Coupling glucose dehydrogenation with co2 hydrogenation by hydrogen transfer in aqueous media at room temperature

Article abstract of DOI:10.1002/cssc.201800570

Conversion of CO₂ into value-added chemicals and fuels provides a direct solution to reduce excessive CO₂ in the atmosphere. Herein, a novel catalytic reaction system is presented by coupling the dehydrogenation of glucose with the hydrogenation of a CO₂-derived salt, ammonium carbonate, in an ethanol–water mixture. For the first time, the hydrogenation of CO₂ to formate by glucose has been achieved under ambient conditions. Under the optimal reaction conditions, the highest yield of formate reached approximately 46 %. We find that the apparent pH value in the ethanol–water mixture plays a central role in determining the performance of the hydrogen-transfer reaction. Based on the¹³ C NMR and ESI–MS results, a possible pathway of the coupled glucose dehydrogenation and CO₂ hydrogenation reactions was proposed.

Full text of DOI:10.1002/cssc.201800570

Accepted Article
Title: Coupling Glucose Dehydrogenation with CO2 Hydrogenation by
Hydrogen Transfer in Aqueous Media at Room Temperature
Authors: Guodong Ding, Ji Su, Cheng Zhang, Kan Tang, Lisha Yang,
and Hongfei Lin
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201800570
Link to VoR: http://dx.doi.org/10.1002/cssc.201800570
A Journal of
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10.1002/cssc.201800570
ChemSusChem
COMMUNICATION
Coupling Glucose Dehydrogenation with CO2 Hydrogenation by
Hydrogen Transfer in Aqueous Media at Room Temperature
Guodong Ding[a]†, Ji Su[b]†, Cheng Zhang[a], Kan Tang[a], Lisha Yang[c] and Hongfei Lin[a]*
Dedication ((optional))
Abstract: Conversion of carbon dioxide into value-added chemicals
and fuels provides a direct solution to reduce excessive CO2 in the
atmosphere. Herein, a novel catalytic reaction system is presented by
coupling the dehydrogenation of glucose with the hydrogenation of a
CO2 derived salt, ammonium carbonate, in the ethanol-water mixture.
For the first time, the hydrogenation of CO2 into formate by glucose
has been achieved under ambient conditions. Under the optimal
reaction conditions, the highest yield of formate reached ~ 46 %. We
find that the apparent pH value in the ethanol-water mixture plays a
central role in determining the performance of the hydrogen transfer
reaction. Based on the 13C NMR and ESI-MS results, a possible
pathway of the coupled glucose dehydrogenation and CO2
hydrogenation reactions was proposed.
stoichiometric proportion with respect to H2, which inherently
demolish the possibility of creating a carbon negative scheme. In
this respect, using biomass-derived compounds, such as
alcohol,[27–31] polyol[32] or sugar,[33–36] as hydrogen donor for
transfer hydrogenation of CO2 is promising as external molecular
H2 is not needed.[37] Recently Beller’s group used ruthenium
pincer complexes to catalyze methanol dehydrogenation and
bicarbonate hydrogenation simultaneously, providing a green
synthesis route of production of formate in high yields (>90 %)[38]
.
However, it is well known that there are significant challenges
related to the separation, reuse, deactivation, and regeneration of
homogeneous catalysts. Several research groups have studied
transfer hydrogenation of CO2 with biomass-derived alcohol or
polyol by transition metal catalysts, such as Fe, Zn, Ni, in high
temperature (300-400 oC) hydrothermal media.[39–43] Instead of
acting as catalysts, the transition metals served as reducing
agents and were oxidized simultaneously. However, the formate
yield in these cases was pretty low (<10 %).[42] Recently, a novel
approach to simultaneously produce value-added carboxylic
acids and formate has been developed by our group via a “one-
pot” aqueous-phase hydrogen transfer (APHT) process, in which
the hydrogen in biomass molecules is transferred to bicarbonates
over the carbon supported Pd nano-catalysts.[44] However in that
study, a high reaction temperature was needed to facilitate the
dehydrogenation of alcohols or polyols. Unfortunately, at the
same time the decomposition of formate was also inevitably
enhanced at elevated temperatures, which limited the formate
yield. Therefore, low-temperature hydrogen transfer from
biomass derived compounds as hydrogen donor to hydrogenate
CO2 is highly desirable and could be a sustainable strategy to
produce formate.
The concentration of atmospheric CO2 increases dramatically in
the recent several decades. Due to its strong connection to
catastrophic global warming and climate change,[1,2] the utilization
and conversion of carbon dioxide (CO2) has received much
attention recently. Although many value-added substances
including methane, methanol, formaldehyde, formic acid, and
organic carbonates can be produced by CO2 hydrogenation,[3–17]
few processes has been successfully realized in an industrial
scale. Part of the reason is the limitation of sustainable and
economically feasible hydrogen supply, which remains one of the
biggest challenges for CO2 hydrogenation. Based on the techno-
economic analysis of the hydrogen production from water
electrolysis, it has been highlighted that the cost of renewable
hydrogen production has to decrease by at least 2.5 times to
make it economically feasible for the hydrogenation of CO2.[18]
Hydrogen generated from renewable resource such as
biomass has been regarded as an promising alternative
renewable energy resource to replace natural gas and
petroleum.[19–22] However, hydrogen production from biomass,
such as dark fermentation,[23] steam-reforming,[24] aqueous phase
reforming,[25] and gasification[26] suffer from low hydrogen
production rate and/or complicated processing requirements.
More crucially, in these processes, CO2 is produced in
Herein, for the first time, we present a new strategy for CO2
reduction via a room-temperature APHT process using sugar as
a
hydrogen donor to reduce ammonium carbonate over
[a]
Dr. G. Ding, C. Zhang, K. Tang, Prof. Dr. H. Lin
Voiland School of Chemical Engineering and Bioengineering
Washington State University
Pullman, WA 99164, USA
E-mail: hongfei.lin@wsu.edu
Dr. J. Su
[b]
Materials Sciences Division, Lawrence Berkeley National Laboratory,
Berkeley, California 94720, United States
Dr. L. Yang
[c]
Department of Pharmacology
University of Nevada, Reno School of Medicine
Reno, NV 89557, USA
Contributed equally
Scheme 1. The proposed primary pathways of the reactions in low
temperature hydrogen transfer reaction system.
†
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201800570
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heterogeneous Pt and Pd bimetallic catalysts. This process
couples the dehydrogenation of sugar, especially glucose, with
Table 1. Effect of solvent composition on room temperature hydrogen transfer.
Entry
Ethanol weight
percentage
wt %
Glucose
Conversion
/%
Product yield / mol%
CO2 hydrogenation in
a
one-pot process under ambient
Gluconate
Sorbitol
Formate
conditions. Under optimized experimental conditions, the yield of
formate and sorbitol in the solution can be approximately 46% and
21%, respectively. We select carbohydrates such as glucose as
the hydrogen source is due to its abundance as it occupies 75 %
of the annual renewable biomass production.[35] At the same time,
earlier work of the dehydrogenation of carbohydrate done by
Bekkum et. al[33,34] also inspires us to search after the possibilities
on its application. It turns out to be that the dehydrogenation of
sugars such as glucose, can be suitably coupled with the
hydrogenation of CO2 in liquid phase reaction. A schematic
illustration of this novel hydrogen transfer reaction is shown in
Scheme 1. Glucose as a hydrogen donor can be dehydrogenated
into gluconate to produce hydrogen species on Pt surface.
Meanwhile part of the glucose can be hydrogenated into sorbitol
by the produced hydrogen species from the dehydrogenation on
Pt surface as well. It is worthwhile to point out that although the
hydrogenation of glucose to sorbitol is intensively reported,[45–47] it
is normally proceeded under rather high temperature and high
pressure. Herein the production of sorbitol through partial
hydrogenation of glucose in the ambient condition provides a new
possibility of sorbitol acquisition. More importantly, formate is also
obtained through the hydrogenation of CO2 in its carbonate at the
same time in an unprecedented manner in the presence of Pd
catalyst. Thus three value added products can be acquired
simultaneously in the present reaction system under ambient
conditions.
As our previous study showed that involving ethanol as a co-
solvent significantly improves the efficiency of CO2 hydrogenation
due to the creation of an active intermediate, ethyl carbonate.[48]
Initially, we started present hydrogen transfer reaction from
investigating the plausible effects of using ethanol-water mixture
as the solvent. As shown in Table 1, ethanol as a co-solvent
indeed significantly enhanced the yields of formate and sorbitol at
room temperature. The formate yield increased steadily from less
than 5 % to above 30 % upon the increase of ethanol content from
10 % to 50 %. At the same time, the yield of sorbitol was also
doubled. Moreover, ethanol also influenced the conversion of
glucose and H2 concentration in the solvents. With 10% ethanol,
the solubility of H2 in the aqueous solvent increased. Higher local
H2 concentration around Pt might hinder the dehydrogenation of
glucose, leading to the decrease of glucose conversion (64.3 %
to 50.5 %). On the other hand, ethanol reacted with ammonium
carbonate in the ethanol-water mixed solvent to generate ethyl
carbonate which has been proved to be a highly active
intermediate for CO2 hydrogenation[48]. Therefore, the formate
yield increased from 3.0 % to 4.4 %( Entries 1 and 2, Table 1). As
the ethanol content further increased from 10% to 50 %, the
concentration of ethyl carbonate increased. However,
hydrogenation of ethyl carbonate consumed H2 and thus the local
concentration of H2 in the solution might decreased, which
indirectly enhanced the dehydrogenation of glucose and led to a
higher glucose conversion (Entries 2 to 4, Table 1). Unfortunately,
when ethanol was presented in excess (70%), the performance of
the hydrogen transfer reaction deteriorates sharply (Entry 5,
Table 1). This phenomenon can be attributed to the fact that the
solubilies of glucose and ammonium carbonate in aqueous
solvent with high ethanol contents are very low. For example,
glucose is almost insoluble in pure ethanol.[49]
1
2
3
4
5*
water
64.3
50.5
60.6
72.6
58.6
43.8
50.9
59.5
49.8
5.6
5.6
7.5
10.7
7.5
3.0
4.4
12.7
32.3
22.1
10% ethanol
30% ethanol
50% ethanol
70% ethanol
56.5
Reaction conditions: Both Pd and Pt on AC is 5wt %, Pt/AC is 0.1 g, the ratio of
Pd to Pt is 4, 30 mL solvent, 0.18 M glucose, 0.1 M (NH4)2CO3, 0.2 M KOH,
20oC, 24 hours. *The solubilites of glucose and ammonium carbonate were very
low in the 70wt% ethanol solution. Thus the undissolved solutes after the
reaction were re-dissolved for analysis by adding another 30mL water into the
solution.
Previous studies also proved that higher pH favors the
dehydrogenation of glucose as stronger base facilitates the
deprotonation of glucose.[34] A detailed discussion on the pH
effect were presented in the supporting information (Figures S1-
S2). It should be noted here, the yields of formate and sorbitol in
pure water were much more inferior to those in ethanol-water
mixed solvents. As mentioned previously, ethanol has been
proved to be able to improve the hydrogenation of CO2 via the
ethyl carbonate intermediate. The superior performance of the
hydrogenation reaction in 50 wt % ethanol indeed facilitated the
coupled dehydrogenation reaction and thus made the conversion
of glucose comparable to that in the pure water. In our opinion,
this is a clear and live example of interpreting how two cascade
reactions synergize in a “one-pot” process.
Base on the outcomes of the examination on solvent effect, as
well as the screening results of multiple combinations of CO2
derived salts and sugars (supporting information Figures S3-S6),
without special notification, the discussions on the room
temperature hydrogen transfer reaction in the following studies
will be focused on glucose (hydrogen donor)/ammonium
carbonate (hydrogen acceptor) system with 50 wt % of ethanol
solution as the solvent.
퐒퐭퐞퐩 ퟏ: NH4+ + CO32− + H2O ↔ HCO−3 + NH3 ∙ H2O
퐒퐭퐞퐩 ퟐ: HCO−3 + NH3 ∙ H2O ↔ NH2CO2− + 2 H2O
퐒퐭퐞퐩 ퟑ: NH2CO−2 + H2O + CH3CH2OH
↔ CH3CH2OCO−2 + NH3 ∙ H2O
퐒퐭퐞퐩 ퟒ: HCO−3 + OH−
↔
CO23− + H2O
Scheme 2. Postulated equilibriums between carbonate/bicarbonate,
carbamate and ethyl carbonate ions in ethanol-water mixture under alkaline
condition. Step 1 and Step 2 can be merged, assuming carbamate is an
intermediate which can be rapidly converted.
To get more information about the reaction system, we began
following investigations. Previous studies proved that ethyl
carbonate ions could be formed in the ethanol solutions when
ammonium carbamate/carbonate was presented, which resulted
in the superior hydrogenation performance.[48,50] Therefore in
order to explain the decrement of the formate yield caused by the
pH change of the solution, the distributions of carbon species in
the solution at various pH conditions are required to be
investigated. The crucial ionic equilibriums in ethanol-water
mixture are proposed in Scheme 2. In the cases referred in the
discussions above, ammonium carbonate is used as carbon
source thus it might be partly converted into ammonium hydroxide
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10.1002/cssc.201800570
ChemSusChem
COMMUNICATION
nd bicarbonate (Step 1). The formed bicarbonate can be in
equilibrium with ammonium carbamate (Step 2), which will finally
promote the formation of ethyl carbonate ions in the presence of
ethanol (Step 3). However the formed ethyl carbonate can also
be transformed back into bicarbonate or even carbonate (Step 4)
especially under basic conditions.
understand how well these two reactions are coupled as a
cascade reaction. The related hydrogen transfer efficiency (THE)
efficiencies of the cascade reactions are displayed in Figure S1
and Figure S2. In Figure S1b, both HTE formate and HTE total
have optimal values when the concentration of KOH is in the
range from 0.15 to 0.2 M. At the same time, this specific range
also corresponds to a minimal net hydrogen production, indicating
that 0.2 M (pH ca. 11.73) is indeed around the optimal KOH
concentration. When the initial pH is fixed at the optimal value
(Figure S2b), the HTE formate and HTE total just rise up upon the
increase of glucose supply. This result suggests that at optimal
initial pH condition, within the limit of glucose solubility, more
glucose feed results in a better and more efficient cascade
reaction. This property is rather ideal in aspects of both scaling up
and atomic efficiency of reactants. As for the selectivity of formate,
it decreases upon approaching the optimal pH condition from
lower ones (Figure S1b). However as long as the optimal pH
condition is assured, the selectivity of formate is always higher
than 60%.
To identify the distributions of carbon species under different
pH conditions, the 13C NMR spectra of 0.1 M ammonium
carbonate solution (50wt
% ethanol) with various KOH
concentrations were collected. As shown in Figure 1, two major
kinds of peaks are identified. The peak located at 160.2 ppm
should be assigned to the carbonyl carbon in ethyl carbonate ion
(donated as “b” in Figure 1). Another peak assigned to the
bicarbonate/carbonate pair which is located between 161.1 and
169.0 ppm (donated as “a” in Figure 1). It should be pointed out
that the position of ethyl carbonate peak in the spectra is rather
fixed regardless of the increasing of pH. While the peak from
bicarbonate/carbonate pair shifts to higher field upon the
increasing of pH due to the proton scrambling. This kind of higher-
field shift was also observed before in the NH3-CO2-water
system.[51] Clearly, when the apparent pH value increases, there
is an unambiguous transition of carbon species from ethyl
carbonate to bicarbonate and carbonate. When the pH value
reaches 13.90, no peak of ethyl carbonate can be found anymore.
Under this conditions the active species such as ethyl carbonate
and bicarbonate are substantially or even completely converted
to inactive carbonate species, the hydrogenation of ammonium
carbonate will be inhibited. The overall observations of the spectra
are consistent with the postulated ionic equilibrium in Scheme 2.
However, the peak of the predicted carbamate ion is presented in
a negligible manner (around 166 ppm) in all pH conditions. That
indicates carbamate is also an intermediate which can be rapidly
converted into other species in the system, so Step 2 and Step 3
in Scheme 2 can be lumped. On the other hands, as higher pH
value facilitates the dehydrogenation of glucose, it does not favor
the preservation of active carbon species for hydrogenation of
ammonium carbonate. Thus an optimized hydrogen transfer
reaction should be a compromise of both dehydrogenation and
hydrogenation, and thus the optimized pH condition is supposed
to be achieved at 0.2 M KOH in this glucose-ammonium
carbonate system.
Figure 2. ESI-MS analysis: Reaction conditions: 0.4 gPd/AC (5wt%), 0.1 g
Pt/AC (5wt%); 30 mL solvent (50wt% ethanol in aqueous solution), 0.2 M
glucose, 0.1 M ammonium carbonate, 20 oC, 24 h. (a) H2O and 0.2 M KOH were
used. (b) D2O and 0.2 M KOD were used.
Deuterium labelling experiments were further employed to
study the reaction pathways and confirm them by the comparison
between ordinary experiments (Figure S7). Glucose or deuterated
glucose is appeared to be completely deprotonated by 0.2M KOH.
This phenomenon has been intensively discussed before. Here
the ESI-MS results proves that the hypothetic deprotonation
indeed happens under alkaline condition. The mass spectrum
after a single run of normal reaction is shown in Figure 2a. The
signals of formate ion (M/Z=45.4), carbonate ion (M/Z=60.2),
bicarbonate ion (M/Z=61.2), ethyl carbonate ion (M/Z=89.2),
glucose (M/Z=179.1), sorbitol (M/Z=181.1), and gluconate
(M/Z=195.1) are observed. As has been mentioned in the 13C
NMR section before, carbonate ion (M/Z=60.2), bicarbonate ion
(M/Z=61.2), and ethyl carbonate ion (M/Z=89.2) are the ions in
equilibrium in ethanol/water solvent when ammonium carbonate
is dissolved. Here, this is the first time of obtaining direct evidence
of the formation of ethyl carbonate species. And gluconate
(M/Z=195.1) can be firmly regarded as the product of glucose
dehydrogenation, and sorbitol (M/Z=181.1) is the product of
glucose hydrogenation. Figure 2b shows the signals of deuterium
labelling experiment. Formate ion (M/Z=45.3 and 46.3),
carbamate ion (M/Z=60.2), bicarbonate ion (M/Z=61.2 and 62.2),
ethyl carbonate ion (M/Z=89.2), glucose and sorbitol (M/Z=182-
187.2) and gluconate (M/Z=197.1-200.2) are shown in the spectra.
In general, the peaks of the substances are split off due to the
involving of deuterium-hydrogen fast exchange. Most critically,
Figure 1. 13C NMR spectra of 0.1M carbonate dissolved in 30 mL ethanol-water
mixed solvent (50/50 wt%) under three different pH values.
Besides discussing the performances of dehydrogenation and
hydrogenation reactions separately, it is also important to
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10.1002/cssc.201800570
ChemSusChem
COMMUNICATION
the split of the peak from formate indicates that glucose is not the
only hydrogen donor in this low temperature hydrogen transfer
reaction. Other hydrogen donor could be D2O and KOD. More
interestingly, the integrals of the peaks at M/Z=45.3 and 46.3 are
rather close, which implies that glucose and liquid phase each
provides roughly 50 % hydrogen, respectively.
Pd has no catalytic activity in both dehydrogenation of glucose
and hydrogenation of glucose. The hydrogen transferred from Pt
to Pd (Step 6), regardless of its form during the transferring, is
utilized in the hydrogenation reaction of ethyl carbonate and
bicarbonate into formate (Step 7). Note that carbonate has no
activity on this step which has been discussed before.
Based on the above experiments, the proposed mechanism of
the low temperature hydrogen transfer reaction is depicted in
Scheme 3. The deprotonation of glucose into glucose ion in a
basic condition is shown in Step 1. Step 2 is the dehydrogenation
of the deprotonated glucose on the surface of Pt nano-particles,
resulting in the creation of a negatively charged hydride species.
It has been proved that this deprotonation only happens on the Pt
surface (in supporting information Figure S8b). Step 3 is the
production of gluconate via a base catalyzed hydrolysis process.
Step 4 is the oxidation of the produced Pt hydride, in which the
hydride atom coming from glucose reacts with water to produce
hydrogen species and hydroxyl ion. The production of hydroxyl
ion is unambiguous consumed by the deprotonation step and has
to be given back. While as for the produced hydrogen species
which is ready for the supply of hydrogenation, there is quite some
room for discussion. It is well known that metal hydride is
extremely sensitive to water or even moisture, therefore the
hydrogen atom (hydride) on the Pt surface is very likely to be
oxidized by water instantaneously. Meanwhile, we also prove that
the hydrogenation of ammonium carbonate only occurs on the
surface of Pd (in supporting information Figure S8a). Therefore
dehydrogenation of glucose and hydrogenation of ammonium
carbonate are spatially separated. Thus it is hard to imagine how
the hydrogen species can be transported from Pt to Pd surface in
the solution if it is not in the form of hydrogen. We also prove that
the hydrogenation of glucose into sorbitol only occurs on Pt
surface (in supporting information Figure S8b). In another word,
In summary, we have shown that for the first time, the low
temperature hydrogen transfer process can be combined with
CO2 reduction. This reaction system couples two reactions:
dehydrogenation of glucose and hydrogenation of ammonium
carbonate. With the Pd/AC and Pt/AC bimetallic catalyst, a 46 %
yield of formate and a 21 % yield of sorbitol were obtained at the
same time from ammonium carbonate and glucose in ethanol-
water mixed solvents at room temperature. In this cascade
reaction system, the formation of the key intermediate, ethyl
carbonate, in the basic aqueous ethanol solutions plays a central
role in the hydrogenation reaction. The amounts of glucose and
ammonium carbonate as reactants, as well as the KOH additives,
affected the initial pH value of the system significantly and
therefore predominately determine the yields of the main products.
The optimal pH value to maximize the formate yield was
approximately 11.73. The efficiency of hydrogenation transfer
was a compromise of the dehydrogenation and hydrogenation
reactions. However, a complete and fulfilled explanation on the
intrinsic mechanism of the transfer hydrogenation on Pd and Pt
surface still needs further investigation.
Acknowledgements ((optional))
This material is based upon work supported by the National
Science Foundation under Grant No. CBET 1748579. The
authors thank Dr. Steven Spain at the University of Nevada Reno
for the chemical analysis in the Shared Instrumentation
Laboratory.
Keywords: Hydrogen transfer • Gluconic acid • Formate • CO2
reduction • Dual Pt/Pd catalyst
[1]
[2]
[3]
T. Sakakura, J. C. Choi, H. Yasuda, Chem. Rev. 2007, 107, 2365–
2387.
G. Centi, E. A. Quadrelli, S. Perathoner, Energy Environ. Sci. 2013,
6, 1711-1731.
C. Federsel, A. Boddien, R. Jackstell, R. Jennerjahn, P. J. Dyson,
R. Scopelliti, G. Laurenczy, M. Beller, Angew. Chemie - Int. Ed.
2010, 49, 9777–9780.
[4]
S. Ghazali-Esfahani, H. Song, E. Păunescu, F. D. Bobbink, H. Liu,
Z. Fei, G. Laurenczy, M. Bagherzadeh, N. Yan, P. J. Dyson, Green
Chem. 2013, 15, 1584-1589.
[5]
[6]
[7]
[8]
[9]
S. Natesakhawat, J. W. Lekse, J. P. Baltrus, P. R. Ohodnicki, B. H.
Howard, X. Deng, C. Matranga, ACS Catal. 2012, 2, 1667–1676.
H. J. Lee, S. Park, I. K. Song, J. C. Jung, Catal. Letters 2011, 141,
531–537.
D. Preti, C. Resta, S. Squarcialupi, G. Fachinetti, Angew. Chemie -
Int. Ed. 2011, 50, 12551–12554.
S. Sharma, Z. Hu, P. Zhang, E. W. McFarland, H. Metiu, J. Catal.
2011, 278, 297–309.
Scheme 3. The proposed reaction process of low temperature hydrogen
transfer reaction system.
C. J. Stalder, S. Chao, D. P. Summers, M. S. Wrighton, J. Am.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201800570
ChemSusChem
COMMUNICATION
Chem. Soc. 1983, 105, 6318–6320.
[39]
[40]
H. Takahashi, T. Kori, T. Onoki, K. Tohji, N. Yamasaki, J. Mater.
Sci. 2007, 43, 2487–2491.
[10]
[11]
[12]
R. Tanaka, M. Yamashita, K. Nozaki, J. Am. Chem. Soc. 2009, 131,
14168–14169.
B. Wu, Y. Gao, F. Jin, J. Cao, Y. Du, Y. Zhang, Catal. Today 2009,
148, 405–410.
S. Wesselbaum, T. Vom Stein, J. Klankermayer, W. Leitner, Angew.
Chemie - Int. Ed. 2012, 51, 7499–7502.
[41]
[42]
Z. Shen, Y. Zhang, F. Jin, Green Chem. 2011, 13, 820–823.
F. Jin, Y. Gao, Y. Jin, Y. Zhang, J. Cao, Z. Wei, R. L. Smith Jr,
Energy Environ. Sci. 2011, 4, 881–884.
C. Ziebart, C. Federsel, P. Anbarasan, R. Jackstell, W. Baumann, A.
Spannenberg, M. Beller, J. Am. Chem. Soc. 2012, 134, 20701–
20704.
[43]
[44]
Z. Shen, Y. Zhang, F. Jin, RSC Adv. 2012, 2, 797–801.
J. Su, L. Yang, X. Yang, M. Lu, B. Luo, H. Lin, ACS Sustain. Chem.
Eng. 2015, 3, 195−203.
[13]
[14]
W. Leitner, Angew. Chemie Int. Ed. English 1995, 34, 2207–2221.
B. An, J. Zhang, K. Cheng, P. Ji, C. Wang, W. Lin, J. Am. Chem.
Soc. 2017, 139, 3834–3840.
[45]
P. Gallezot, N. Nicolaus, G. Flèche, P. Fuertes, A. Perrard, J. Catal.
1998, 180, 51–55.
[15]
[16]
[17]
[18]
[19]
[20]
S. Kar, A. Goeppert, J. Kothandaraman, G. K. S. Prakash, ACS
Catal. 2017, 7, 6347–6351.
[46]
[47]
H. Li, W. Wang, J. Fa Deng, J. Catal. 2000, 191, 257–260.
B. Kusserow, S. Schimpf, P. Claus, Adv. Synth. Catal. 2003, 345,
289–299.
J. Schneidewind, R. Adam, W. Baumann, R. Jackstell, M. Beller,
Angew. Chemie - Int. Ed. 2017, 56, 1890–1893.
J. Wang, G. Li, Z. Li, C. Tang, Z. Feng, H. An, H. Liu, T. Liu, C. Li,
Sci. Adv. 2017, 3, e1701290.
[48]
[49]
J. Su, M. Lu, H. Lin, Green Chem. 2015, 17, 2769–2773.
G. L. Bockstanz, M. Buffa, C. T. Lira, J. Chem. Eng. Data 1989, 34,
426–429.
M. Pérez-Fortes, J. C. Schöneberger, A. Boulamanti, E. Tzimas,
Appl. Energy 2016, 161, 718–732.
[50]
[51]
F. Barzagli, M. Di Vaira, F. Mani, M. Peruzzini, ChemSusChem
2012, 5, 1724–1731.
M. Ni, D. Y. C. Leung, M. K. H. Leung, K. Sumathy, Fuel Process.
Technol. 2006, 87, 461–472.
F. Mani, M. Peruzzini, P. Stoppioni, Green Chem. 2006, 8, 995-
1000.
R. M. Navarro, M. C. Sánchez-Sánchez, M. C. Alvarez-Galvan, F.
Del Valle, J. L. G. Fierro, Energy Environ. Sci. 2009, 2, 35–54.
H. Balat, E. Kırtay, Int. J. Hydrogen Energy 2010, 35, 7416–7426.
M. Trincado, D. Banerjee, H. Grützmacher, Energy Environ. Sci.
2014, 7, 2464–2503.
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
M.-L. Chong, V. Sabaratnam, Y. Shirai, M. A. Hassan, Int. J.
Hydrogen Energy 2009, 34, 3277–3287.
E. B. Pereira, P. Ramírez de la Piscina, S. Martí, N. Homs, Energy
Environ. Sci. 2010, 3, 487–493.
R. D. Cortright, R. R. Davda, J. A. Dumesic, Nature 2002, 418, 964–
967.
A. C. C. Chang, H.-F. Chang, F.-J. Lin, K.-H. Lin, C.-H. Chen, Int. J.
Hydrogen Energy 2011, 36, 14252–14260.
M. Nielsen, A. Kammer, D. Cozzula, H. Junge, S. Gladiali, M. Beller,
Angew. Chem. Int. Ed. Engl. 2011, 50, 9593–9597.
R. E. Rodríguez-Lugo, M. Trincado, M. Vogt, F. Tewes, G. Santiso-
Quinones, H. Grützmacher, Nat. Chem. 2013, 5, 342–347.
K. N. T. Tseng, J. W. Kampf, N. K. Szymczak, Organometallics
2013, 32, 2046–2049.
K. Shimizu, K. Kon, M. Seto, K. Shimura, H. Yamazaki, J. N. Kondo,
Green Chem. 2013, 15, 418–424.
S. Chakraborty, P. O. Lagaditis, M. Förster, E. A. Bielinski, N.
Hazari, M. C. Holthausen, W. D. Jones, S. Schneider, ACS Catal.
2014, 4, 3994–4003.
[32]
[33]
[34]
Y. Li, M. Nielsen, B. Li, P. H. Dixneuf, H. Junge, M. Beller, Green
Chem. 2015, 17, 193–198.
G. de Wit, J. J. de Vlieger, A. C. Kock-van Dalen, A. P. G. Kieboom,
H. van Bekkum, Tetrahedron Lett. 1978, 19, 1327–1330.
G. de Wit, J. J. de Vlieger, A. C. Kock-van Dalen, R. Heus, R. Laroy,
A. J. van Hengstum, A. P. G. Kieboom, H. van Bekkum, Carbohydr.
Res. 1981, 91, 125–138.
[35]
[36]
[37]
[38]
J. Song, H. Fan, J. Ma, B. Han, Green Chem. 2013, 15, 2619-2635.
H. Kobayashi, A. Fukuoka, Green Chem. 2013, 15, 1740-1763.
M. B. Ansari, S.-E. Park, Energy Environ. Sci. 2012, 5, 9419-9437.
Q. Liu, L. Wu, S. Gülak, N. Rockstroh, R. Jackstell, M. Beller,
Angew. Chem. Int. Ed. Engl. 2014, 53, 7085–7088.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201800570
ChemSusChem
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
A novel catalytic reaction system is
presented by coupling the
G.Ding, J. Su, C. Zhang, K. Tang, L.
Yang, H. Lin*
dehydrogenation of glucose with the
hydrogenation of a CO2 derived salt in
the ethanol-water mixture at room
temperature. Based on the 13C NMR
and ESI-MS results, the possible
mechanism was also proposed.
Page No. – Page No.
Coupling Glucose Dehydrogenation
with CO2 Hydrogenation by Hydrogen
Transfer in Aqueous Media at Room
Temperature
This article is protected by copyright. All rights reserved.