Diamondoid Nanostructures as sp3-Carbon-Based Gas Sensors

Article abstract of DOI:10.1002/anie.201903089

Diamondoids, sp³-hybridized nanometer-sized diamond-like hydrocarbons (nanodiamonds), difunctionalized with hydroxy and primary phosphine oxide groups, enable the assembly of the first sp³-C-based chemical sensors by vapor deposition. Both pristine nanodiamonds and palladium nanolayered composites can be used to detect toxic NO₂ and NH₃ gases. This carbon-based gas sensor technology allows reversible NO₂ detection down to 50 ppb and NH₃ detection at 25–100 ppm concentration with fast response and recovery processes at 100 °C. Reversible gas adsorption and detection is compatible with 50 % humidity conditions. Semiconducting p-type sensing properties are achieved from devices based on primary phosphine–diamantanol, in which high specific area (ca. 140 m² g^?1) and channel nanoporosity derive from H-bonding.

Full text of DOI:10.1002/anie.201903089

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Accepted Article
Title: Diamondoid Nanostructures as sp3-Carbon-Based Gas Sensors
Authors: Jean Cyrille Hierso
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201903089
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Diamondoid Nanostructures as sp3-Carbon-Based Gas Sensors
Oana Moncea,[a,b] Juan Casanova-Chafer,[c] Didier Poinsot,[a] Lukas Ochmann,[b] Clève D. Mboyi,[a] Houssein
O. Nasrallah,[a] Eduard Llobet,[c]* Imen Makni,[a] Molka El Atrous,[a] Stéphane Brandès,[a] Yoann Rousselin,[a]
Bruno Domenichini,[d] Nicolas Nuns,[e] Andrey A. Fokin,[b,f] Peter R. Schreiner,[b]* and Jean-Cyrille Hierso[a,g]
*
Abstract: Diamondoids, sp3-hybridized nanometer-sized diamond-
like hydrocarbons (nanodiamonds), difunctionalized with hydroxyl and
primary phosphine oxide groups enable the assembly of the first sp3-
C-based chemical sensors by vapor deposition. Both pristine
nanodiamonds and palladium nanolayered composites can be used
to detect toxic NO2 and NH3 gases. This carbon-based gas sensor
technology allows reversible NO2 detection down to 50 ppb and NH3
detection at 25–100 ppm concentration with fast response and
recovery processes at 100 °C. Reversible gas adsorption and
detection is compatible with 50% humidity conditions.
Semiconducting p-type sensing properties are achieved from devices
based on primary phosphine-diamantanol, in which high specific area
(ca. 140 m2 g–1) and channel nanoporosity derive from H-bonding.
from relative humidity. Because of the emergence of
nanotechnology a shift in sensor materials occurred toward more
sensitive recognition increasingly elaborate
layers,[6]
architectures,[7,8] and reduced dimensionality.[2,9] Research
addresses low-power devices from sensitive and stable sensors
usable at moderate temperatures, and thus suited for trace
detection for a wide spectrum of applications ranging from lab-on-
a-chip and in vivo biosensors to environmental monitoring and
warfare agent detection.[10] In 2000, the Dai group demonstrated
the potential of carbon nanotube (CNT)-based gas sensors.[3] The
role of graphene in fabricating gas sensors for the detection of
various hazardous gases, including NO2 rapidly emerged.[11,12]
Thus, sensor development experienced a remarkable rise in
attention focusing on sp2-hybridized carbon structures.[13] There is,
however, a large group of sp3-hydridized carbon semiconductor
materials, the so-called diamondoids, which essentially are hydro-
Outdoor air pollution, associated with global climate change,
causes several million deaths per year.[1] Many toxic gases are
produced through combustion processes from vehicles as well as
industrial plants. Nitrogen dioxide (NO2) is the most hazardous
gas with a 3 ppm threshold limit value (TLV, human level of
exposure to be strictly controlled).[2] NO2 plays a role in
atmospheric reactions causing acid rain, and contributing to
ozone formation, which is the major cause of photochemically
produced smog.[1,2] Detection and emission control of nitrogen
oxides are thus essential objectives to reduce their hazardous
effects on environment and mankind.[1-3]
gen-terminated
diamond
nanoparticles
(i.e.,
pristine
nanodiamonds).[14] These mechanically rigid and thermo-
dynamically extremely stable structures[15] are available in large
quantities from fossil resources and in part through chemical
synthesis.[16] Diamondoids are promising for nanoelectronics,[17]
since they exhibit unique effects such as quantum confinement,
hence offering possibilities for band gap tuning.[18,19] Diamondoid
derivatives serve as building blocks in “bottom-up” strategies to
build unique sp3-carbon-based nanocomposites.[20,21]
Metal oxide semiconductors are low-cost, robust sensors most
frequently used for the NO2 detection.[4,5] These usually operate
at temperatures of a few hundred degrees Celsius, which is costly
and reduces sensor lifetime. Other significant limitations are
cross-sensitivities with other gases, and detrimental interference
Surfaces of CNT-based NO2 sensor materials react with the
detected gas in mechanisms involving charge-transfer or
Schottky-barrier modification[2,22] which results in a measurable
change in resistance. In semiconducting p-type sensors, electron-
donation into the valence band results in charge-carrier
recombination causing an increase in resistance. Conversely,
electron-withdrawing effects increase the hole concentration in
the material, leading to lower resistance.[2] Additionally, NO2
adsorption is more favorable on CNTs with high metallic character
than on semiconducting nanotubes.[23] We thus envisioned that
nanocomposites combining sp3-carbon 3-D molecular-size
diamondoids coated with thin metal nanolayers would yield hybrid
materials with electronically modified surfaces. These materials
would then be potential catalysts or sensors. This band-structure
doping inspired approach would combine sp3-C nanodiamond
semiconductors with transition metals. Accordingly, we recently
reported robust self-assemblies of volatile P-functionalized
diamondoids into nanocrystals via mild vapor deposition,[20]
followed by Pd nanolayer coating under mild CVD conditions.[21]
Here we present the first use of sp3-C-based nanostructures as
high sensitivity gas sensors for the reversible detection of NO2,
NH3, and H2. These new materials were structurally characterized
at different scales (single-crystal X-ray diffraction, powder X-Ray
diffraction, porosity measurements, Time-of-Flight Secondary Ion
Mass Spectrometry, ToF-SIMS). The materials proved gas
responsive both in pristine form and used as metal composite with
[a] Dr. O. Moncea, D. Poinsot, Dr. C. D. Mboyi, Dr. H. O. Nasrallah, I.
Makni, M. El Altrous, Dr. Y. Rousselin, Dr. S. Brandès, Prof. Dr. J.-C.
Hierso Institut de Chimie Moléculaire de l’Université de Bourgogne
(ICMUB) UMR-CNRS 6302, Université de Bourgogne Franche-Comté
(UBFC), 9 avenue Alain Savary 21078, Dijon, France
E-mail: jean-cyrille.hierso@u-bourgogne.fr
[b] Dr. O. Moncea, L. Ochmann, Prof. Dr. A. A. Fokin, Prof. Dr. P. R.
Schreiner Institute of Organic Chemistry, Justus Liebig University
Heinrich-Buff-Ring 17, 35392 Giessen, Germany and Center for
Materials Research (LaMa), Justus Liebig University, Heinrich-Buff-
Ring 16, 35392 Giessen, Germany
E-mail: prs@uni-giessen.de
[c] J. Casanova-Chafer, Pr. Dr. E. Llobet MINOS-EMaS, University Rovira
i Virgili, Avda. Països Catalans, 26, 43007 Tarragona, Spain
E-mail: eduard.llobet@urv.cat
[d] Prof. Dr. B. Domenichini Laboratoire Interdisciplinaire Carnot de
Bourgogne (ICB), UMR-CNRS 6303, Université de Bourgogne
Franche-Comté (UBFC), 9 avenue Alain Savary 21078, Dijon, France
[e] Dr. N. Nuns Unité de Catalyse et de Chimie du Solide, UMR 8181,
Université Lille1 Sciences et Technologies, Cité Scientifique, bâtiment
C3 59655, Villeneuve d’Ascq, France
[f] Prof. Dr. A. A. Fokin Department of Organic Chemistry, Kiev Polytechnic
Institute Pr. Pobedy 37, 03056 Kiev, Ukraine
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10.1002/anie.201903089
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a thin Pd nanolayer in surface. These chemical p-type sensors
promote reversible NO2 detection at 50 ppb to 100 ppm
concentration with fast response and recovery processes at
100 °C; NO2 detection was even possible in 50% relative humidity.
NH3 detection at 25–100 ppm was also found to be highly efficient.
The primary phosphine 9-(hydroxydiamant-4-yl)phosphine
(H2P–DiamOH, 1) and its oxide (H2(O)P–DiamOH, 2) were
synthesized from diamantane (Figures 1 and S1-S2). These
diamondoid derivatives were used in powder form, first for their
vapor-phase self-assembly, then for generating the metal
composites Pd@PH2–DiamOH (3) and Pd@P(O)H2–DiamOH (4),
respectively.[21] This was achieved by low-temperature chemical
vapor deposition of a Pd nanolayer over the crystal self-
assembly.[24] We elucidated the structure of 1 by growing single
crystals in the vapor phase since all our attempts in solution failed.
We found for 1 tetragonal symmetry (space group I-4, with a = b
= 17.8965(4) Å, c = 8.1224(2) Å,  =  =  = 90°, V = 2601.48(13)
Å3, Tables S1–S4). There is a single molecule in the asymmetric
unit with strong H-bonding that leads to tetrameric arrangement
(Fig.1).[25] We observed a large-scale arrangement of the
crystalline structure in which a significant nanoporosity appears.
Channel voids with a total volume of 168 Å3 (~ 6.4% of unit cell,
Figure 2) is accessible to small molecules or solvent. We
examined voids within related diamondoid structures to establish
that cavities in 1 are larger (or exist) than observed for related
crystalline diamantane derivatives (see details in Figures S3).
XRD structure of Cl2(O)P–DiamCl,[15a] clearly reveals no voids. A
SBET = 54 m2 g–1 was found for the oxide H2(O)P–DiamOH, 2.
Figure 2. View of accessible channel voids in diamondoid 1 (Platon program
crystallographic tool; probe 1.2 Å, grid 0.2 Å).
Figure 1. 9-(Hydroxydiamant-4-yl)phosphine 1 and its oxide 2 (left). Tetramer
arrangement for 1 with O1–H1•••O1i = 2.737(4) Å and O1–H–O1i = 164.8° (right).
Ortep thermal ellipsoids are drawn at 50% probability level.
Figure 3. Scanning electron microscopy (SEM) of 1 (top left) and 2 (top right),
The powder X-ray diffraction (PXRD) confirmed that this
crystalline arrangement is conserved in the granular materials
arising from diamantane functionalization, which was used for
vapor phase self-assembly of 1 and 2. We found excellent
agreement between the experimental (Figures S4) and simulated
PXRD patterns that were obtained from the single crystal unit cell
by Le Bail refinement. Two major peaks at 2θ 15.2° and 15.8°,
completed with smaller peaks at 6.9, 9.8, 13.9, and 18.2 ° were
observed and calculated. In relation with the XRD channel voids
and the highly textured surface observed from SEM (Figure 3, top
left), we measured from the crystalline powder the surface area of
1 following the Langmuir method using CO2 absorption at 198 K
(Figures S5a-c). We surprisingly found for this purely organic
phosphine a SBET = 138 m2 g–1, which is significantly higher than
several reported porous composite materials.[26] Accordingly, we
measured the surface area of the parent diamantyl phosphine (9-
hydroxydiamant-4-yl)phosphonic dichloride[15a] (5, named
and metal nanocomposites Pd@PH2–DiamOH,
Pd@P(O)H2–DiamOH 4 (bottom right).
3
(bottom left) and
The nanolayering of palladium over self-assembled 1 and 2 led
to nanocomposites 3 and 4, respectively, for which scanning
electron microscopy views are given in Fig. 3. The self-
assemblies of 1-4 were produced with high structural uniformity
and reproducibility.[21] The surfaces composition of these
materials has been characterized by XPS, showing covalently
built robust Pd@diamondoid hybrids that incorporate Pd–O–
P(H)n–diamantane binding motifs. Our initial studies had been
limited to a low surface depth below 10 nm, and we thus achieved
bulk characterization of these materials in view of gas sensing.
ToF-SIMS analyses (Table S5, Figures S6-S9) from self-
assembly of 1 indicated that the surface of primary diamantanol
phosphines is mostly in the oxidized form. Additionally, in
composite 3 the palladium interactions with oxygen are prevalent,
with the palladium isotopic distribution visible in many mass
fragments attributable to palladium phosphorus oxides (Table S5,
Fig. S6-S9). This is in full agreement with a Pd–O–P bonding
scheme suggested by XPS. The ToF-SIMS technique also
allowed monitoring and quantifying the different elements of our
Cl2(O)P–DiamOH)
and
its
chlorinated
analogue
(9-
chlorodiamant-4-yl)phosphonic dichloride (6, Cl2(O)P–Diam–Cl)
to found much lower values SBET = 40 and 25 m2 g–1, respectively
(Fig. S5d). While single crystals of 5 could not be obtained, the
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materials in-depth (bulk) owing to dual beam sputtering and
analysis. Figure 4 represents the profile of the elements of interest
(Pd, P, C, Si) as a function of sputter time for nanocomposite
Pd@PH2–DiamOH 3. The clearly distinguishable areas
correspond to the palladium layer (I), diamondoid phosphine
deposit (II), and silicon support (III). The steep decrease of curve
I from an initially dominant detection attested the Pd present as a
thin nanolayer on the surface. The monitoring of phosphorus and
carbon from the diamondoid cages (curves II) was achieved
through the detection of characteristic fragments (Fig. S6-S9). P
and C content detection follow first an increase, while the Pd trace
diminishes (the lines cross at 70 s), then they decrease with the
emergence of signals from the silicon wafer (curve III, line
crossing at 4000 s). The profiles for P-containing and C-
containing fragments follow a remarkable parallel evolution that
attests to excellent homogeneity of the phosphine diamondoid
deposit. According to Yamamura’s sputter yield calculation as a
function of the sputter type and energy,[27] it is possible to estimate
sputter rate for Pd nanolayer (≤ 0.07 nm s–1). ToF-SIMS depth
profiling indicates thus a Pd nanolayer thinner than 5 nm. From
SEM the diamondoid deposit thickness was estimated above 175
nm.
resolved detection in Fig. 6c and 6d, respectively, and Figure 7a).
Exposure to NH3 (as an electron-donating species) resulted in a
resistance increase while the presence of NO2 (electron-
withdrawing) resulted in resistance decrease, which correspond
to a typical semiconducting p-type behavior for all samples.
Consistently, we found that uptake of H2 was also possible with
nanomaterials 1–4, inducing resistance increase (Figures S12)
that confirms the p-type character of these gas sensors. Using the
diamondoid phosphine 5 Cl2(O)P–DiamOH,[21] we checked that
efficient gas sensing properties were related to the primary
phosphine-based diamantanol compounds. We observed for
Cl2(O)P–DiamOH-based materials much lower H2 uptake (if any)
compared to 1 (Fig. S12a). This is visibly consistent with the high
surface area for gas adsorption in 1 which is found 3.5 time higher
than in 5 (138 vs 40 m2 g–1).
Figure 5. NO2 response with chemical sensors 1-4 at increasing 25 to 100 ppm
concentration:  = H2P–DiamOH (1),  = H2(O)P–DiamOH (2),  = Pd@PH2–
DiamOH (3),  = Pd@P(O)H2–DiamOH (4). Response is defined as the relative
(Rair – Rgas)/Rair after 10 min exposure to NO2. See also in supporting information
(Figures S11).
Figure 4. ToF-SIMS depth profile of nanocomposite Pd@PH2–DiamOH, 3.
NO2 gas sensing experiments were conducted with Pd
nanocomposites 3 and 4, but for comparison also with crystal self-
assemblies of 1 and 2. We conducted our experiments in a 35
cm3 airtight test chamber, with the pieces of silicon wafers glued
to a miniaturized ceramic hotplate and connected to a printed
circuit board (Figures S10-S11). The exposure to NO2 was 10 min
with a recovery process of 30 min at 100 mL min–1 flow of dry air.
Nanocomposites operated at 100 °C and their electrical
resistance was monitored within repeated response-recovery
cycles. The materials were all found responsive (Figure 5). The
self-assembly of diamondoid phosphine H2P–DiamOH 1 showed
a NO2 response (3.0% at 100 ppm, cycling time-resolved
detection in Figure 6a) slightly superior to its oxide H2(O)P–
DiamOH 2 (1.5% at 100 ppm) and its Pd nanocomposite
Pd@PH2–DiamOH 3 (2.1% at 100 ppm). A significant NO2
response was achieved with metal nanocomposite Pd@P(O)H2–
DiamOH 4 with fast response and recovery processes (4.8% at
100 ppm, cycling detection in Fig. 6b).
Figure 6a,b. Reversible NO2 detection for sensors of higher sensitivity at 25,
50, 75, and 100 ppm: H2P–DiamOH 1 (chart a), Pd@P(O)H2–DiamOH 4 (chart
b). Signals smoothed using the Savitzky-Golay method.
The same samples were used for NH3 detection in the 25–100
ppm concentration range under the same conditions (air flow 100
mL min–1, 100 °C, 35 cm3 chamber) showing an even higher
sensitivity for the NH3 response (>10.0% for H2P–DiamOH 1 and
>7.0% for Pd@PH2–DiamOH 3 at 100 ppm NH3, see cycling time-
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An issue of low-temperature sensing is the potential
interference of relative humidity and the sensitivity to water is a
factor to consider for practical devices.[2,10] For NO2 detection we
compared the performances of nanomaterials 1–4 under dry and
humid atmospheres (50% relative humidity) as illustrated in
Figure 7b with 4 and 2 (1 and 3 in Fig. S11.5). The detection of
NO2 was effective under either set of conditions, with different
behavior still to rationalize, since 2 (and 3) increases the
sensitivity in humid atmosphere compared to dry conditions, while
4 (and 1) performed better under dry conditions. In any case the
responses were kept detectable in the same range (1–4%).
Remarkably, uptake experiments reported in Fig. 7 were achieved
six months (NO2 sensing) to ten months (NH3 sensing) after
device preparation, attesting their robustness upon storing.
Operational devices for toxic gas request a TLV at low level of
25 ppm for NH3 and 3 ppm for NO2.[2] While our sp3-C-based
diamondoid sensors efficiently detected NH3 at this environmental
level requirement (Figs. 6 and 7b), we further explored the
detection limit of our systems for NO2 in a 13 cm3 airtight test
chamber, reducing the dead volume with unchanged operating
temperature (100 °C) and exposure/recovery times. Under these
conditions, the detection of NO2 concentrations from 50 to 1000
ppb was successfully achieved, and confirmed the suitability of
sp3-carbon-based sensors for detecting few ten ppb of nitrogen
dioxide.
Figure 6c,d. Reversible NH3 detection for sensors of higher sensitivity at 25, 50,
75, and 100 ppm: H2P–DiamOH 1 (chart c) and Pd@PH2–DiamOH 3 (chart d).
Signals smoothed using the Savitzky-Golay method.
Figure 8. Reversible NO2 detection at 50–250 ppb level for high sensitivity
hybrid nanostructure sensor Pd@PH2–DiamOH 3.
In summary, we report the first application of sp3-C-based gas
sensors (NO2, NH3, and H2). Remarkably, they tolerate humid
conditions and achieve sensing of NO2 at ppb levels at 100 °C.
Pristine and metal-nanolayered diamondoids can both be gas
responsive. Such gas sensing properties are related to primary
phosphine-diamantanol based compounds for which channel
nanoporosity (and SBet ca. 140 m2 g–1) derives from H-bonding in
the solid state. We aim at extending our new approach to other
metals and nanoobjects built on suitably functionalized
diamondoid sp3-carbon-based nanostructures.
Acknowledgments
This work was supported by the ANR-DFG program
HYBRIDIAMS (ANR-16-CE92-0037-01 and Schr 597/31-1),
CNRS, ISITE-BFC, Région BFC and FEDER BFC in 2019. In
Tarragona it was supported by MINECO, FEDER (TEC 2015-
71663-R) and AGAUR (2017SGR418). EL was supported by the
ICREA Academia Award 2018. The work in Giessen was
supported by the U.S. Department of Energy (Contract No. DE-
Figure 7. (a) NH3 response of 1 and 3 at increasing 25–100 ppm concentrations
(after 10 months storing); (b) NO2 response with sensors 2 and 4 in dry or humid
conditions (after six months storing):
 = H2P(O)–DiamOH (2),  =
Pd@P(O)H2–DiamOH (4) in dry conditions;  = H2P(O)–DiamOH (2),  =
Pd@P(O)H2–DiamOH (4) in humid conditions (50% relative humidity).
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Keyword: gas sensing • hybrid materials • nanodiamonds •
phosphine • palladium •
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10.1002/anie.201903089
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
O. Moncea, J. Casanova-Chafer, D.
Poinsot, L. Ochmann, C. D. Mboyi, H. O.
Nasrallah, E. Llobet,* I. Makni, M. El
Atrous, S. Brandès, Y. Rousselin, B.
Domenichini, N. Nuns, A. A. Fokin, P. R.
Schreiner,* and J.-C. Hierso*
NO2
sensing
sp3-C
Page No. – Page No.
A nanodiamond-based chemical nose: sp3-C-based diamondoid nanostructures,
either Pd-coated or pristine, detect NO2 and NH3 at ppb to ppm levels at low
operating temperature
Diamondoid Nanostructures as sp3-
Carbon-Based Gas Sensors
This article is protected by copyright. All rights reserved.