFT results are consistent with
experimental ndings that hydrogen atoms were abstracted by
pre-adsorbed oxygen species [17,29]. At the temperature range
423523 K, it is energetically possible for surface oxygen atoms
reacting with ethanol to form acetaldehyde (e.g. an activation bar-
rier of 38.6 kJ/mol). The acetaldehyde on the surface is difcult
to further react with surface oxygen to form CO2 owing to a rel-
atively high barrier of 126.4 kJ/mol for C C cleavage. However,
the activation of C C bonds can be enhanced remarkably at tem-
peratures higher than 573 K, thus may lead to the formation of
CO2 . In general, the DFT results provide the origin of high selec-
tivity to acetaldehyde in molecular level in term of slow kinetics
for C C bond breaking on Ag nanoparticles under the mild condi-
tions.
3.2.3. Plausible mechanism for the selective oxidation of ethanol
on Ag/HAp
On the basis of above analysis, we propose that the oxidization of
ethanol can be divided into two regions by different temperatures,
as illustrated by Fig. 7, while the elementary steps were expressed
by Eqs. (4)(7): (I) Oxygen molecules (O2 (g)) are adsorbed on
Ag/HAp; (II) Atomic oxygen (O) is formed via the dissociation of
O2 ; (III) CH3 CH2 OH* is oxidized to CH3 CHO* mainly by O in the
lower temperature range 423523 K; (IV) CH3 CHO* is further oxi-
dized to CO2 with oxidant species (OS), including O and hydroxyl
species (OH) produced in the reactions at above 523 K:
O2 (g) + O2 (4)

Please cite this article in press as: J. Xu, et al., Silver/hydroxyapatite foam as a highly selective catalyst for acetaldehyde production via
ethanol oxidation, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.03.001
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CATTOD-10061; No. of Pages 9 ARTICLE IN PRESS
8 J. Xu et al. / Catalysis Today xxx (2016) xxxxxx
Fig. 7. Plausible mechanism for the selective oxidation of ethanol on Ag/HAp.
Hydrogen atoms are shown in white, carbon in grey, oxygen in red, Ag in blue,
calcium in green and phosphorus in pink; OS: oxidant species; *: surface active
sites. (For interpretation of the references to color in this gure legend, the reader
is referred to the web version of this article.)
O2 + 2O
CH3 CH2 OH + O CH3 CHO + H2 O (6)
CH3 CHO + 6OS 2CO2 (g) + 3H2 O
In the temperature range 423523 K, it is energetically possible
for surface oxygen species reacting with ethanol to form acetalde-
hyde (e.g. an activation barrier of 35.9 kJ/mol). There are always two
potential reaction pathways competing in this reaction system: (i)
Acetaldehyde is weakly adsorbed on the metal surfaces, such as
Au(1 1 1) [30] and Pt(1 1 1) [31], being facile for desorption from
the surface; (ii) Acetaldehyde formed may be further reacted with
oxidative species and completely oxidized to produce CO2 . In fact,
the pathway (ii) is not favorable below 523 K, owing to a relatively
high barrier for CO2 formation. At above 573 K, the activation of
C C bonds could happen, thus may lead to the formation of CO2 .
In addition, HAp has proved good ability to disperse Au and Pd
nanoparticles [20,32,33]. Surface hydroxyl groups and nonporous
structure of HAp have been suggested to stabilize metal precur-
sors to distribute uniformly on the HAp surface. Actually, the TEM
images in Fig. 2 also reveals that Ag nanoparticles can be stabilized
well on the HAp surface during the reaction. We deduce the active
sites may be located at Ag nanoparticles, being responsible for the
excellent selectivity. Nevertheless, the effects of interface between
Ag nanoparticles and HAp matrix cannot be ruled out completely.
Owing to possessing cation-exchange and adsorption capacity,
well-dened monomeric active species can also be immobilized on
the HAp surface. Based on the above-mentioned properties, HAp
can effectively disperse and stabilize Ag particles with a narrow
nano-sized distribution. However, there are still some puzzles to
be unsolved: (i) The mild growth of Ag nanocrystalline on the HAp
surface; (ii) The interaction between HAp and Ag, especially the ne
structure of Ag atoms at the interfaces; (iii) The reaction mechanism
for ethanol oxidation, such as the effect of steps, defects and terrace
of Ag nanoparticles on the reaction. The studies are still ongoing in
this group.
Please cite this article in press as: J. Xu, et al., Silver/hydroxyapatite foam as a highly selective catalyst for acetaldehyde production via
ethanol oxidation, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.03.001
4. Conclusions
A highly dispersed Ag(0.5 wt%)/HAp catalyst showed unex-
pected high activity (1.78 103 mol s1 g Ag 1 in mass-specic
rate, almost one order of magnitude higher than industrial silver
catalysts), selectivity (100%) and durability (100 h) in the oxida-
tive dehydrogenation of ethanol to acetaldehyde in a temperature
range 450550 K. Using in-situ and ex-situ XPS, HRTEM and TPSR,
we found the metallic Ag nanoparticles remained unchanged dur-
ing reaction; and the adsorbed oxygen played an important role in
the reaction.
Theoretical study of the oxidative dehydrogenation of ethanol to
form CH3 CHO* were performed on Ag(1 1 1) using DFT calculations.
Several conclusions on dominant Ag(1 1 1) surface are derived as:
(1) The oxidative species, such as O* and OH*, are necessary for
ethanol dehydrogenation; (2) The higher barrier (126.4 k J/mol) for
the activation of the C C bond in CCOO* indicates that it is the rate-
limiting step for CO2 formation; (3) The diffusion of atomic O* and
OH* is facile on the Ag surface, but plays trivial role in the reaction.
In general, this study provides a successful case for the devel-
opment of highly selective catalysts for the transformation of
biomass-based material to value-added chemicals. Insight into the
mechanism of alcohol dehydrogenation may be potentially used
for coinage metal catalysts, such as Au and Cu.
Acknowledgements
The authors are grateful to the support from the National Science
(5)
Foundation (21273070, 21576084, and 91534127) and Chinese
Education Ministry 111 project (B08021).
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Please cite this article in press as: J. Xu, et al., Silver/hydroxyapatite foam as a highly selective catalyst for acetaldehyde production via
ethanol oxidation, Catal. Today (2016), http://dx.doi.org/10.1016/j.cattod.2016.03.001