Catalytic Transfer Hydrogenolysis of Switchgrass Lignin With Ethanol Using Spinel Type Mixed Metal Oxide Catalysts Affords Control of The Oxidation State of Isolated Aromatic Products

Catalytic transfer hydrogenolysis of switchgrass
lignin with ethanol using spinel-type mixed-metal
oxide catalysts affords control of the oxidation state
of isolated aromatic products
James A. Godwin,1 Jonah P. Babusci,1 Nichole M. Wonderling,2 Jeffrey R. Shallenberger,2
Kendhl Seabright,3 David P. Harper,3 Stephen C. Chmely1*
1
Department of Agricultural and Biological Engineering, The Pennsylvania State University,
University Park, PA 16802 USA.
2
Materials Research Institute, The Pennsylvania State University, University Park, PA 16802
USA.
3
Center for Renewable Carbon, University of Tennessee Institute of Agriculture, Knoxville, TN
37996 USA.
KEYWORDS: lignin, biorefining, catalytic transfer hydrogenation, catalytic transfer
hydrogenolysis, spinel, metal oxide.
https://doi.org/10.26434/chemrxiv-2023-qdbkr-v3 ORCID: https://orcid.org/0000-0002-2637-9974 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0
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Abstract:
Chemical reductions of lignin are useful to remove oxygen and create product slates that can
function as renewable platform molecules for new fuels and chemicals. Catalytic transfer
hydrogenolysis (CTH) is an underexplored method to reduce lignin that obviates the use of
dangerous and non-renewable hydrogen gas. While noble metals are used extensively as catalysts
for transfer hydrogenation, sustainability remains a major challenge to their deployment. In this
work, we synthesized mixed-metal oxides of earth-abundant Co and Ni and characterized the
catalysts using powder x-ray diffraction (XRD). Catalyst reactivity for CTH of acetophenone was
also assessed. Among the catalysts tested, spinel NiCo2O4 demonstrated the highest conversion of
acetophenone (75%) and the highest selectivity for ethylbenzene (90%); thus, we applied it to
valorize switchgrass lignin, extracted under mild operating conditions by cosolvent enhanced
lignocellulosic fractionation (CELF). The catalytically depolymerized lignin showed an increase
in selectively deoxygenated monomeric compounds. As demonstrated using 2D-NMR
spectroscopy, the lignin displayed highly reduced aliphatic carbons resulting from the catalyst-
mediated reduction reaction at the Cα sites. These results are critical to the further development of
the lignin-first biorefinery, as they demonstrate the use of sustainable catalyst materials and mild
transformation conditions to generate and refine a suite of new bioproducts.
2
INTRODUCTION
Lignocellulosic biomass has garnered attention as a renewable carbon feedstock because of its
abundance and potential to replace petroleum as a source of fuels and chemicals. Lignin is a multi-
alkyl-aromatic heteropolymer and a primary component of lignocellulosic biomass.1 It holds great
potential to be directly incorporated into a variety of consumer products or otherwise chemically
processed in a manner analogous to petrochemical refining.2 Traditional biomass processing
technologies, including pulping for papermaking and newer cellulosic ethanol refining, focus on
isolating pure cellulose and maximizing pulp yield by removing lignin, which is considered a
source of biomass recalcitrance.3,4 Technologies used to isolate cellulose, including Kraft pulping,
acidic pretreatments, and even early organosolv fractionation schemes, typically sacrifice lignin
structural quality for high cellulose yield.
However, because of the unique structural features of lignin, including its abundance of aromatic
groups and chemically reactive handles (e.g., hydroxyl and carboxylate groups), new fractionation
technologies have focused on depolymerizing and stabilizing lignin to ensure high purity and a
product slate with limited structural heterogeneity. The resultant molecular product platform
would incur minimal separation costs and maximize utility as a source of new bio-privileged
molecules.5 This type of lignin-first biorefining6 is alternatively referred to as catalytic upstream
biorefining,7,8 early-stage catalytic conversion of lignin,9–11 or reductive catalytic fractionation
(RCF),12 each with subtle but important differences in reaction conditions. Ultimately, these
technologies are designed to isolate high-yield and high-purity lignin for conversion into new
industrially relevant products.13,14
Hydrogenation and hydrodeoxygenation reactions are a central focus of lignin valorization
schemes because the catalytic cleavage of ether bonds in lignin necessarily requires hydrogen.
3
However, hydrogen is highly flammable and challenging to use at scale, primarily because of its
limited solubility in solvents relevant to biomass conversion,15which necessitates high operating
pressures. A recent technoeconomic analysis of a biorefinery using RCF showed that high-pressure
reactors required for traditional hydrogenations account for nearly 60% of the installed capital
costs of the biorefinery.16 Moreover, despite the significant research efforts dedicated to producing
renewable hydrogen,17 steam reforming of non-renewable natural gas continues to supply 95% of
global hydrogen demand,18 offsetting the potential sustainability gains of biorefining processes.16
Transfer hydrogenation is emerging as a more sustainable alternative to deoxygenate and
depolymerize lignin.19–23 Formic acid, alcohols, alkanes, ammonia borane, hydrazine, and even
biomass fractions can serve as hydrogen donors in methods to achieve transfer hydrogenation and
circumvent the use of molecular hydrogen.19 Alcohol solvents are, perhaps, the most intriguing
hydrogen donors; they are readily synthesized from the polysaccharide fractions of biomass and
can function simultaneously as the reducing agent and reaction solvent. Several existing examples
of catalytic transfer hydrogenation/hydrogenolysis (CTH) of lignin employ ethanol or 2-propanol
with a variety of catalysts, including those based on Ni,24–28 Cu,29–31 Ru,32–37 Cs,38 bimetallic
species,39–43 and noble metals.44–47 These and other catalysts and systems for lignin transfer
hydrogenation and hydrogenolysis have been thoroughly reviewed elsewhere. 22,48–52
Spinel-type mixed-metal oxide catalysts are a particularly exciting class of catalyst materials for
CTH. Their chemical reactivity can be tuned by altering the ratios of metals in the material, and
they are air-stable metal oxides that do not require a reducing environment for activation.
Furthermore, mixtures containing iron, cobalt, and nickel are ferromagnetic, meaning the catalysts
are readily magnetically separable from batch reaction mixtures.53 Although these materials have
been deployed for lab-scale catalytic hydrogenation of furan-based molecules (derivable from
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biomass polysaccharides),21 their utility for CTH of biomass-derived lignin remains largely
unexplored, despite their apparent usefulness for such a process.
Controlling the oxidation state of the alpha-C in lignin (Scheme 1) can bestow industrially-
valuable material properties. For example, maximally oxidized Cα (i.e., a ketone) yields highly
conjugated systems capable of absorbing UV light, lending light-blocking capabilities.54 On the
other hand, a Cα hydroxyl group provides a chemical platform to access new small molecules55 or
polymer compounds56 through judicious chemical modification. The Cα oxidation state is sensitive
to lignin isolation procedures, whereby oxidizing acid (e.g., H2SO4) can oxidize the naturally
occurring alpha-hydroxy group to a ketone. Therefore, exerting control over the Cα oxidation state
can be used to explore the chemical and photo-properties of lignin, potentially introducing a
scheme to enhance lignin’s industrial utility.
Scheme 1. Labeling scheme and potential industrial applications of lignin.
Accordingly, we evaluated spinel-type mixed-metal oxides of cobalt and nickel as lignin CTH
catalysts and present the findings here. Using acetophenone, we demonstrated differences in
reactivity and selectivity at the meso (benzylic) carbon based on the atomic composition of the as-
tested catalysts. As the mixed Co-Ni species showed enhanced ability to reduce aliphatic carbons,
this catalyst was applied to switchgrass lignin isolated via the co-solvent enhanced lignocellulosic
5
fractionation (CELF) process.57–59 Our findings from gel permeation chromatography (GPC), gas
1
chromatography-mass spectrometry (GC/MS), and H-13C heteronuclear single-quantum
coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy indicate the catalyst species
can selectively deoxygenate biomass-derived lignin using ethanol via CTH. We comment on the
relative sustainability of spinel-type mixed-metal oxide catalysts and state-of-the-art supported
metal catalysts and consider these catalysts’ role in a lignocellulosic biorefinery that employs
reductive catalytic fractionation.
EXPERIMENTAL SECTION
Biomass and other reagents
Alamo switchgrass (Panicum virgatum) was obtained from Ernst Conservation Seeds. The
plants were harvested after senescence from a plot in Meadville, northwestern PA, USA. The
biomass material was size reduced to 1 mm using a knife mill (Model 4 Wiley mill, Arthur H.
Thomas Company, Philadelphia, PA USA). All other chemical reagents used were of analytical
grade with at least 95% purity unless otherwise specified, and they were used as received.
Quantification of Lignin in Switchgrass
The lignin content of the switchgrass was determined using the acetyl bromide soluble lignin
(ABSL) assay protocol as described elsewhere.60 In brief, 5 g of milled switchgrass was used for
the lignin quantification, as described in the protocol, and the percentage of ABSL was then
computed using the absorbance and extinction coefficient of switchgrass reported from previous
studies.61
Biomass fractionation and isolation of lignin
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Lignin extraction from switchgrass was achieved using cosolvent enhanced lignocellulosic
fractionation (CELF process) as described previously.57–59 Briefly, a 1.0-L Parr reactor with
Inconel wetted parts was charged with 360 mL deionized water containing 3.6 mL concentrated
H2SO4 (98%, 18.4 M), 360 mL tetrahydrofuran (THF), and 80 g switchgrass. An aluminum block
heater was pre-heated above the desired reaction temperature and subsequently applied to the
reactor to quickly heat it to the desired temperature, which was controlled externally by
simultaneously monitoring the temperature of the reactor skin and the internal reactor contents.
This allowed for a rapid heat-up time of the room-temperature reactor contents to reaction
temperature in 20 min. The CELF process was conducted at 150 °C for 20 min (measured after the
reactor reached the final temperature) with constant stirring at 200 rpm. The reactor was
subsequently cooled in an ice bath and the contents were collected and filtered through a glass
fiber filter with a pore size of 0.5 micron. The lignin-rich liquid phase was neutralized with
ammonium hydroxide and concentrated with a rotary evaporator to precipitate the dissolved lignin.
The remaining liquor was decanted, and the lignin precipitate was washed with deionized water
and diethyl ether and dried under vacuum at 40 °C for 20 h.
Catalyst preparation
A urea-assisted synthesis procedure was adapted to synthesize various Co and Ni metal oxides
using CoCl2•6H2O and NiCl2•6H2O as precursors.62 For mono-metallic oxides, a
poly(tetrafluoroethylene)-lined (PTFE) hydrothermal autoclave (Parr Model 4744A, Parr
Instrument Company, Moline, IL USA) was charged with a 36-mL aqueous solution containing
25 g of the desired metal chloride hydrate and 11 g urea (7:3 total metal salt : urea by weight) and
heated to 180 °C for 16 h. After the reaction was complete, the resulting product was removed
from the reactor and washed with deionized water and ethanol and dried under vacuum at 40 °C
7
for 16 h. Before catalytic reactions, this powder was calcined for 2 h at 500 °C under flowing air
to produce the metal oxide. The procedure for mixed-metal oxides was identical except the ratios
of trivalent to divalent metals (e.g., Co:Ni) was 2:1.
Catalyst characterization
X-ray diffraction patterns were collected at 40 kV and 40 mA on a 240 mm
radius Panalytical Empyrean® theta-theta X-ray diffractometer equipped with a line source [Co
K-α 1-2 (1.789010/1.792900 Å)] X-ray tube. The instrument is equipped with a flat programmable
Z-stage and used for phase identification. Data was collected with a step size of 0.0167° from 10-
85° 2-theta. The incident optics consisted of a Bragg-Brentano HD® Co optic fitted with 0.04
rad Soller slits, a 10 mm beam mask, 1/8° and 1/2° divergence, and anti-scatter slit, respectively.
The diffracted optics included a X’Celerator® detector with a 2.1223 active length in scanning
line mode with a 1/4° programmable anti-scatter slit and 0.04 rad Soller slits. Phase identification
was carried out using Jade software (version 8.5) from Materials Data Inc. (MDI) and the
International Centre for Diffraction Data (ICDD) PDF4 database.
Major elemental concentrations were determined using a Cameca SXFive Electron Probe Micro-
Analyzer (EPMA). The instrument is equipped with five wavelength dispersive spectrometers and
a LaB6 electron source. An accelerating voltage of 20 keV and a beam current of 20 nA were used
with a defocused 3 µm beam. The produced X-ray intensities were subject to a PAP (phi-rho-z)
matrix correction algorithm as described by Pouchou and Pichoir (1987) and reported by Christien
et al.,63 and converted to concentrations by comparison to metal oxide standards. The concentration
data for the major elements were collected on pressed power samples. Multiple point analyses (5
for CoO and 10 for CoNiO spinel) were averaged with associated errors to obtain the material
compositions.
8
X-ray photoelectron spectroscopy (XPS) experiments were performed using a Physical
Electronics VersaProbe III instrument equipped with a monochromatic Al kα x-ray source (hν =
1,486.6 eV) and a concentric hemispherical analyzer. Charge neutralization was performed using
both low energy electrons (<5 eV) and argon ions. The binding energy axis was calibrated using
sputter cleaned Cu (Cu 2p3/2 = 932.62 eV, Cu 3p3/2 = 75.1 eV) and Au foils (Au 4f7/2 = 83.96 eV).
Peaks were charge referenced to CHx band in the carbon 1s spectra at 284.8 eV. Measurements
were made at a takeoff angle of 45° with respect to the sample surface plane. This resulted in a
typical sampling depth of 3-6 nm (95% of the signal originated from this depth or shallower).
Quantification was done using instrumental relative sensitivity factors (RSFs) that account for the
x-ray cross section and inelastic mean free path of the electrons. On homogeneous samples major
elements (>5 atom%) tend to have standard deviations of <3% while minor elements can be
significantly higher. The analysis size was ~200µm in diameter.
Catalytic transfer hydrogenation/hydrogenolysis (CTH) of acetophenone
A stock solution containing 0.1 g acetophenone, 0.1 g durene, and 9.8 g anhydrous ethanol was
prepared (10 g total mass). Then, a stainless steel microreactor consisting of a 0.5-in MNPT
stainless steel pipe fitting (Swagelok, P/N: SS-8-HN) and a pair of 0.5-in FNPT stainless steel pipe
caps (Swagelok, P/N: SS-8-CP) was charged with 0.01 g catalyst of interest and 1.0 mL of the
stock solution. The resulting suspension was diluted with 6 mL anhydrous ethanol, and the reactor
was sealed with Teflon tape. The entire reactor was submerged in a molten salt bath (50:50
NaNO2:KNO3) and heated to 320 °C for 2 h. The reactor was subsequently quenched in an ice-
water bath and allowed to equilibrate over 10 min, after which time it was carefully opened to
remove an aliquot of the reaction mixture for analysis by GC/MS. Caution! Acetaldehyde, the
product of dehydrogenation of ethanol, has a boiling point of 20 °C. Opening the reactor directly
9
after removal from the ice water bath helps to prevent rapid escape of gaseous acetaldehyde. The
reactions were performed in triplicate.
CTH of CELF lignin
The CTH of CELF lignin was carried out in a manner like that described above, with some
adaptations of a procedure reported previously.64 Briefly, a stainless steel microreactor (Swagelok,
P/N: SS-16-HLN-3.00) and a pair of 1.0-in FNPT stainless steel pipe caps (Swagelok, P/N: SS-
16-CP) was charged with 0.600 g CELF lignin, 0.060 g catalyst of interest (10% (w/w)), and 10
mL anhydrous ethanol. The microreactor was sealed and heated in the manner described above to
320 °C for 2 h. Subsequently, the reactor was quenched in an ice-water bath, opened, and decanted
through a glass fiber filter with a pore size of 0.5 micron. The lignin-rich filtrate was washed with
water and, subsequently, dichloromethane in a separatory funnel. The collected organic fractions
were dried over anhydrous sodium sulfate and evaporated to dryness to afford a brown lignin oil,
which was further characterized as described below. The reactions were performed in triplicate.
Characterization of products
All catalytic products (acetophenone and lignin) were characterized by GC/MS using an Agilent
7890A GC coupled with an Agilent 5975 MS (Agilent Technologies, Santa Clara, CA USA).
Chromatographic separation of a 1.0 μL injection aliquot was achieved on a 30-m Rxi-5MS GC
column (Restek, Bellefonte, PA USA) with a 0.25 mm ID and a 0.25 μm film. Helium was used
as the carrier gas with a flow rate of 1.0 mL/minute with the following GC oven parameters: hold
at 50 °C for 2.5 min, followed by a ramp of 10 °C/min to 275 °C, with a final hold of 5 min. The
mass spectrometer detector was operated in electron ionization mode with the following
parameters: transfer line at 275 °C, ion sources at 230 °C, full scan of m/z 30-550.
10
Lignin molecular weight (MW) analyses were performed using a Tosoh EcoSEC gel permeation
chromatography (GPC) system with a refractive index (RI) detector equipped with a flow reference
cell (Tosoh Bioscience, LLC, King of Prussia, PA USA). Lignin samples were modified by
acetobromination to enhance their solubility in THF using a procedure described elsewhere.65 The
flow rates of the instrument and reference cell were set to 0.35 mL/min and the analysis was
performed at 40 °C using 2 Tosoh TSKgel SuperMultipore HZ-M (4.6 x 150 mm; 4 μm) columns
and a TSKgel SuperMultipore HZ-M guard column. The instrument was calibrated using
polystyrene standards (580 Da – 2.379 MDa).
Band-selective gradient heteronuclear (1H-13C) single quantum coherence (HSQC) NMR
spectroscopy was performed using a Bruker AV III 600 equipped with a 5 mm TCI z-axis gradient
helium-cooled cryoprobe operating at 600.130 MHz for 1H and 150.903 MHz for 13C. Samples
were prepared using ~20 mg lignin dissolved in 0.5 mL dimethylsulfoxide-d6 (DMSO-d6). Data
collection and processing were performed as described elsewhere.66
RESULTS AND DISCUSSION
Catalyst synthesis and characterization
Metal oxide catalysts were synthesized using a urea-assisted synthesis.62 This method is useful
because it smoothly transforms the water-soluble metal salt precursors to metal carbonates by
thermal decomposition of urea to ammonium carbonate, which serves to raise the pH of the
aqueous solution, thereby precipitating the precursors as metal carbonate materials. Then, these
materials can be collected and transformed into the related metal oxides by calcining in flowing
air. In fact, the morphology of the resulting metal oxide particles can be controlled by using various
surfactants,67,68 although we made no attempts to exert such control for these experiments. In
addition, we used this process for the mono-metal oxides to synthesize bimetallic structures of
11
cobalt and nickel. Overall, this process could be relatively environmentally benign as it employs
aqueous solutions. Some additional wastewater treatment to remove nitrogen may be necessary,
which would negatively impact the overall process sustainability. These studies are ongoing in our
laboratory.
The atomic structure of the resulting metal oxides were characterized using powder x-ray
diffraction (Figure 1).
Figure 1. X-ray diffraction (XRD) pattern for synthesized (a) NiO and related ICDD card, (b)
NiCo2O4 and related ICDD cards, and (c) Co3O4 and related ICDD card.
12
The mono-metal nickel and cobalt oxide samples (Figure 1a and 1c) did not show any crystalline
impurities, nor were any indicators of amorphous material present. As expected,69 the cobalt oxide
crystallized as the mixed-valence Co3O4 spinel structure, with no evidence of CoO or Co2O3
present.
Powder XRD is insufficient to discriminate between the mixed-metal spinel NiCo2O4 and the
mono-metallic parent Co3O4 (Figure 1b and c). However, we used EPMA to determine the atomic
ratio of the mixed-metal spinel. These results show the atomic percentage of cobalt and nickel to
be 35 ± 6% and 15 ± 5% (w/w), respectively. This corresponds to a Co:Ni ratio of approximately
2:1 as expected for NiCo2O4. In addition, the shape and position of the Ni 2p spectrum of NiCo2O4
(Figure S1 in the Supporting Information) was similar to two other Ni-based spinels (NiFe2O4 and
NiCr2O4).70 The Co:Ni ratio was less than the expected 2:1, but XPS is extremely surface sensitive,
and there was evidence of hydroxides in the O 1s spectra. We interpret these observations as
evidence of a mixture of NiCo2O4 and nickel hydroxide at the surface of the powder.
We used the whole-pattern-fitting module in Jade (pseudo-Voigt fitting algorithm and third order
polynomial fitted background) to determine the amounts of spinel and excess NiO. We determined
that the sample contained 97.4% (w/w) NiCo2O4 and 2.6% (w/w) excess crystalline NiO. We
caution the reader that this amount falls within the standard error of the mean of measurements
using EPMA above (5-6%). Based on all these data, although we are unable to unequivocally
determine the amount of excess NiO present, the existence of a small amount of it in the NiCo2O4
sample is a reasonable conclusion.
Catalyst screening for transfer hydrogenation/hydrogenolysis
We then moved to screen our putative catalyst species for catalytic transfer
hydrogenation/hydrogenolysis of acetophenone using ethanol. While we are ultimately interested
13
in CTH reactions of lignin, and acetophenone is not a particularly realistic lignin model compound,
we chose acetophenone because it is a straightforward model to demonstrate whether our catalyst
species could moderate transformations of polar double bonds (i.e., the C=O bond in
acetophenone) in the presence of non-polar double bonds (i.e., the aromatic ring in acetophenone).
For example, Gilhaume and coworkers demonstrated reduction of meso carbons in lignin model
compounds was possible using Pt/C in ethanol/water mixtures.46 Both carbonyl and alcohol groups
could be reduced to alkanes using a Pt-containing catalyst. Such reactivity is crucial to controlling
the oxidation state at the meso (benzylic) carbon in lignin, which we and others have identified as
important for controlling the chemical and physical properties of isolated lignin with respect to its
use in industrially relevant products.
We initially hypothesized a CTH product slate based on sequential transfer hydrogenation of
acetophenone to 1-phenylethanol followed by transfer hydrogenolysis of 1-phenylethanol to
ethylbenzene. We also hypothesized that 1-phenylethanol could undergo a dehydration reaction to
form styrene. This product slate and related reaction scheme are depicted in Scheme 2 below.
Scheme 2. Hypothetical reaction scheme for CTH of acetophenone using metal oxide catalysts
and ethanol.
The hypotheses were tested by conducting the CTH reactions in stainless steel microreactors at
320 °C for 2 h. Ethanol was used as the solvent and reductant (Scheme 2) because it can be easily
14
isolated from biomass; in an industrial biorefinery, isolating cellulosic ethanol and upgraded small
molecules from lignin as coproducts represents an economically and ecologically favorable
industrial process.71–73 GC/MS was used to monitor the concentrations of the molecules shown in
Scheme 2, using durene as an internal standard and constructing a response factor curve for each
molecule. Each catalyst species was tested as was a blank reaction with no catalyst present. The
results of these experiments are summarized in Table 1.
Table 1. Catalyst screening and reactivity test.
Catalysts Xa (%) Y; Sb (%) Y; S (%) Y; S (%)
Blank 50.8(2)c 51.3(8); 101(2) NDd ND

NiO 76.9(1) 1.8(1); 2.3(1) ND 23.1(9); 30(1)
Co3O4 42.2(3) 8.3(2); 19.7(5) ND 29(3); 69(7)
NiCo2O4 74.5(4) 7.0(1); 9.4(1) ND 66.6(4); 89.4(7)
a
X = conversion
b
Y = yield, S = selectivity
c
Number in parentheses shows the standard error of the mean in the preceding digit.
d
ND = not detected
In the absence of catalyst, roughly half of the acetophenone present was converted to products.
This is perhaps unsurprising given the harsh reaction conditions (320 °C for 2 h); yet, we were
intrigued by the result that, in the absence of catalyst, the reaction is 100% selective for reduction
of acetophenone to 1-phenylethanol. No other products were detectable in this reaction, including
the hypothesized ethylbenzene or styrene.
15
When using NiO, the conversion of acetophenone rises to 77%. However, the selectivity for 1-
phenylethanol decreases substantially. We were also able to detect ethylbenzene, albeit with
relatively low selectivity (30%). Although not quantified, both butylbenzene and 1-
ethoxyethylbenzene (the ethyl ether of 1-phenylethanol) were detected. The formation of
butylbenzene occurs via aldol condensation as seen in other Meerwein-Ponndorf-Verley (MPV)
reductions of aldehydes and ketones to alcohols,39 whereas dehydrative etherification could afford
1-ethoxyethylbenzene. The presence of these molecules could account for the poor carbon
recovery shown for this reaction.
In the case of Co3O4, the conversion of acetophenone (42%) was comparatively low, but the
selectivity for 1-phenylethanol (69%) was higher than that of NiO. We again noted the presence
of butylbenzene and 1-ethoxyethylbenzene. However, their formation was evidently suppressed as
more of the desired 1-phenylethanol and ethylbenzene were formed, despite the lower overall
conversion of acetophenone.
When using NiCo2O4, conversion of acetophenone is comparatively high (75%), with high
selectivity for formation of ethylbenzene (89%). While we are unsure of the exact reason for the
enhanced conversion and selectivity when using the spinel as compared to the monometallic
species, there are likely structural differences in the active sites of these materials that warrant
further inquiry. These investigations are ongoing in our laboratory.
Styrene was undetectable in any of the reactions we performed. This was surprising because the
alcohol should be dehydrated with relative ease to form the alkene. Xu and coworkers
demonstrated this reactivity on birch lignin using supported Ni(0) catalysts.74 They demonstrated
a Cα=Cβ bond formation in monomers isolated from birch lignin via transfer hydrogenolysis in
methanol. The ensuing C=C bond was further hydrogenated to alkane using Ni/C. For the case
16
reported here, we speculate that the relative reaction kinetics preclude styrene accumulation in our
system. Specifically, as shown in Scheme 2, the rate constant for dehydration (kdehydration) may be
much lower than the rate constant for hydrogenation of styrene (khydrogenation). In this case, styrene
would be formed slowly and quickly consumed to form ethylbenzene. We are currently exploring
this reactivity for our system using isotopic labeling experiments.
CTH of CELF Lignin
Turning our attention to CTH of lignin using the Co-Ni spinel catalyst, we isolated lignin using
the CELF process from switchgrass. The switchgrass contained 23% (w/w) lignin as shown using
the ABSL protocol,60 which is in agreement with previous results.75 From a feedstock of 80 g, 5.4
g of high purity lignin on dry weight basis (29% yield) was obtained.
A series of experiments analogous to those for our model compound above were performed
using our as-isolated CELF lignin as the substrate with the NiCo2O4 spinel catalyst in ethanol at
320 °C for 2 h. The molecular weight of the lignin samples before and after reaction was
determined using gel permeation chromatography, and the results of these measurements are
shown in Table 2. Apparent molecular weight distributions are displayed in the Supporting
Information (Figure S2).
Table 2. Average Molecular Weight Distribution for CELF Lignin before and after CTH
Sample Mw (g/mol) Mn (g/mol) Ð
CELF lignin (Starting material) 3604 1851 1.947

Control reaction 1533 866 1.77
Reaction with NiCo2O4 2128 984 2.16
17
The as-isolated CELF lignin had a weight-average molecular weight (Mw) of 3604 g/mol, a
number-average molecular weight (Mn) of 1851 g/mol, and a dispersion (Ð, sometimes called
polydispersity, PDI) of 1.947. These values are within the range of molecular weights and Ð
reported previously for CELF-derived lignins for the reaction conditions explored here.76,77 The
control reaction (320 °C for 2 h in the absence of catalyst) and the catalytic reaction produced
lignin samples that displayed nominally smaller molecular weights with a tighter dispersion for
the control reaction. Our overall conclusion is that the reaction conditions and the presence of the
catalyst produce lignin fractions with lower molecular weight distributions. This result agrees with
our previous results using mixed-metal B-containing catalysts.39
A semi-quantitative analysis of the product slate from both the uncatalyzed and catalyzed
reactions on CELF lignin was performed using GC/MS. 1,2,4,5-tetramethylbenzene (durene) was
used as an internal standard, and the peak areas of 10 compounds were normalized to track how
their concentrations changed under reaction conditions with and without catalyst. Each experiment
was performed three times. A nonparametric Mann-Whitney U test was applied to determine the
relative statistical certainty of the noted changes of the product slate using the achieved confidence
level. For example, a confidence level > 95% is mathematically equivalent to a p-value less than
α = 0.05 and indicates, with at least 95% certainty, that the amount of compound either increased
or decreased in the presence of catalyst. The results of these experiments are displayed in Figure
2.
18
Figure 2. Plot of the means (3 replicates) of normalized peak area of 10 compounds tracked in the
product slate of the catalytic reaction using CELF lignin. Peak areas were normalized against an
internal standard of durene. For each compound 1-10, the left peak is the normalized peak area for
the uncatalyzed reaction, and the right peak is that for the catalytic reaction. The probability that
the median values are statistically different with an achieved confidence of 90, 80, and 30% (as
verified by a Mann-Whitney U test using Minitab) are shaded dark gray, light gray, and white,
respectively. Error bars represent the standard error of the mean.
The tracked product compounds can be roughly divided into H- (1-2), G- (3-8), and S-type (9-
10) monomers. We attempted to track the change in concentration of each of these as catalyst was
applied to the reaction. Given our interest in the oxidation state of the meso (benzylic) carbon, we
19
chose compounds that both do (8-10) and do not (1-6) contain a ketone (or aldehyde) at the α-
position (see Scheme 1 above). In addition, we also tracked eugenol (7) since it contains a reducible
double bond.
Overall, the concentrations of compounds such as 2 and 4-6 increased with a high degree of
statistical certainty (α = 0.1). The NiCo2O4 catalyst appears to enhance the formation of these
compounds that contain unoxidized meso carbons (i.e., methyl, ethyl, and propyl side chains). This
agrees with the model compound studies described above, which show that acetophenone is
converted to ethylbenzene with near 90% selectivity.
In addition, the concentration of compounds such as 9 decreased with a high-to-moderate degree
of statistical certainty (α = 0.2). Based on the model compound studies, we expected a decrease in
concentration of compounds containing an aldehyde (or ketone, see below). In those cases, the
oxygen-containing moiety would be reduced to an aliphatic side chain (analogous to the reduction
of acetophenone to ethylbenzene).
In contrast, the concentration of acetovanillone (8) remained constant per the low statistical
certainty displayed (α = 0.7). Our expectation was that the amount of acetovanillone would
decrease in the presence of the catalyst since it contains a reducible ketone moiety and is
structurally like acetophenone. The reason for this deviation from our hypothesis is unclear; the
reactivity of this substrate with the Co-Ni spinel catalyst may be different due to the presence of
electronic-modulating groups on the aromatic ring.
Interestingly, the concentration of eugenol (7) was reduced in the presence of the catalyst with
high-to-moderate statistical certainty (α = 0.2). If the catalyst was able to moderate C=C bond
reduction reactions, this could explain why styrene was not a detectable product in the model
compound reactions (see above). If styrene was formed, it could be immediately reduced to
20
ethylbenzene based on the relative reaction kinetics (Scheme 2). In any event, these two results
suggest there is some selectivity that can be leveraged for this catalyst. We acknowledge the
limited statistical power of our analysis in this determination and are continuing to investigate
these phenomena.
Although GC/MS is a useful tool to separate and identify mixtures of compounds, using it to
unambiguously describe the effects of a catalytic reaction with a complex product slate containing
several oligomeric (or polymeric) compounds is challenging. The resulting chromatogram may
have dozens of peaks, some overlapping, and the limited volatility of some products may make
them undetectable in the mass spectral detector. Alternatively, 2D NMR spectroscopy has been
successfully used to characterize lignin, since it will provide structural information on all the
soluble components in the sample. As above, 2D 1H-13C HSQC NMR spectroscopy was used to
characterize the product slates of the reactions (Figure 3).
Figure 3. Two-dimensional 1H-13C HSQC NMR spectra of untreated CELF lignin (A) and
catalytically treated CELF lignin using NiCo2O4 catalyst (B). Peaks are marked with triangular
flags and structural information is color-coded as shown on the right.
21
2D NMR spectroscopy was used to determine the chemical shift values of the aromatic
hydrogens and carbons, which are sensitive to the oxidation state of the meso (benzylic) carbon.
Chemical shift values were assigned based on the seminal work on 2D HSQC spectroscopy of
biorefinery switchgrass lignin by Bozell and coworkers66 Their study includes a thorough
assignment of peaks arising from changes in the oxidation state at the alpha-carbon in the so-called
“aromatic region” of lignin (colored labels in Figure 3).
As-isolated CELF lignin contains myriad oxidized moieties (Figure 3a), including S-, G-, and
H-type units with carbonyl groups at the alpha position and hydroxycinnamic (caffeic, CA) and
ferulic acid (FA). The molecular symmetry-dependent chemical shift values for the 2,6 (for H- and
S-type moieties) and the 2, 5, and 6 (for G-type moieties) H–C groups are highly sensitive to the
oxidation state of the alpha-carbon, and these moieties resonate far downfield in the proton
dimension of the related standard S-, G-, and H- signals. For example, the peak for oxS2,6 (yellow)
is clearly distinguishable from other S2,6 signals (labeled in gray).
Unsurprisingly, the peaks associated with oxS2,6, oxH2,6, and CA/FA are undetectable in the NMR
spectrum associated with catalytically treated lignin (Figure 3b). This agrees with our model
compound studies and the GC/MS results above, which indicate that the NiCo2O4 can reduce
oxidized alpha-carbon moieties to the associated aliphatic side chain. The region associated with
G-type aromatic H–C groups is of lower resolution, given the molecular asymmetry of a guaiacyl-
ox
type molecule (Figure 3, blue color). The presence of G groups is less easily resolvable.
However, our GC/MS results suggest that acetovanillone is relatively unchanged with catalytic
reaction, which further suggests there could be some electronic differences with this substrate-
catalyst combinations containing G-type moieties, warranting further investigation.
Sustainability of Cobalt
22
No modern catalyst study would be complete without considering the long-term sustainability
issues of the catalyst materials. Transition metals are widely regarded as effective catalysts; their
relative abundance within the Earth’s crust could enable their long-term adoption for use as
industrial catalyst materials. We selected Ni- and Co-based catalysts for this study because their
estimated concentrations within the Earth’s crust are around 90 ppm and 30 ppm, respectively. In
contrast, metals commonly used for hydrogenolysis catalysts, such as Pd and Ru, have estimated
concentrations of 6.3 parts per billion and 1 ppb, respectively.78 However, relative abundance is
not the only aspect to consider when evaluating the sustainability of catalyst materials.
Most lifecycle assessment studies performed for cobalt-based catalysts have focused on the
environmental impact of cobalt mining (environmental lifecycle assessment, e-LCA). Social
lifecycle assessment (s-LCA) is gaining interest as a complementary method, because, despite
cobalt’s high earth abundance,79 the social impacts of metal extraction draws sharp criticism from
some stakeholders. These social impacts include exposure to metals through consumption of edible
products around the mine fields, reduced air quality from the dust particles generated during
mining activities, exploitation of mine workers and mining-adjacent communities, and use of child
labor, among other environmental and social justice issues.80
Studies related to cobalt mine fields in the Democratic Republic of Congo (DRC) is essential,
as the DRC holds over half of the world cobalt reserves. To responsibly source cobalt, one study
proposed implementing a system that considers artisanal and small-scale mining (ASM) and the
more established downstream sectors, which can help improve quality of data needed for s-LCA.81
The United Nations Environment Program (UNEP) proposed guidelines for studying the social
impact through the life cycle of products effectively, including impacts on workers, the local
community, and value chain actors such as consumers, children, and society as a whole.82,83 In
23
addition to promoting uniform evaluations of the social and socio-economic impacts of products
throughout their lifecycle, the UNEP guidelines will help companies make informed decisions,
improve their social performance, and meet the expectations of socially responsible consumers.84
While cobalt’s effectiveness in materials for chemical catalysis and as critical components for
emerging technologies such as electric vehicles is well-documented, the need to consider its social
impact in future sustainability studies cannot be overstated.
CONCLUSION
We have demonstrated the effectiveness of NiCo2O4 as a catalyst for transfer hydrogenolysis of
CELF lignin using biomass-derivable ethanol as the solvent and reductant. Using acetophenone to
probe this reactivity, we obtained 75% conversion with ethylbenzene selectivity nearing 90%.
Moreover, we observed a statistically significant increase in deoxygenated compounds in CELF
lignin after catalytic transfer hydrogenolysis with NiCo2O4. GC/MS and NMR spectroscopy
results confirm the reduction occurs at the alpha carbon, which could unlock lignin’s potential for
conversion to platform molecules for new biopriviledged materials. Further studies to characterize
the mechanism of this reaction as well as the lifecycle implications of using cobalt for lignin
valorization are ongoing in our laboratory.
AUTHOR INFORMATION
Corresponding Author
* E-mail: sc411@psu.edu
ORCID
Stephen C. Chmely: 0000-0002-2637-9974
24
Notes
The authors declare no competing financial interest.
Author Contributions
The manuscript was written through contributions of all authors. All authors approve of the final
version of the manuscript.
Funding Sources
This work was supported by funding from USDA-NIFA Project PEN04671 and Accession number
1017582.
SUPPORTING INFORMATION
Supporting information: High-resolution Ni 2p and Co 2p XPS spectra for all catalyst species
and GPC molecular weight distribution curves for lignin samples.
ACKNOWLEDGMENT
The authors wish to acknowledge the Penn State Materials Characterization Lab for use of the
Malvern Panalytical Empyrean diffractometer, the Cameca SXFive Electron Probe Micro-
Analyzer (EMPA), and the Physical Electronics VersaProbe III x-ray photoelectron spectrometer
(XPS). We would also like to acknowledge the support of Dr. Christy George and Dr. Tapas Mal
for their help with collecting 2D-HSQC NMR data and Dr. Christy Payne for her helpful
discussions about the manuscript. Finally, we wish to acknowledge the support of Prof. Charles
25
Anderson, Dr. Niroshan Siva, and Hannah Klatte for their help with the ABSL assay data
collection.
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Catalytic Transfer Hydrogenolysis of Switchgrass Lignin With Ethanol Using Spinel Type Mixed Metal Oxide Catalysts Affords Control of The Oxidation State of Isolated Aromatic Products

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Catalytic Transfer Hydrogenolysis of Switchgrass Lignin With Ethanol Using Spinel Type Mixed Metal Oxide Catalysts Affords Control of The Oxidation State of Isolated Aromatic Products

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Catalytic transfer hydrogenolysis of switchgrass

lignin with ethanol using spinel-type mixed-metal

oxide catalysts affords control of the oxidation state

of isolated aromatic products

James A. Godwin,1 Jonah P. Babusci,1 Nichole M. Wonderling,2 Jeffrey R. Shallenberger,2

Kendhl Seabright,3 David P. Harper,3 Stephen C. Chmely1*

University Park, PA 16802 USA.

KEYWORDS: lignin, biorefining, catalytic transfer hydrogenation, catalytic transfer

hydrogenolysis, spinel, metal oxide.

work, we synthesized mixed-metal oxides of earth-abundant Co and Ni and characterized the

lignocellulosic fractionation (CELF). The catalytically depolymerized lignin showed an increase

in selectively deoxygenated monomeric compounds. As demonstrated using 2D-NMR

transformation conditions to generate and refine a suite of new bioproducts.

alkyl-aromatic heteropolymer and a primary component of lignocellulosic biomass.1 It holds great

potential to be directly incorporated into a variety of consumer products or otherwise chemically

processed in a manner analogous to petrochemical refining.2 Traditional biomass processing

structural quality for high cellulose yield.

molecules.5 This type of lignin-first biorefining6 is alternatively referred to as catalytic upstream

biorefining,7,8 early-stage catalytic conversion of lignin,9–11 or reductive catalytic fractionation

industrially relevant products.13,14

Hydrogenation and hydrodeoxygenation reactions are a central focus of lignin valorization

limited solubility in solvents relevant to biomass conversion,15which necessitates high operating

Transfer hydrogenation is emerging as a more sustainable alternative to deoxygenate and

of catalytic transfer hydrogenation/hydrogenolysis (CTH) of lignin employ ethanol or 2-propanol

hydrogenation and hydrogenolysis have been thoroughly reviewed elsewhere. 22,48–52

unexplored, despite their apparent usefulness for such a process.

conjugated systems capable of absorbing UV light, lending light-blocking capabilities.54 On the

scheme to enhance lignin’s industrial utility.

Scheme 1. Labeling scheme and potential industrial applications of lignin.

relative sustainability of spinel-type mixed-metal oxide catalysts and state-of-the-art supported

reductive catalytic fractionation.

Biomass and other reagents

Quantification of Lignin in Switchgrass

Biomass fractionation and isolation of lignin

and diethyl ether and dried under vacuum at 40 °C for 20 h.

using CoCl2•6H2O and NiCl2•6H2O as precursors.62 For mono-metallic oxides, a

poly(tetrafluoroethylene)-lined (PTFE) hydrothermal autoclave (Parr Model 4744A, Parr

of trivalent to divalent metals (e.g., Co:Ni) was 2:1.

X-ray diffraction patterns were collected at 40 kV and 40 mA on a 240 mm

International Centre for Diffraction Data (ICDD) PDF4 database.

significantly higher. The analysis size was ~200µm in diameter.

Catalytic transfer hydrogenation/hydrogenolysis (CTH) of acetophenone

reactions were performed in triplicate.

CTH of CELF lignin

adaptations of a procedure reported previously.64 Briefly, a stainless steel microreactor (Swagelok,

Chromatographic separation of a 1.0 μL injection aliquot was achieved on a 30-m Rxi-5MS GC

polystyrene standards (580 Da – 2.379 MDa).

Band-selective gradient heteronuclear (1H-13C) single quantum coherence (HSQC) NMR

collection and processing were performed as described elsewhere.66

RESULTS AND DISCUSSION

Catalyst synthesis and characterization

diffraction (Figure 1).

be 35 ± 6% and 15 ± 5% (w/w), respectively. This corresponds to a Co:Ni ratio of approximately

sample is a reasonable conclusion.

Catalyst screening for transfer hydrogenation/hydrogenolysis

hydrogenation/hydrogenolysis of acetophenone using ethanol. While we are ultimately interested

we chose acetophenone because it is a straightforward model to demonstrate whether our catalyst

use in industrially relevant products.

We initially hypothesized a CTH product slate based on sequential transfer hydrogenation of

acetophenone to 1-phenylethanol followed by transfer hydrogenolysis of 1-phenylethanol to

ethylbenzene. We also hypothesized that 1-phenylethanol could undergo a dehydration reaction to

molecules from lignin as coproducts represents an economically and ecologically favorable

results of these experiments are summarized in Table 1.