pubs.acs.

org/est Article

Effect of Formaldehyde in Selective Catalytic Reduction of NOx by

Ammonia (NH3‑SCR) on a Commercial V2O5‑WO3/TiO2 Catalyst under
Model Conditions
Anh Binh Ngo, Thanh Huyen Vuong, Hanan Atia, Ursula Bentrup, Vita A. Kondratenko,
Evgenii V. Kondratenko, Jabor Rabeah, Udo Ambruster, and Angelika Brückner*
Cite This: Environ. Sci. Technol. 2020, 54, 11753−11761 Read Online
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ACCESS Metrics & More Article Recommendations *

sı Supporting Information

ABSTRACT: The impact of formaldehyde (HCHO, formed in vehicle exhaust

Downloaded via SETON HALL UNIV on October 1, 2023 at 23:43:23 (UTC).

gases by incomplete combustion of fuel) on the performance of a commercial

V2O5-WO3/TiO2 catalyst in NH3-SCR of NOx under dry conditions has been
analyzed in detail by catalytic tests, in situ FTIR and transient studies using
temporal analysis of products (TAP). HCHO reacts preferentially with NH3 to a
formamide (HCONH2) surface intermediate. This deprives NH3 partly from its
desired role as a reducing agent in the SCR and diminishes NO conversion and N2
selectivity. Between 250 and 400 °C, HCONH2 decomposes by dehydration
(major pathway) and decarbonylation (minor pathway) to liberate toxic HCN and
CO, respectively. HCN was proven to be oxidized by lattice oxygen of the catalyst
to CO2 and NO, which enters the NH3-SCR reaction.

■ INTRODUCTION
Removal of nitrogen oxides (NOx) from exhaust gases of
industrial plants and transportation facilities is a major global
challenge, since these pollutants cause serious problems such
as acid rain, smog, ozone depletion, and global warming.
Selective catalytic reduction with NH3 (NH3-SCR, eqs 1−3)
by catalysts based on V2O5, WO3, and TiO2 (VWT) is an
established commercial process to remove NOx from sta-
tionary and mobile sources driven by fossil fuel.1,2 In addition
to complete NOx conversion and N2 selectivity at high flow
rates and in a broad temperature range, stability especially in
the presence of SO2 and H2O is another crucial requirement.3
4 NH3 + 4 NO + O2 → 4 N2 + 6 H 2O
2 NH3 + NO + NO2 → 2 N2 + 3 H 2O
8 NH3 + 6 NO2 → 7 N2 + 12 H 2O
Apart from NOx, the exhaust gas can also contain certain
amounts of formaldehyde (HCHO), resulting from incomplete
combustion of hydrocarbon fuels.4−10 This pollutant is toxic
and hazardous for human health even at low concentrations.11
HCHO concentrations in exhaust gases vary depending on the
types of fuel, engines, and combustion conditions. Its
formation is a special problem in gas engines driven by
methane with port injection or homogeneous charge supply12
and also in diesel/methanol dual fuel engines.13 A report from
the United States Environmental Protection Agency indicated
that the emission rate of HCHO can reach 0.008−0.032 g/
mile in light-duty vehicles and trucks, which correspond to
about 2−7% of the total NOx emission rate.6 In commercial
marine shipping, HCHO emissions of 0.11 to 0.15 g per kg
fuel14 and 0.01 to 4.38 mg h−1 (corresponding to 1−40% of
NOx emission) were found in the exhaust gas of diesel engines,
depending on the type of fuel (biodiesel B20, ultralow sulfur
diesel) and engine (light duty, medium duty).15 In many cases,
a diesel oxidation catalyst (DOC)-installed upstream oxidizes
already a certain amount of HCHO before entering the SCR
catalyst. Supported Pt catalysts, being frequently part of those
DOCs, can oxidize HCHO already close to room temper-
ature.16 However, also the opposite effect has been observed.
Thus, when alcohol-containing fuels such as diesel/methanol
mixtures13 or biodiesel17 were used, additional HCHO was
(1)
formed in the DOC due to oxidation of the alcohol, especially
(2) at low temperature and low engine speed.
Surprisingly, despite the fact that HCHO emission from
(3) combustion engines is a serious problem in exhaust gas
treatment, there are only very few investigations on its effect in
NH3-SCR of NOx. Thus, Bertole has studied the inhibition
effect of unburned hydrocarbons on the HCHO oxidation rate
in V-W/Ti NH3-SCR catalysts.18 Very recently, Zheng et al.
performed the NH3-SCR of NOx over 3 wt % V-W(Mo)Ti
Received: February 14, 2020
Revised: July 17, 2020
Accepted: August 13, 2020
Published: August 13, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.est.0c00884

11753 Environ. Sci. Technol. 2020, 54, 11753−11761
Environmental Science & Technology pubs.acs.org/est Article

catalysts in the presence of propylene, dodecane, and NO, NO2, and NH3 concentrations were measured with an
HCHO.19 Partial oxidation of these hydrocarbons led to a ultraviolet multigas sensor detector (ABB gas analyzer models
slight increase of the HCHO concentration and high CO AO2020, Limas 11HW, Mannheim, Germany). Simultane-
emissions. It was also found that the presence of HCHO ously, the contents of N2 and N2O formed during the SCR
hindered the NH3-SCR of NOx below 250 °C and led to reaction were analyzed with an Agilent HP 6890 GC equipped
higher CO emissions. However, to the best of our knowledge, with a molecular sieve 5A and a Porapak Q capillary column,
no detailed mechanistic studies on the role of HCHO under respectively.
NH3-SCR conditions and its reactions with the various feed Conversion of NOx, NH3, and HCHO was calculated from
components have been performed. the concentration ratios at the reactor inlet and outlet (eqs
It is therefore the aim of this work to explore (i) the effect of 5−7). N2 selectivity was calculated from the ratio of the N2
HCHO on the performance of a commercial V2O5-WO3/TiO2 concentration to the total reacted concentration of NOx and
catalyst in NH3-SCR of NOx and (ii) the role of HCHO in the NH3 (eq 8). The selectivity of products formed from HCHO
formation pathway of intermediates and products. To this end, was calculated according to eqs 9−12.
the interaction of HCHO with different single feed [NOx ]in − [NOx ]out
components as well as with their mixtures under dry SCR X NOx = ·100%
model conditions has been studied in detail by in situ/ [NOx ]in (5)
operando IR spectroscopy as well as temporal analysis of
products with sub millisecond resolution, and a mechanistic [NH3]in − [NH3]out
X NH3 = ·100%
proposal is put forward. Under real NH3-SCR conditions, [NH3]in (6)
significant amounts of water are present in the feed, especially
when aqueous solutions of urea (ad blue) are used as the [HCHO]in − [HCHO]out
XHCHO = ·100%
source for NH3. Nevertheless, we decided not to add water in [HCHO]in (7)
this stage of the study, since our aim here was to gather first
information on basic reaction steps that can form the basis for 2[N2]
S N2 = ·100%
subsequent investigations, which are currently under way. [NOx ]in + [NH3]in − [NOx ]out − [NH3]out
These comprise the impact of catalyst composition on the (8)
formation of sites involved in these steps, including the effect
of water. [CO2 ]out

■
EXPERIMENTAL SECTION
Catalytic Tests. NH3-SCR of NOx was performed in a
fixed-bed quartz plug-flow reactor. HCHO (100−200 ppm)
was injected into a feed gas of 0.1 vol % NH3, 0.1 vol % NO,
and 5 vol % O2/He. Though HCHO concentrations entering
the SCR catalyst of certain engines might be below 100 ppm,
we used 100−200 ppm HCHO to ensure comparable
conditions in catalytic tests and in situ FTIR studies, for
which lower concentrations led to too low signal-to-noise
ratios. The total flow rate for all experiments was 100 mL
min−1, corresponding to a gas hourly space velocity (GHSV) of
70,000 h−1. For each experiment, 100 mg of particles (250−
315 μm) of a commercial VWT catalyst (1 wt % V, 6 wt % W/
TiO2, Argillon GmbH) diluted with 500 mg of α-Al2O3 were
used. HCHO was generated by thermal decomposition of
trioxane (eq 4) and transported into the SCR reactor by
flowing helium.20
(CH 2O)3 → 3 HCHO
(4)
A scheme of the set-up for the catalytic tests including the
HCHO generation unit is shown in Figure S1 of the
Supporting Information. The HCHO containing He flow
was injected into the NH3-SCR feed gas. The concentration of
HCHO (100−200 ppm) was adjusted by the flow rates of the
two streams and calibrated by its oxidation to CO2 and CO in
the NH3-SCR reactor (eq 2, Supporting Information) with an
online FTIR spectrometer (ThermoFisher Scientific). Admis-
sion of the HCHO-containing gas stream to the reactor was
started after reaching a stable HCHO concentration. The
products (i.e., HCN, CO, CO2, and hexamethylenetetramine,
(CH2)6N4 (HMT)) of HCHO conversion were also analyzed
with the above mentioned FTIR spectrometer. Respective
bands used for calibration including calibration curves are
shown in Figure S2.
11754
SCO2 = ·100%
[HCHO]in − [HCHO]out (9)
[CO]out
SCO = ·100%
[HCHO]in − [HCHO]out (10)
[HCN]out
SHCN = ·100%
[HCHO]in − [HCHO]out (11)
6[(CH 2)6 N4]out
S(CH2)6 N4 = ·100%
[HCHO]in − [HCHO]out (12)
To separately study the oxidation and decomposition of
HCONH2, which revealed to be an intermediate in NH3-SCR,
the same reactor and conditions (temperature, GHSV, and
catalyst) as in the NH3-SCR reaction were used. A beaker with
liquid HCONH2 inside a glass tube was placed in an aluminum
block at 100 °C, and 5 mL/min He was flushed through to
inject HCONH2 into a feed of 5 vol % O2/He (100 mL/min).
Products generated from the reaction of HCONH2 were also
detected with the same equipment described above (Figure
S1).
In Situ FTIR Experiments. In situ FTIR experiments were
carried out with a Thermo Scientific Nicolet 6700
spectrometer in transmission mode equipped with a custom-
made heatable reaction cell with CaF2 windows connected to a
gas dosing system. For each experiment, the VWT sample (40
mg) was pressed into a self-supporting wafer (Ø 20 mm) and
pretreated at 350 °C for 1 h in a 5 vol % O2/He flow (50 mL
min−1) followed by cooling to 150 °C. After pre-adsorbing
HCHO/O2 (200 ppm HCHO, 5 vol % O2/He) for 60 min
and subsequent flushing with He, the catalyst was exposed to
0.5 vol % NH3/He for 10 min, and then, the cell was closed to
follow the reaction of the adsorbed species for 50 min. The
reverse experiment was carried out by pre-adsorbing 0.1 vol %
NH3/He and subsequent exposure to 400 ppm HCHO and 5
https://dx.doi.org/10.1021/acs.est.0c00884
Environ. Sci. Technol. 2020, 54, 11753−11761
Environmental Science & Technology
Figure 1. (a) NOx conversion, (b) NH3 conversion, and (c) N2 selectivity in the presence of 0−200 ppm HCHO, and selectivity of other products
(based on HCHO) for (d−f) different concentrations of HCHO. HCHO conversion was 100% for all HCHO concentrations at all temperatures
and is not shown.
vol % O2/He. In a further experiment, pre-adsorbed NH3 was
subjected to a mixture of 400 ppm HCHO, 0.2 vol % NO, and
5 vol % O2/He. Moreover, the catalyst was exposed to a
continuous flow (50 mL min−1) of 200 ppm HCHO, 0.1 vol %
NH3, and 5 vol % O2/He for 60 min followed by turning off
the feed, closing the cell, and heating to 350 °C to study the
decomposition of the adsorbed species. For studying
adsorption of HCONH2 on the VWT catalyst, liquid
HCONH2 (Fluka, purity >99.0%, CAS 75-12-7) was dropped
directly onto the catalyst wafer after pretreatment at 350 °C in
a flow of 5 vol % O2/He for 1 h. This wafer was then
transferred into the IR cell and heated at 150 °C under He
flow for 1 h before recording the spectrum. Generally,
difference spectra are shown, obtained by subtraction of the
spectrum measured at 150 °C after pretreatment in 5 vol %
O2/He at 350 °C from the respective adsorbate spectra.
Oxidation and Decomposition of HCN on V2O5-WO3/
TiO2 under Transient Conditions. HCN oxidation tests
over V2O5-WO3/TiO2 were carried out in the temporal
analysis of products (TAP-2) reactor, a time-resolved
technique with a resolution of about 100 μs.21−23 The catalyst
(m = 41 mg, sieve fraction of 315−710 μm) was packed
between two layers of quartz particles (sieve fraction of 250−
350 μm) within the isothermal zone of the microreactor made
of quartz. Prior to the tests, it was treated in a flow of O2 (3
mL/min) at 500 °C for 0.5 h. Hereafter, two types of pulse
experiments were performed between 350 and 500 °C. The
ability of lattice oxygen to oxidize HCN was tested by pulsing a
mixture of HCN/N2 = 1:9. To elucidate the role of adsorbed
oxygen species in HCN oxidation, 18O2/Ar = 1:2 and HCN/
N2 = 1:9 were pulsed with a time delay of 0.5 s between the
pulses. In the latter tests, the catalyst was treated at each
experimental temperature in a flow of O2 (3ml/min) for 5 min
to remove 18O species remaining on the surface after the
11755
pubs.acs.org/est Article
previous experiment. A HCN/N2 mixture was supplied by
Linde. An 18O2/Ar mixture was prepared using 18O2 (97% 18O,
Campro Scientific) and Ar (5.0, Air Liquide). All gases or
mixtures used in the transient experiments were applied
without additional purification.
Transient responses of pulsed gases and formed reaction
products were monitored at the reactor outlet with a quadruple
mass spectrometer (HAL RD 301 Hiden Analytical) at atomic
mass units (AMUs) related to these substances: 48 (C18O2),
46 (N16O2), 44 (C16O2, N216O), 36 (18O2), 32 (N18O), 30
(N16O), 28 (CO, N2), 27 (HCN), 29 (C3H8), 20 (H218O, Ar),
18 (H216O), 2.0 (H2), and 40 (Ar). For each AMU, pulses
were repeated 10 times and averaged in order to improve the
signal-to-noise ratio.
■ RESULTS AND DISCUSSION
Catalytic Tests. The effect of HCHO on the conversion of
NH3 and NO over the VWT catalyst in NH3-SCR of NOx as
well as on product selectivity is shown in Figure 1. In the
absence of HCHO, NOx conversion reaches its maximum
above 250 °C (90−96%) and declines again above 400 °C
(Figure 1a). Such a decline is due to partial oxidation of NH3
as has been confirmed in a separate experiment (Figure S3).
NH3 is converted almost completely above 250 °C (95−
100%) (Figure 1b). N2 is the only product below 400 °C
(Figure 1c), while its selectivity declines above 400 °C due to
formation of N2O as a side product.
In the presence of 100−200 ppm HCHO, almost the same
amount of N2O is formed above 400 °C (Figure S4); however,
the N2 selectivity is lowered in the whole temperature range
(Figure 1c). The same is true for the NOx conversion (Figure
1a), while the NH3 conversion was almost not influenced and
remained complete above 250 °C (Figure 1b). This suggests
that HCHO reacts preferentially with NH3, thus reducing the
https://dx.doi.org/10.1021/acs.est.0c00884
Environ. Sci. Technol. 2020, 54, 11753−11761
Environmental Science & Technology
Figure 2. Conversion of HCHO, NO, and NH3 (dashed lines) and selectivity of products based on HCHO for different feed compositions: (a) 100
ppm HCHO and 5 vol % O2/He, (b) 100 ppm HCHO, 0.1 vol % NO, and 5 vol % O2/He, (c) 100 ppm HCHO, 0.1 vol % NH3, and 5 vol % O2/
He.
amount of the latter available for the SCR reaction with NO
(eqs 1−3). Consequently, also the N2 selectivity decreased in
the presence of HCHO, especially at low temperatures (Figure
1c). The direct reaction between HCHO and N2O can be
excluded, since HCHO is completely converted already well
below the onset of N2O formation (Figure 1) and, therefore, is
no more available for reaction with N2O.
HCHO conversion remained unchanged at 100% during
NH3-SCR at all concentrations and in the whole temperature
range. Therefore, only NOx and NH3 conversion together with
the selectivity of products formed from HCHO is plotted in
Figure 1. In general, the selectivity trends are similar for all the
HCHO concentrations tested. HCN is the main product,
reaching its maximum yield in the range of 250−400 °C.
Below 250 °C, a small amount of hexamethylenetetramine,
(CH2)6N4 (HMT), was observed. Above 450 °C, CO2 is
formed significantly whereby this total oxidation is less
pronounced for the lowest HCHO concentration. Interest-
ingly, CO2 formation shows a small maximum at 200 °C for all
HCHO concentrations, which matches with a weak minimum
in NH3 conversion at 200 °C (Figure 1b). This was surprising
since an increase rather than a drop of NH3 conversion would
have to be expected when NH3 reacts not only with NOx but
also with HCHO. The reason for this may be the simultaneous
formation of CO 2 and NH 3 upon decomposition of
HCOONH4 that may be formed as intermediate species, as
discussed in more detail in Section 3.3. Significant formation of
CO is observed in the range of 250−400 °C. Surprisingly, the
selectivity of products below 250 °C does not add to 100%,
though no HCHO has been detected at the reactor outlet
(Figure 1d−f). This suggests that surface intermediates formed
from HCHO are quite stable at low temperature and still
remain on the surface of the catalyst.
To analyze possible reactions of HCHO with single
components of the NH3-SCR feed, flows of 5 vol % O2/He,
0.1 vol % NO, 5 vol % O2/He, and 0.1 vol % NH3, 5 vol % and
O2/He, each containing 100 ppm HCHO, were passed
separately over the VWT catalyst (Figure 2). The conversion
of HCHO in the HCHO/O2 feed below 200 °C was 75−90%,
but only 30−70 ppm of CO, being the only gaseous product at
low temperature, was detected (Figure 2a). CO was the main
product also at higher temperature and passed its maximum
around 300 °C (Figure 2a).
When 0.1 vol % NO was added to the feed of 100 ppm
HCHO, 5 vol % O2/He, HCHO conversion was 100% at all
temperatures and CO2 was detected as a product in addition to
11756
pubs.acs.org/est Article
CO, but the total selectivity of both products reached only up
to 88% below 200 °C (Figure 2b). Surprisingly, the apparent
conversion of NO remained zero during this experiment,
though it is well known that NO can react with O2 to NO2 and
form adsorbed nitrates on the surface of VWT.24 This suggests
that the higher HCHO conversion and formation of CO2 in
the presence of NO below 300 °C (Figure 2b) may be due to
the reaction of HCHO with nitrates (eq 13) and/or with NO2
(generated from the partial oxidation of NO), liberating NO
again and, thus, keeping its net concentration constant (eqs 14
and 15).25 This has been confirmed by separate experiments in
which mixtures of 100 ppm HCHO, 100 ppm NO2, 0.1 vol %
O2/He, 100 ppm HCHO, and 100 ppm NO/He were
converted over the VWT catalyst at 150 °C (Figure S5). It
was found that NO2 oxidizes HCHO to CO and CO2, being
itself reduced to NO, which does not react directly with
HCHO. This explains the results shown in Figure 1 and
confirms that the lower NO conversion in the presence of
HCHO is due to reaction of the latter with NH3, which is then
no more available for SCR of NO. This is also evident by
comparing the NH3 conversion in Figure 2c with that in Figure
S3 showing the reaction of NH3 with O2 only.
HCHO + 4 NO3− + 4 H + → CO2 + 4 NO2 + 3 H2O
(13)
NO2 + HCHO → NO + CO + H 2O (14)
2 NO2 + HCHO → 2 NO + CO2 + H 2O (15)
Significant changes occur when 0.1 vol % NH3 is added to
the feed of 100 ppm HCHO and 5 vol % O2 (Figure 2c). In
this case, a small amount of (CH2)6N4 is formed at low
temperature, while HCN is the main product up to 450 °C.
The selectivity of products is very similar to that observed
when HCHO was added to the total SCR feed (cf. Figure 1),
confirming that HCHO reacts preferentially with NH3 as
discussed above. In all cases shown in Figure 2a−c, the
selectivity of products at low temperature does not add to
100%, suggesting the formation of stable surface adsorbates.
While it has been shown that (CH2)6N4 can be formed by the
gas-phase reaction of HCHO and NH3 (eq 16),26 the
formation of HCN from the reaction of HCHO and NH3 in
NH3-SCR has not been reported so far. However, there is
some information available for pathways of HCN formation in
other exhaust gas cleaning processes.
6 HCHO + 4 NH3 → (CH 2)6 N4 + 6 H 2O (16)
https://dx.doi.org/10.1021/acs.est.0c00884
Environ. Sci. Technol. 2020, 54, 11753−11761
Environmental Science & Technology
Figure 3. (a) FTIR spectra of the VWT catalyst obtained after pre-adsorption of HCHO/O2 and subsequent exposure to NH3 in the closed cell for
60 min (upper part), and after pre-adsorption of NH3 and subsequent exposure to HCHO/O2 for 60 min in the closed cell (lower part); (b) final
FTIR spectra measured after the 60 min reaction of the dosed gas mixtures with respective adsorbates formed by pre-adsorption of HCHO/O2 and
NH3, respectively; the spectrum of HCONH2 adsorbed on VWT is shown for comparison.
Thus, Voorhoeve et al. reported that HCN is formed from
NO, CO, and H2 at 400−800 °C on a Pt-containing three-way
catalyst (eq 17),27 while Suárez and Löffler postulated HCN
formation from NH3 and CH4 (eq 18) on catalysts containing
platinum,28 rhodium, or iridium.29 Cant et al. have found that
HCN can be formed by dehydration of formamide (eq 19),
which they used as the reducing agent instead of NH3 in SCR
of NO on Co/Cu-ZSM-5 catalysts.30 Small traces of HCN
(<10 ppm) were also observed by Kröcher et.al when a
mixture containing equal amounts of HCOOH and NH3 was
used as the reducing agent in the SCR reaction. In this case,
HCN was formed from decomposition of a HCONH2
intermediate (eq 19).31 This differs very much from our
results in which HCN was the main product when HCHO
instead of HCOOH was present in the feed, though in both
cases HCONH2 was formed as the intermediate. The reason
might be that Kröcher et al. used a feed composition closer to
real vehicle exhaust streams, which contained also 5% of water.
As they have shown in a comprehensive study on HCN
hydrolysis, the presence of water in the feed shifts the
equilibrium in eq 19 to the left.32 Though water is known to
reduce the activity of VWT SCR catalysts,33 it may be
beneficial for suppressing conversion of HCHO to HCN. The
joint effect of water and HCHO on structure−reactivity
relationships in VWT catalysts of different elemental
compositions is currently being studied in our group and will
be the subject of a future publication.
NO + CO + 5/2 H 2 → HCN + 2 H 2O (17)
NH3 + CH4 → HCN + 3 H 2 (18)
HCONH 2 → HCN + H 2O (19)
To elucidate the reaction network and identify surface
intermediates in NH3-SCR of NOx in the presence of HCHO,
comprehensive in situ FTIR studies have been performed, the
results of which are described in the following sections.
In Situ FTIR Investigations. Interaction between HCHO/
O2 and NH3. As discussed above, the negative effect of HCHO
on the performance of the VWT catalyst in NH3-SCR is
supposed to result from its reaction with NH3. Therefore, the
interaction of these two feed components has been studied
11757
pubs.acs.org/est Article
separately. The FTIR spectra of the VWT catalyst obtained
after 60 min pre-adsorption of 200 ppm HCHO and 5 vol %
O2/He and subsequent flushing with He at 150 °C show an
intense broad band around 1578 cm−1 and a slightly weaker
band at 1410−1350 cm−1, which are related to the νas(COO−)
and νs(COO−) + δ(CH) vibrations of formate species (Figure
3a).34 Formation of formate suggests that HCHO is oxidized
upon interaction with the catalyst surface, probably on V5+ = O
and W6+ = O surface species, as indicated by negative bands of
the corresponding 2ν overtone vibrations at 2043 cm−135,36
and 2006 cm−1,37,38 respectively, in Figure S6a. Simulta-
neously, a negative band appeared around 3650 cm−1,
indicating the consumption of OH surface groups (Figure
S6a). This suggests that HCHO adsorption and formate
formation occur preferentially on Brønsted sites. After
subsequent dosing of 0.1 vol % NH3/He (Figure 3a, top),
the formate bands disappeared completely after 5 min and new
bands appeared at 1685, 1602, and 1394 cm−1, which can be
assigned to ν(CO), δ(NH2), and δ(C−H) of adsorbed
formamide HCONH2.39,40 The excess of NH3 was adsorbed
on Brønsted sites indicated by the band at 1432 cm−1.41,42 This
is supported by a more pronounced consumption of surface
OH moieties, evidenced by negative bands at 3690−3650
cm−1 (Figure S6a). The band at 1602 cm−1 in Figure 3a stems
from NH3 coordinated to Lewis sites. With increasing time of
exposure to NH3, an additional band at 1720 cm−1 appeared.
As discussed in the literature, formamide molecules adsorb
with different symmetries depending on temperature, which is
reflected by either a transverse optical (TO) ν(CO) or a
longitudinal optical (LO) ν(CO) band at different wave-
numbers.43,44 According to this, the bands at 1685 and 1720
cm−1 are assigned to ν(CO) of adsorbed formamide in TO
and LO symmetry.
When NH3 was dosed first, it adsorbed mainly on Brønsted
sites (NH4+ band at 1423 cm−1, negative bands at 3650−3690
cm−1 for consumed OH in Figure S6b), but a small amount
coordinated also to Lewis sites indicated by the band at 1602
and 1230 cm−1 (Figure 3a). Moreover, the negative intensity of
the two 2ν overtone vibrations of V5+ = O at 2043 cm−135,36
and of W6+ = O at 2006 cm−137,38 is more pronounced than
that with HCHO alone, indicating a stronger reducing effect of
https://dx.doi.org/10.1021/acs.est.0c00884
Environ. Sci. Technol. 2020, 54, 11753−11761
Environmental Science & Technology pubs.acs.org/est Article

NH3. Upon subsequent exposure of the catalyst to a flow of

200 ppm HCHO and 5 vol % O2/He, the bands of adsorbed
NH4+ and NH3 decreased, while those of adsorbed HCONH2
(discussed above) arose, indicating the reaction of adsorbed
NH3 with HCHO to adsorbed HCONH2.
Though both reactants, HCHO and NH3, compete for the
same adsorption sites, this does not hinder their mutual
conversion, since the two experiments demonstrate that
adsorbed HCONH2 can be formed by the reaction of pre-
adsorbed formate species with NH3 as well as by the reaction
of pre-adsorbed NH4+ and NH3 species with HCHO.
The formation of HCONH2 upon the reaction of pre-
adsorbed NH3 with HCHO has also been studied in the
presence of NO. Therefore, the VWT catalyst was first exposed
to NH3/He and subsequently to a flow of 400 ppm HCHO,
0.2 vol % NO, and 5 vol % O2/He. The spectrum measured at
the end of the experiment is shown in Figure 3b (green
Figure 4. FTIR spectra of the VWT catalyst recorded after 1 h
spectrum). For comparison, the final spectra of the already exposure to 200 ppm HCHO, 0.1 vol % NH3, and 5 vol % O2/He at
discussed experiments (cf. Figure 3a) are also shown together 150 °C and at different temperatures after subsequent heating in the
with the spectrum of HCONH2, which was directly adsorbed. closed IR cell. For comparison, the spectrum measured after pre-
By comparing the blue and the green spectra in Figure 3b, it is adsorption of NH3 and subsequent exposure to HCHO/O2 for 60
obvious that, when NO is present in the feed, bands of min at 150 °C is also shown.
adsorbed NH3 and NH4+ are completely missing and only
those of adsorbed HCONH2 are seen. In addition, bands at
1630 and 1379 cm−1 arose, which can be assigned to adsorbed of CO2 and CO (traces only) appeared. However, surprisingly
nitrate species. Time dependent spectra of the interaction of no HCN was observed, though its formation was expected (cf.
pre-adsorbed NH3 with the HCHO/NO/O2 mixture at 150 Figure 2c, eq 19). Probably, HCN was indeed formed, but it
°C are shown in Figure S7a in comparison to the same desorbed quickly into the gas phase, and the concentration was
experiment without HCHO (Figure S7b). From these two too low to be detected. In a corresponding operando DRIFTS
plots, it is clearly seen that, in the absence of HCHO, only experiment (Figure S8), HCN has been detected in the
adsorbed nitrate was formed, while HCONH2 appeared in effluent leaving the DRIFTS cell by online MS. On the other
addition when HCHO was present (Figure S7a). Very similar hand, fast oxidation of adsorbed HCN by lattice oxygen
results were obtained in an operando DRIFTS experiment with (evidenced by transient experiments shown below) might have
the full HCHO/NO/NH3/O2 feed, while HCN was detected prevented its accumulation on the catalyst surface.
by online mass spectrometry (Figure S8). Decomposition and Oxidation of Pristine HCONH2.
It is well known for NH3-SCR of NOx on VWT catalysts As suggested by the in situ FTIR measurements, HCONH2
that oxidation of NO to adsorbed nitrate is the initial step and seems to be a key intermediate in the reaction with HCHO,
these nitrate species are subsequently reduced by adsorbed NH3, and O2, though it could not be detected in the effluent of
NH3 and NH4+ species.45 Thus, the spectra in Figure 3b the catalytic reactor. To study its role in more detail, a helium
indicate clearly that adsorbed nitrate and HCHO compete flow containing 300 ppm HCONH2 and 5 vol % O2 was
with each other for reaction with adsorbed NH3/NH4+ to N2 directly flushed over the VWT catalyst in the NH3-SCR reactor
and HCONH2, respectively. Formation of HCONH2 con- (Figure 5).
sumed a part of NH3/NH4+, which was then no more available HCONH2 was converted completely above 200 °C. This
for nitrate reduction, leading to diminished NOx conversion could have happened in two ways by decomposition (a) to CO
and N2 selectivity at low temperatures as discussed above (cf. and NH3 (eq 20) or (b) to HCN and H2O (eq 19). Above 250
Figure 1a,c). °C, the pathway (b) leads to preferential formation of HCN,
Simultaneous Interaction of HCHO/NH 3 /O 2 . When
HCHO/O2 and NH3 were adsorbed simultaneously on
VWT for 60 min at 150 °C, the red spectrum in Figure 4
was obtained. By comparing this with the spectrum measured
after pre-adsorption of NH3 followed by HCHO/O2 (grey
spectrum), similar bands can be seen, in particular the
characteristic ν(CO) band of adsorbed formamide at 1676
cm−1 as well as that of adsorbed NH4+ species at 1405 cm−1. In
addition, there are bands at 2955, 2886, 1462, and 1261 cm−1,
which are related to the ν(C−H), δ(C−H), and ν(C−N)
vibrations of adsorbed (CH2)6N4 (HMT)46,47 formed by the
gas-phase reaction of HCHO and NH3 (eq 18). These bands
decline strongly upon heating, reflecting only traces of residual
adsorbed HMT at 250 °C, which vanish completely at higher
temperature, since HCONH2 decomposes and/or is oxidized.
This result matches with the detection of HMT in the catalytic Figure 5. Reaction of 300 ppm HCONH2 and 5 vol % O2 over the
test (Figure 2c). The band at 1676 cm−1 declined, and bands VWT catalyst.

11758 https://dx.doi.org/10.1021/acs.est.0c00884
Environ. Sci. Technol. 2020, 54, 11753−11761
Environmental Science & Technology
Figure 6. Oxidation of HCN in the absence of gas-phase O2 over the VWT catalyst: (a) temperature-induced changes of the amount of C16O2 and
N16O upon pulsing of HCN (10 vol % in N2) and (b) normalized transient responses of HCN, C16O2, and N16O recorded at 500 °C.
confirming that HCONH2 is the source for this undesired
compound. Simultaneously, the concentration of NH3 formed
by the pathway (a) drops below that of CO due to oxidation
by the VWT catalyst. This agrees with the results plotted in
Figure S3. Above 350 °C, the concentration of HCN declined,
while that of CO2 increased concomitantly. In agreement with
Figure 2c, showing a strong increase of CO2 selectivity above
350 °C when HCN is present, this suggests that oxidation of
the latter might be the main source of CO2 formation, though
oxidation of CO to CO2 cannot be excluded. Interestingly, the
CO2 concentration passes a maximum around 200 °C (Figure
5). As mentioned above, this was also observed during catalytic
tests in the total SCR feed and coincides with a slight
minimum in NH3 conversion (Figure 1). A possible reason
may be that water formed upon decomposition of HCONH2
after the pathway (b) (eq 19) adds to unconverted HCONH2.
This forms HCOONH4, which can decompose to CO2 and
NH3, as reported by Hudson et al. (eqs 21 and 22).48
HCONH 2 → CO + NH3 (20)
HCONH 2 + H 2O → HCONH4 (21)
HCOONH4 → CO2 + NH3 + H 2 (22)
2 HCN + 7/2 O2 → 2 CO2 + 2 NO + H 2O (23)
In order to analyze the oxidation of HCN on the VWT
catalyst in more detail, transient pulse experiments were
performed using the TAP-2 reactor in which HCN was pulsed
in the absence of gas-phase O2 over the pre-oxidized VWT
catalyst. As CO2 and NO were observed in these experiments,
it can be concluded that lattice oxygen of the catalyst is
involved in HCN oxidation (eq 23). Both reaction products
were observed starting from 400 °C (Figure 6a). It should,
however, be mentioned that the contact time in these tests was
significantly shorter than in our steady-state tests (1 ms vs
about 60 ms). As a consequence, HCN oxidation should also
take place at lower temperatures when the contact time is long
enough. Therefore, the discrepancy in the temperature
dependence of product formation between transient and
steady-state tests can be related to the effect of experimental
conditions.
It is worth mentioning that the outlet concentrations of CO2
and NO in the TAP tests increased differently with reaction
temperature. In contrast to CO2, NO was hardly detected
below 450 °C. This can be explained by stronger adsorption of
the latter, which is also evident in Figure 6b from the very
broad shape of NO response. This is a typical fingerprint for
strong reversible adsorption even at 500 °C, which may be one
11759
pubs.acs.org/est Article
reason for the low amount of NO detected in the gas phase
when HCONH2 is oxidized directly (Figure 5).
To check if adsorbed oxygen species are also involved in
HCN oxidation, sequential pulse experiments with 18O2 and
HCN were carried out. C16O2 and N16O were the only
products detected in the HCN pulse (Figure S9). If C18O2 and
N18O with labeled oxygen were formed, their concentration
should be below the detection limit of the mass spectrometer
used. On this basis, we can conclude that lattice oxygen of the
catalyst is the main species responsible for HCN oxidation.
This may also explain why no adsorbed HCN could be
detected in the in situ FTIR experiments.
In summary, to the best of our knowledge, we presented
here the first study on the effect of formaldehyde on the
performance of a commercial V2O5-WO3/TiO2 catalyst in
NH3-SCR of NOx. It was found that HCHO has a detrimental
effect, since it reduces NO conversion by consuming NH3,
which is thereby deprived from its desired role as the reducing
agent in the SCR reaction (Scheme 1). Consequently, this
lowers also N2 selectivity in the whole temperature range.
Scheme 1. Pathway of the HCHO Reaction in NH3-SCR of
NO on a Commercial V2O5-WO3/TiO2 Catalyst
In situ FTIR results have shown that HCHO is oxidized to
adsorbed formate species, which react with NH3 and NH4+
species to form adsorbed formamide (HCONH2) as the
intermediate. At the same time, NO is oxidized to adsorbed
nitrate, which reacts with NH3/NH4+ to form N2 in the desired
SCR pathway. Thus, both nitrate and formate formed from
oxidation of NO and HCHO, respectively, compete with each
other for reaction with NH3/NH4+ to form either N2 by SCR
(desired) or HCONH2. Formation of the latter is highly
undesired, since it decomposes by dehydration (major
pathway) and decarbonylation (minor pathway) to liberate
toxic HCN and CO, respectively, with maximum concen-
trations in the range between 250 and 400 °C (Scheme 1).
HCN is oxidized above 400 °C to CO2 and NO, whereby
the latter enters the desired SCR reaction again. As revealed by
https://dx.doi.org/10.1021/acs.est.0c00884
Environ. Sci. Technol. 2020, 54, 11753−11761
Environmental Science & Technology
transient pulse experiments with 18O2 in the TAP-2 reactor,
HCN oxidation is driven by lattice oxygen according to a
Mars-van Krevelen mechanism. This might be the reason why
HCN could not be detected as the surface intermediate by in
situ FTIR spectroscopy.
In situ FTIR results suggest also that surface V5+ = O and
6+
W = O moieties are involved in NH3 activation and/or NO
oxidation. Detailed spectroscopic in situ/operando studies by
FTIR and EPR spectroscopy are currently under way to
unravel the role of these species within the reaction network,
depending on the composition of the catalyst. It has to be
taken into account that the gas-phase composition will change
along the catalyst bed from the entrance to the outlet, as it is
probable for any heterogeneous catalytic gas-phase reaction
performed in a plug-flow reactor. However, the reaction steps
in Scheme 1 are certainly relevant in the section following the
reactor entrance in which all feed components are still present
in close to initial concentrations.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.est.0c00884.
Experimental setups and calibration of product concen-
trations; HCHO concentration in the total NH3-SCR
feed flow; FTIR spectra; conversion of NH3 and the
concentration of products; formation of N2O; in situ
FT-IR spectra; time-dependent FTIR spectra; difference
DRIFT spectra; and transient responses (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Angelika Brückner − Leibniz Institute for Catalysis, D-18059
Rostock, Germany; orcid.org/0000-0003-4647-1273;
Phone: +49(381)1281-244; Email: angelika.brueckner@
catalysis.de
Authors
Anh Binh Ngo − Leibniz Institute for Catalysis, D-18059
Rostock, Germany
Thanh Huyen Vuong − Leibniz Institute for Catalysis, D-
18059 Rostock, Germany
Hanan Atia − Leibniz Institute for Catalysis, D-18059 Rostock,
Germany
Ursula Bentrup − Leibniz Institute for Catalysis, D-18059
Rostock, Germany; orcid.org/0000-0002-1043-2881
Vita A. Kondratenko − Leibniz Institute for Catalysis, D-18059
Rostock, Germany
Evgenii V. Kondratenko − Leibniz Institute for Catalysis, D-
18059 Rostock, Germany; orcid.org/0000-0003-0431-
6937
Jabor Rabeah − Leibniz Institute for Catalysis, D-18059
Rostock, Germany; orcid.org/0000-0003-2162-0981
Udo Ambruster − Leibniz Institute for Catalysis, D-18059
Rostock, Germany
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.est.0c00884
Notes
The authors declare no competing financial interest.
11760
■
pubs.acs.org/est Article
ACKNOWLEDGMENTS
Anh Binh Ngo acknowledges a grant of the RoHan Project
funded by the German Academic Exchange Service (DAAD,
No. 57315854) and the Federal Ministry for Economic
Cooperation and Development (BMZ) inside the framework
“SDG Bilateral Graduate School Program”. We thank Mr. R.
Eckelt, Mr. D. Seeburg, and S. Keller for experimental support.
■
REFERENCES
(1) Lietti, L.; Nova, I.; Ramis, G.; Dall’Acqua, L.; Busca, G.;
Giamello, E.; Forzatti, P.; Bregani, F. Characterization and Reactivity
of V2O5−MoO3/TiO2 De-NOx SCR Catalysts. J. Catal. 1999, 187,
419−435.
(2) Nova, I.; Tronconi, E. Kinetic study of the NO/NO2-NH3 SCR
reactions over a V2O5−WO3/TiO2 commercial catalyst for the after
treatment of Diesel engines exhausts. IFAC Proceedings Volumes 2009,
42, 183−190.
(3) Han, L.; Cai, S.; Gao, M.; Hasegawa, J.-Y.; Wang, P.; Zhang, J.;
Shi, L.; Zhang, D. Selective Catalytic Reduction of NOx with NH3 by
Using Novel Catalysts: State of the Art and Future Prospects. Chem.
Rev. 2019, 119, 10916−10976.
(4) Cazier, F.; Delbende, A.; Nouali, H.; Hanoune, B.; Pillot, D.;
Vidon, R.; Perret, P.; Tassel, P., Determination of VOC components
in the exhaust of light vehicles fuelled with different biofuels. 18th
International Symposium “Transport and Air Pollution” 2010, (TAP
2010 May 2010, Switzerland), 260−266.
(5) Clairotte, M.; Adam, T. W.; Zardini, A. A.; Manfredi, U.;
Martini, G.; Krasenbrink, A.; Vicet, A.; Tournié, E.; Astorga, C. Effects
of low temperature on the cold start gaseous emissions from light duty
vehicles fuelled by ethanol-blended gasoline. Appl. Energy 2013, 102,
44−54.
(6) United States Environmental Protection Agency Light-Duty
Vehicles and Light-Duty Trucks: Clean Fuel Fleet Exhaust Emission
Standards. EPA-420-B-006, March 2016, https://www.epa.gov/
emission-standards-reference-guide/epa-emission-standards-light-
duty-vehicles-and-trucks
(7) Herndon, S. C.; Rogers, T.; Dunlea, E. J.; Jayne, J. T.; Miake-
Lye, R.; Knighton, B. Hydrocarbon Emissions from In-Use
Commercial Aircraft during Airport Operations. Environ. Sci. Technol.
2006, 40, 4406−4413.
(8) He, Z.; Li, J.; Mao, Y.; Yu, L.; Zhou, Q.; Qian, Y.; Lu, X. A
comprehensive study of fuel reactivity on reactivity controlled
compression ignition engine: Based on gasoline and diesel surrogates.
Fuel 2019, 255, 115822.
(9) Rodrigues, M. C.; Guarieiro, L. L. N.; Cardoso, M. P.; Carvalho,
L. S.; da Rocha, G. O.; de Andrade, J. B. Acetaldehyde and
formaldehyde concentrations from sites impacted by heavy-duty
diesel vehicles and their correlation with the fuel composition: Diesel
and diesel/biodiesel blends. Fuel 2012, 92, 258−263.
(10) Suarez-Bertoa, R.; Clairotte, M.; Arlitt, B.; Nakatani, S.; Hill, L.;
Winkler, K.; Kaarsberg, C.; Knauf, T.; Zijlmans, R.; Boertien, H.;
Astorga, C. Intercomparison of ethanol, formaldehyde and acetalde-
hyde measurements from a flex-fuel vehicle exhaust during the
WLTC. Fuel 2017, 203, 330−340.
(11) Collins, J. J.; Esmen, N. A.; Hall, T. A. A review and meta-
analysis of formaldehyde exposure and pancreatic cancer. Am. J. Ind.
Med. 2001, 39, 336−345.
(12) Int. Council of Combustion Engines, Methane and Form-
aldehyde Emissions of Gas Engines. CIMAC Position Paper 2014,
WG 17.
(13) Wei, H.; Yao, C.; Dou, Z.; Wang, B.; Chen, C.; Liu, M.
Comparison of the conversion efficiency of DOC and DPOC to
unregulated emissions from a DMDF engine. Fuel 2017, 204, 71−84.
(14) Williams, E. J.; Lerner, B. M.; Murphy, P. C.; Herndon, S. C.;
Zahniser, M. S. Emissions of NOx, SO2, CO, and HCHO from
commercial marine shipping during Texas Air Quality Study
(TexAQS) 2006. J. Geophys. Res. 2009, 114, D21.
https://dx.doi.org/10.1021/acs.est.0c00884
Environ. Sci. Technol. 2020, 54, 11753−11761
Environmental Science & Technology
(15) Chin, J. Y.; Batterman, S. A.; Northrop, W. F.; Bohac, S. V.;
Assanis, D. N. Gaseous and Particulate Emissions from Diesel Engines
at Idle and under Load: Comparison of Biodiesel Blend and Ultralow
Sulfur Diesel Fuels. Energ. Fuel. 2012, 26, 6737−6748.
(16) Torkashvand, B.; Maier, L.; Hettel, M.; Schedlbauer, T.;
Grunwaldt, J. D.; Deutschmann, O. On the challenges and constrains
of ultra-low emission limits: Formaldehyde oxidation in catalytic
sinusoidal-shaped channels. Chem. Eng. Sci. 2019, 195, 841−850.
(17) Shukla, P. C.; Gupta, T.; Agarwal, A. K. Performance evaluation
of a biodiesel fuelled transportation engine retrofitted with a non-
noble metal catalysed diesel oxidation catalyst for controlling
unregulated emissions. J. Hazard. Mater. 2018, 344, 615−625.
(18) Bertole, C., Formaldehyde Oxidation over Emission Control
Catalysts. No. 2018-01-1274. SAE Technical Paper, 2018.
(19) Zheng, L.; Casapu, M.; Stehle, M.; Deutschmann, O.;
Grunwaldt, J.-D. Selective Catalytic Reduction of NOx with Ammonia
and Hydrocarbon Oxidation Over V2O5−MoO3/TiO2 and V2O5−
WO3/TiO2 SCR Catalysts. Top. Catal. 2019, 62, 129−139.
(20) Brewer, P. J.; di Meane, E. A.; Vargha, G. M.; Brown, R. J. C.;
Milton, M. J. T. Gaseous reference standards of formaldehyde from
trioxane. Talanta 2013, 108, 83−87.
(21) Gleaves, J. T.; Yablonskii, G. S.; Phanawadee, P.; Schuurman, Y.
TAP-2: An interrogative kinetics approach. Appl. Catal A, Gen. 1997,
160, 55−88.
(22) Pérez-Ramírez, J.; Kondratenko, E. V. Evolution, achievements,
and perspectives of the TAP technique. Catal. Today 2007, 121, 160−
169.
(23) Morgan, K.; Maguire, N.; Fushimi, R.; Gleaves, J. T.; Goguet,
A.; Harold, M. P.; Kondratenko, E. V.; Menon, U.; Schuurman, Y.;
Yablonsky, G. S. Forty years of temporal analysis of products. Catal.
Sci. Technol. 2017, 7, 2416−2439.
(24) Suárez, S.; Jung, S. M.; Avila, P.; Grange, P.; Blanco, J. Influence
of NH3 and NO oxidation on the SCR reaction mechanism on
copper/nickel and vanadium oxide catalysts supported on alumina
and titania. Catal. Today 2002, 75, 331−338.
(25) Healy, T. V. The Reaction of nitric acid with formaldehyde and
with formic acid and its application to the removal of nitric acid from
mixtures. J. Appl. Chem. 1958, 8, 553−561.
(26) Richmond, H. H.; Myers, G. S.; Wright, G. F. The Reaction
between Formaldehyde and Ammonia. J. Am. Chem. Soc. 1948, 70,
3659−3664.
(27) Voorhoeve, R. J. H.; Patel, C. K. N.; Trimble, L. E.; Kerl, R. J.
Hydrogen Cyanide Production During Reduction of Nitric Oxide
over Platinum Catalysts. Science 1975, 190, 149.
(28) Suárez, M. P.; Löffler, D. G. HCN synthesis from NH3 and
CH4 on Pt at atmospheric pressure. J. Catal. 1986, 97, 240−242.
(29) Suárez, M. P.; Löffler, D. G. HCN synthesis from NH3 and
CH4 on Rh and Ir. React. Kinet. Catal. Lett. 1991, 43, 195−199.
(30) Cant, N. W.; Cowan, A. D.; Liu, I. O. Y.; Satsuma, A. The
reactions of possible intermediates in the selective catalytic reduction
of nitrogen oxides by hydrocarbons. Catal. Today 1999, 54, 473−482.
(31) Kröcher, O.; Elsener, M.; Jacob, E. A model gas study of
ammonium formate, methanamide and guanidinium formate as
alternative ammonia precursor compounds for the selective catalytic
reduction of nitrogen oxides in diesel exhaust gas. Appl. Catal. B 2009,
88, 66−82.
(32) Kröcher, O.; Elsener, M. Hydrolysis and oxidation of gaseous
HCN over heterogeneous catalysts. Appl. Catal. B 2009, 92, 75−89.
(33) Vuong, T. H.; Bartling, S.; Bentrup, U.; Lund, H.; Rabeah, J.;
Atia, H.; Armbruster, U.; Brückner, A. Synergistic effect of VO x and
MnO x surface species for improved performance of V2O5/
Ce0.5Ti0.5− xMnxO2−δ catalysts in low-temperature NH3-SCR of NO.
Catal. Sci. Technol. 2018, 8, 6360−6374.
(34) Busca, G.; Lamotte, J.; Lavalley, J. C.; Lorenzelli, V. FT-IR
study of the adsorption and transformation of formaldehyde on oxide
surfaces. J. Am. Chem. Soc. 1987, 109, 5197−5202.
(35) Busca, G.; Centi, G.; Marchetti, L.; Trifiro, F. Chemical and
spectroscopic study of the nature of a vanadium oxide monolayer
11761
pubs.acs.org/est Article
supported on a high-surface-area TiO2 anatase. Langmuir 1986, 2,
568−577.
(36) Went, G. T.; Oyama, S. T.; Bell, A. T. Laser Raman
spectroscopy of supported vanadium oxide catalysts. J. Phys. Chem.
1990, 94, 4240−4246.
(37) Busca, G.; Lavalley, J. C. Use of overtone bands to monitor the
state of the catalyst active phases during infrared studies of adsorption
and catalytic reactions. Spectrochim. Acta A 1986, 42, 443−445.
(38) Ramis, G.; Cristiani, C.; Elmi, A. S.; Villa, P.; Busca, G.
Characterization of the surface properties of polycrystalune WO3. J.
Mol. Catal. 1990, 61, 319−331.
(39) Mortensen, A.; Faurskov Nielsen, O. Vibrational spectra in the
carbonyl stretching region of isotopomers of formamide in the
gaseous and liquid states. Spectrochim. Acta A 1995, 51, 1345−1354.
(40) Parmeter, J. E.; Schwalke, U.; Weinberg, W. H. Interaction of
formamide with the Ru(001) surface. J. Am. Chem. Soc. 1988, 110,
53−62.
(41) Lercher, J. A.; Gründling, C.; Eder-Mirth, G. Infrared studies of
the surface acidity of oxides and zeolites using adsorbed probe
molecules. Catal. Today 1996, 27, 353−376.
(42) Busca, G. The surface acidity of solid oxides and its
characterization by IR spectroscopic methods. An attempt at
systematization. Phys. Chem. Chem. Phys. 1999, 1, 723−736.
(43) Elisabetta Palumbo, M.; Baratta, G. A.; Collings, M. P.;
McCoustra, M. R. S. The profile of the 2140 cm−1 solid CO band on
different substrates. Phys. Chem. Chem. Phys. 2006, 8, 279−284.
(44) Urso, R. G.; Scirè, C.; Baratta, G. A.; Brucato, J. R.;
Compagnini, G.; Kaňuchová, Z.; Palumbo, M. E.; Strazzulla, G.
Infrared study on the thermal evolution of solid state formamide.
Phys. Chem. Chem. Phys. 2017, 19, 21759−21768.
(45) Vuong, T. H.; Radnik, J.; Rabeah, J.; Bentrup, U.; Schneider,
M.; Atia, H.; Armbruster, U.; Grünert, W.; Brückner, A. Efficient
VOx/Ce1−xTixO2 Catalysts for Low-Temperature NH3-SCR: Reaction
Mechanism and Active Sites Assessed by in Situ/Operando
Spectroscopy. ACS Catal. 2017, 7, 1693−1705.
(46) Pirali, O.; Boudon, V.; Carrasco, N.; Dartois, E. Rotationally
resolved IR spectroscopy of hexamethylenetetramine (HMT)
C6N4H12. Astron. Astrophys. 2014, 561, A109.
(47) Bertie, J. E.; Solinas, M. Infrared and Raman spectra and the
vibrational assignment of hexamethylenetetramine-h12 and -d12. J.
Chem. Phys. 1974, 61, 1666−1677.
(48) Hudson, J. S.; Eberle, J. F.; Vachhani, R. H.; Rogers, L. C.;
Wade, J. H.; Krishnamurthy, R.; Springsteen, G. A Unified
Mechanism for Abiotic Adenine and Purine Synthesis in Formamide.
Angew. Chem., Int. Ed. 2012, 51, 5134−5137.
https://dx.doi.org/10.1021/acs.est.0c00884
Environ. Sci. Technol. 2020, 54, 11753−11761