pubs.acs.

org/journal/ascecg Research Article

Strategy for Efficient H2 Production from a Mixture of Formic Acid

and Formate using Operando pH Measurements
Chan Kim,⊥ Kimoon Lee,⊥ Il-Han Yoo, Yu-Jin Lee, Safira Ramadhani, Hyuntae Sohn, Suk Woo Nam,
Joohoon Kim, Yongmin Kim,* and Hyangsoo Jeong*
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ABSTRACT: Formic acid (FA) is a promising hydrogen carrier because it contains 4.3 wt
% H2 (53 g H2/L) and releases hydrogen under mild conditions (<80 °C). Previous
studies revealed that the coexistence of formate during FA dehydrogenation increases the
evolved gas quantity and reaction rate. Most of these studies considered formate a
promoter, notwithstanding that formate is a source of H2 and can be dehydrogenated by
reacting with water molecules under Pd nanoparticle catalysis. Moreover, formate is
considered an intermediate species during FA dehydrogenation. Although the reaction
pathways of the dehydrogenation of admixtures of FA and formate are diverse, the determinants thereof remain elusive. We
demonstrate that the system proton concentration determines the hydrogen generation pathway. The system pH and composition of
the accumulated gas were measured under operando conditions. We introduce the “threshold” point, defined by the specific pH
values at which the dehydrogenation pathway utilizes formate instead of FA. The quantity and composition of the produced gas can
be actively controlled by tuning the reaction system pH using the threshold point as a standard. Operando monitoring of the pH can
help discern whether the gas evolution from the mixture originates from chemical equilibrium or catalyst deactivation.
KEYWORDS: Formic acid, Formate, Hydrogen storage and production, Operando pH, Dehydrogenation

■ INTRODUCTION
Using hydrogen as an energy vector is one of the leading
excellent activities and catalyst longevities.7,8 Heterogeneous
catalystswith a higher recyclability than that of their
options in the transition from fossil fuels to clean and homogeneous counterpartscomprising noble metals such
as Pt,9 Ru,10 Au,11 and Pd,12−14 have been developed. Pd
renewable energy fuels.1 To utilize hydrogen as a widely
supported on carbon-based materials exhibits both a high
available fuel, it must be produced from clean energy sources,
reactivity and high selectivity toward FA dehydrogenation
and its distribution should be made economically viable by
instead of FA dehydration.15,16 The use of Pd as a
utilizing the existing infrastructure. Therefore, chemically
monometallic catalyst is the most efficient for FA dehydrogen-
bound forms of hydrogen, that is, chemical hydrides, are
ation (initial rate of HCOOH dehydrogenation of 0.1 mmol
attractive alternatives for storing and transporting hydrogen in
h−1) because of its optimal d-band center position (−1.83
a stable liquid form at room temperature and atmospheric
eV).17 However, research on optimizing the reaction
pressure.2
conditions for FA dehydrogenation has also received increased
As a promising candidate among liquid-phase hydrogen
attention. Previous studies reported that formate coexisting
carriers, formic acid (FA) has garnered substantial attention
with FA serves as an additive for FA dehydrogenation,
owing to its hydrogen content (4.3 wt %, 53 g H2/L) and the
increasing the reactivity and suppressing the detrimental CO
mild conditions required for hydrogen release (low temper-
formation.13,18,19 However, most of these studies focused on
ature <80 °C).3 Currently, FA is mostly derived from fossil fuel
the dehydrogenation of FA and formate mixtures and
resources, but the oxidation of biomass to FA is gaining
overlooked the potential of formate as a hydrogen source.20,21
impetus.4 In addition, FA is the first product of CO 2
Previous studies that utilized Pd as a catalyst for the
hydrogenation and can be further upgraded to high-value dehydrogenation of formate demonstrated that formate itself
chemicals.5 Recently, the electrochemical reduction of CO2 to can be dehydrogenated by reacting with water molecules.22−28
FA in the absence of elevated H2 pressures has provided an
added advantage to utilizing FA as an H2 carrier.6
However, advances in both the catalyst and reaction system Received: September 27, 2021
designs for FA dehydrogenation are required to effectively Revised: December 18, 2021
retrieve the hydrogen chemically stored in FA. Numerous Published: January 5, 2022
studies have focused on devising novel catalysts to increase the
hydrogen yields from FA dehydrogenation. Homogeneous
catalysts composed of Ru- or Ir-based metals exhibited

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888 ACS Sustainable Chem. Eng. 2022, 10, 888−898
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Therefore, clarifying whether FA or formate is the major
hydrogen source during the dehydrogenation of the admixtures
(which might be highly related to reaction conditions, for
example, reactant ratios, pH, and reaction temperature) is
crucial for expanding upon the mechanistic insights. The
reaction pathways during the dehydrogenation of the
admixtures and their decisive factors must be elucidated to
establish the major hydrogen source. To the best of our
knowledge, a facile strategy for the enhancement of the
hydrogen yield from the dehydrogenation of mixtures of FA
and formate with concrete insights about the reaction path has
never been suggested.
Herein, we consider the mixture of FA and formate as a
buffer system having a conjugate acid−base pair relationship;
that is, the pH dictates the molar concentration ratio between
FA and formate. Therefore, we monitored the pH variation
and volume of evolved gas during the dehydrogenation of the
mixtures under operando conditions using a unique customized
reaction evaluation system (Figure S1). We analyzed the gas
composition at the designated times using gas chromatography
(GC). Using these combinatory approaches, we demonstrate
that the molar concentration of FA and the pH of the mixture
are decisive factors determining the reaction path. On the basis
of these mechanistic insights, we further demonstrate that the
quantity of gas generated via the dehydrogenation of the
admixtures of FA and formate can be controlled by
maintaining the FA−formate buffer system. Indeed, when the
FA−formate buffer system was maintained by the periodic
injection of FA and formate mixture, a 16% increase in the
hydrogen yield was obtained compared to that obtained when
the reaction was performed without controlling the buffer
system. Furthermore, we extend our findings and demonstrate
that real-time monitoring of the pH allows a preliminary test to
examine whether gas evolution terminates because of the
chemical equilibrium between FA and formate (eq 14) or
catalyst deactivation.
■ EXPERIMENTAL SECTION
Materials. Formic acid (FA, reagent grade, ≥95%) and palladium
on carbon (Pd/C, Pd loading of 3 wt %; 237515, lot no. MKBR8734
V) were purchased from Sigma-Aldrich. Sodium formate (SF, ACS
reagent) was purchased from Acros Organics. Potassium formate (PF,
ReagentPlus, 99%), citric acid monohydrate (C6H8O7·H2O, ACS
reagent, 99.0%−102.0%), monopotassium phosphate dibasic
(KH2PO4, ACS reagent, ≥98%), and dipotassium phosphate dibasic
(K2HPO4, ACS reagent, ≥98%) were purchased from Sigma-Aldrich.
Hydrochloric acid (HCl, special grade, 35.0%−37.0%) and potassium
chloride (KCl, extra pure grade, 99.0%) were purchased from
Samchun. All reagents were used as received, without further
purification.
Catalytic Dehydrogenation of FA and PF Mixture: General
Procedure. In our previous work on formate dehydrogenation, Pd
nanoparticles supported on a carbon substrate at a concentration of 3
wt % proved the most efficient for H2 generation; this catalyst was
adopted for the dehydrogenation of the mixture of FA and potassium
formate (PF) in this study.29 We employed a three-necked glass
reactor for the reaction system for the kinetic studies with or without
operando pH measurements. When only the produced gas volume was
measured, the neck positioned in the middle of the reactor was sealed
with a rubber septum, and the other necks were connected either to
an oil-filled buret (outlet) or a nitrogen gas stream (inlet). A reactor
containing the catalyst (3 wt % Pd/C, 41.7 mg) was purged with
nitrogen and placed in an oil bath at 65 °C (see Supporting
Information, Figure S2, for why 41.7 mg of 3 wt % Pd/C was used). A
preheated FAx PFy solution, (FA x mmol and PF y mmol; x + y = 10)
was dissolved in 10 mL of aqueous solution and added to the reactor
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with stirring (800 rpm). The volume of the gas produced was
measured in real time using an automatic gas buret system (Figure
S1). When measuring the produced gas volume and the pH change of
the aqueous solution, the middle neck of the reactor was integrated
with an electrode directly connected to a pH meter (Hanna
Instruments, HI 5221).
After the reaction was complete, a portion of the gas generated was
collected using a gastight syringe (VICI Pressure-Lok A-2 series
syringe), and the composition ratio of H2:CO2 was analyzed using gas
chromatography (GC, Model 8890, Agilent Technologies) via manual
injection. The GC was equipped with FID and TCD detectors
connected to two different columns (J&W MolSieve 13X GC
Column, G3591-80012; J&W HayeSep N GC Column, G3591-
81045).
Catalytic Dehydrogenation of FA and PF Mixture in a Buffer
solution. Dehydrogenation of the FA and PF mixture in a buffer
solution was performed using citric acid and K2HPO4 buffer solutions
at different pH values. Buffer solutions with pH 3.1, 4.2, 5.4, and 6.5
were prepared by mixing a citric acid (0.25 M) solution and a
K2HPO4 (0.5 M) solution in different ratios. Additionally, a buffer
solution of pH 5.4 was prepared by mixing a KH2PO4 (1.0 M)
solution and a K2HPO4 (0.5 M) solution to prove that no reaction
was induced by citric acid. A reactor charged only with a catalyst (3 wt
% Pd/C 41.7 mg) was purged with nitrogen and preheated to 65 °C
in an oil bath. A preheated FA/PF (0.1/0.1 M) buffer solution (65
°C, 10 mL) was added to the reactor with stirring (800 rpm). Once all
the gas was released, neat FA (2 mmol) was injected three times every
30 min. The volume of the produced gas was measured using an
automatic gas buret system for real-time volumetric measurements.
Catalytic Dehydrogenation of PF with Proton Injection.
Dehydrogenation of the PF solution with proton injection was
performed using hydrochloric acid as the proton source. A reactor
charged only with a catalyst (3 wt % Pd/C 41.7 mg) was purged with
nitrogen and preheated to 65 °C in an oil bath. A preheated PF (1 M)
solution (65 °C, 10 mL) was added to the reactor with stirring (800
rpm). Five minutes after adding the PF solution, hydrochloric acid
(10 M) (0.1, 0.2, and 0.3 mL; three separate experiments) was
injected twice every 15 min. The produced gas volume was measured
using an automatic gas buret system for real-time volumetric
measurements.
Recyclability Test of Spent Catalyst. The recyclability of the
spent catalyst was regenerated by following procedure. The spent
catalyst was washed twice with excessive amount of DI water and once
with ethanol. In each step, a membrane filter having a pore size of
0.45 μm was used to separate the washed particles. The thoroughly
washed particles were dried in 65 °C oven overnight. To fully get rid
of residual reactants, the dried particles were heat treated in a tube
furnace at 120 °C for 2 h under a N2 atmosphere. The
dehydrogenation efficiency of the recycled catalyst was tested by
following the same procedure mentioned in the above section. In
addition, the recycled particles were characterized by using inductively
coupled plasma optical emission spectroscopy (ICP-OES, iCAP 7000
series, ThermoFisher Scientific) and transmission electron micros-
copy (TEM, TitanTM 80-300, FEI).
■
RESULTS AND DISCUSSION
Proposed Reaction Mechanism and Dehydrogen-
ation of Pure Formic Acid and formate. Previous reports30
state that FA dehydrogenation (eq 1) occurs via the following
reaction mechanism (steps 1−5: eqs 2−6), where ∗ denotes
the active sites. Hereafter, we denote this reaction path as the
FAD route.
HCOOH(aq) F H 2(g) + CO2 (g);
ΔGr = −29.4kJ mol−1 at 65 °C (1)
HCOOH F HCOO− + H+ (2)
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Figure 1. (A) Accumulated volume of gas released during the dehydrogenation of the mixture (upper) and the operando pH measurement (lower).
(B) Gas composition (H2:CO2) variation depending on elapsed reaction time (initial, threshold, and final time points are displayed in panel A).
(C) H2 yield under mixture conditions (panel A) and nonmixture conditions (Figure S3).

HCOO− + * F HCOO− * (3) We derived two major assumptions for our discussion based
on the suggested reaction mechanisms. First, both the FAD
HCOO− * → H− * + CO2 (4) and FMD routes are initiated by the adsorption of formate on
the surface of the catalysts (i.e., Pd nanoparticles). Second, the
H− * + H+ + * → 2H* (5) major reaction path can be determined by the origin of the
protons. If the protons originate from FA, dehydrogenation
2H* → H 2 + 2* (6)
takes place following the FAD route. However, if the protons
Shin et al. reported that formate dehydrogenation (eq 7) originate from water molecules, the FMD route is followed.
follows the reaction path shown below (steps 1′−5′: eqs We analyzed the proton concentration in the reaction system
8−12), denoted as the FMD route henceforth.16,28 because the proton source could be a decisive factor in
determining the reaction route under these assumptions.
HCOO−(aq) + H 2O(l) F HCO3−(aq) + H 2(g); The volume of gas produced from the dehydrogenation of
ΔGr = −0.4kJ mol−1 at 65 °C (7) pure FA and PF with respect to the reaction time is shown in
Figure S3; key results such as the H2:CO2 molar ratios, iTOF,
HCOO− + * F HCOO− * (8) and H2 yields, with the respective reaction conditions, are
tabulated in Table S1. For the pure FA dehydrogenation
HCOO− * F H− * + CO2* (9) (denoted as FA10), the H2 yield was 16% with an iTOF of
1236 h−1 and an H2:CO2 molar ratio of 51:49, which is similar
CO2* + H− * + OH− F HCO3− * + H− * (10) to the theoretically expected ratio of 50:50 for the FA
dehydrogenation represented by eq 1. Meanwhile, the absence
HCO3− * + H− * F HCO3− + H− * (11) of CO in the generated gas (based on GC analysis with a
detection limit <10 ppm) supports the high selectivity of the
H− * + H + F H 2 (12) Pd/C catalyst toward FAD (eq 1) instead of FA dehydration
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(eq 13) and allows the consideration of the FAD route as the
only available gas-generation pathway from FA.
HCOOH(aq) F H 2O(g) + CO(g);
ΔGr = −6.4kJ mol−1 at 65 °C
(13)
Pure PF dehydrogenation (PF10) (eq 7), with predom-
inantly H2 as a gaseous product, exhibits an H2 yield of 50%
with an iTOF of 1534 h−1 and an H2:CO2 molar ratio of 87:13.
The CO2 contained in the product gas originates from the
decomposition of KHCO3, producing CO2 and K2CO3 above
50 °C in aqueous conditions.31
FA and Potassium Formate Ratio, and Solution pH
Effect upon Dehydrogenation. Dehydrogenation reactions
of mixtures of FA and formate (hereafter denoted as MIX)
were performed at 65 °C over a Pd/C (3 wt %) catalyst, where
the sum of the initial concentrations of FA and PF ([FA]0 +
[PF]0) remained constant at 1.0 mol L−1. In previous studies,
the dehydrogenation yield from MIX was explored by fixing
the quantity of FA while varying the quantity of formate.20,21
However, since both FA and PF can theoretically produce 1
mol of H2 gas, we considered it necessary to fix the [FA]0 +
[PF]0 at 1.0 mol L−1 to explore their synergistic roles in the
dehydrogenation without changing the hydrogen sources vs
catalyst ratio.
The volume of gas generated from the admixtures with
different molar ratios of FA:PF (FAx PFy; x mmol of FA and y
mmol of PF in a 10 mL solution) is displayed in Figure 1A
(top). Noticeably, the iTOF for the mixture conditions
exhibited higher values compared to those of the non-mixture
condition; a maximum iTOF of 6465 h−1 at FA4PF6 (Table
S1) was obtained with a maximum H2 yield of 70% (Figure
1C). On the basis of previous reports on MIX dehydrogen-
ation,32−34 it is known that mixtures of FA and formate
accelerate the H2 production rate and produce more gas with
heterogeneous catalysts than those from pure FA or formate
solutions until the reaction ends. In addition, the kinetic
enhancement resulting from mixing FA and formate was
recently explained by DFT calculations;19 FA forms highly
stable bimolecular hydrogen-bonded complexes with formate
on the catalyst surface and helps to stabilize monodentate
formate resulting from the rotational transition of bidentate
formate, which is one of the potential rate-limiting steps in
formate dehydrogenation. Hereafter, we denote the suggested
boosting effect of the coexistence of FA and formate on the
dehydrogenation yield as the synergetic ef fect.
One noticeable difference between the MIX conditions and
the FA10 and PF10 conditions is that MIX is a buffer system
composed of FA and formate, a conjugate acid−base pair.
Therefore, under the MIX conditions, the consumed protons
are replenished by the common ion effect of the FA−formate
mixture solution, while the dissociation of FA maintains the
pH of the system. Moreover, the molar ratio of FA and formate
is determined by the pH of the system, following the
Henderson−Hasselbalch equation (eq 14).
HCOOH(aq) F HCOO−(aq) + H+(aq);
ΔGr = 23.5kJ mol−1 at 65 °C (14)
The pH changes for the selected FA:PF ratios (FA6PF4,
FA5PF5, FA4PF6, and FA3PF7) are presented in Figure 1A
(bottom). The initial pH values for FA6PF4, FA5PF5,
FA4PF6, and FA3PF7 were 3.5, 3.7, 3.9, and 4.1, respectively,
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similar to the theoretical values derived by the Henderson−
Hasselbalch equation (see Supporting Information for details).
Although the degree of the pH change varies with the reactant
ratio, the solution pH was observed to increase as the reaction
proceeded, aligned with the previous results obtained from the
FA and sodium formate mixture dehydrogenation.13,33 The
final pH values were 3.9, 7.7, 8.2, and 8.3 for FA6PF4,
FA5PF5, FA4PF6, and FA3PF7, respectively. As the reaction
solution contained a higher initial PF content, a larger pH
change was observed during the reaction. Importantly, a
marked change in pH was observed under the FA5PF5,
FA4PF6, and FA3PF7 conditions. We defined certain points of
this pH variation as the “threshold” point (hereafter denoted as
TP). The TP was derived by plotting the intersection point of
two tangent lines, one from the initial pH increase slope and
the other from the marked pH increase slope (Figure S4). The
TP can vary depending on the initial FA:PF molar ratio but
remained closely within the pH range of 4.74−4.90. The
mixture condition can be further classified into two different
conditions, x > y and x ≤ y, depending on the existence of the
TP.
Case 1: FAxPFy (x > y). When the initial molar
concentration of FA exceeds that of PF (FA6PF4),
dehydrogenation takes place along the FAD route, as
evidenced by the fixed H2:CO2 molar ratio of 50:50, which
is the theoretically expected value, throughout the entire
reaction (Figure 1B). The simultaneous consumption of
formate and protons for H2 and CO2 formation during the
FAD route was offset by the supply of these from the FA
dissociation. As a result, the system pH could be maintained at
a constant value, as evidenced by the operando pH analysis of
FA6PF4 (Figure 1A, red). Furthermore, since the FAD route
consumes the protons generated by FA dissociation, this
relatively constant pH indicates that the formate and proton
replenishing rate (that is, the forward reaction of eq 14) is
faster than that of the dehydrogenation of FA.
Case 2: FAxPFy (x ≤ y). At the initial stage of
dehydrogenation, formate adsorbed on the surface of the Pd
nanoparticles is preferentially decomposed into H2 and CO2
via the FAD route (eq 1). The GC analysis confirmed this by
showing that the H2:CO2 molar ratio was fixed at nearly 50:50,
as in the x > y case. Concomitantly, FA dissociated into
formate and protons, thereby replenishing the consumed
formate and proton. Initially, the proton concentration
remained relatively constant, as evidenced by the relatively
constant value of the initial pH (Figure 1A). However, the
continuous consumption of both formate and protons
eventually “depletes” FA, which initiates the marked pH
variation in the system. The FA molar concentration at TP,
where the “depletion” of FA occurs, can be derived (5.7 × 10−2
mol L−1) by adopting the Henderson−Hasselbalch equation
(see Supporting Information for details). Moreover, the
concentration variation of FA from the initial pH to the TP
can be mathematically derived; the detailed results are
displayed in Figure S5.
The gas composition varies considerably for FA3PF7 and
FA4PF6 after the TP, thereby demonstrating that both proton
sources required for the hydrogen generation and dehydrogen-
ation path change (Figure 1B). After TP, the increased molar
ratio of H2:CO2 indicates that the dehydrogenation of MIX
occurs via the FMD route (eq 7), in which water molecules
serve as proton sources instead of FA. We highlight that our
operando pH analysis with respect to the reaction time allows
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Scheme 1. (A) Key concepts of Dehydrogenation of FA−formate Mixturea (B) Mechanistic Approach That Introduces the
Concept of Threshold Point as the Specific Point at Which the Proton Source Changes

a
Noticeable effects of the dehydrogenation of the FA and formate mixture originate from the coexistence of FA and formate. These effects
contribute to the dehydrogenation comprehensively.

us to discern the TP, at which the major source of protons
required for hydrogen evolution changes. This is denoted by
the stark increment in pH.
We could explain the initial suspension of gas evolution
observed under all reaction conditions using the TP and
chemical equilibrium between FA and formate. The proton
concentration dictates the allowed molar ratio of FA and
formate under chemical equilibrium (eq 15).
K a = [H+] × ([formate] /[FA]) (15)
892
When FA accounts for a greater proportion than formate
(i.e., FA10, FA6PF4), the TP was not observed. The pH
remained relatively constant for the entire dehydrogenation
reaction, and the gas generation terminated within 20 min.
When gas is generated via the FAD route, the dissociation of
FA simultaneously supplies formate and protons, maintaining
the molar concentrations of both formate and protons constant
throughout the dehydrogenation reaction. Under low pH
range, the allowed molar ratio between formate and FA in eq
15 is small. Therefore, the allowed number of FA molecules
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that can be dissociated is limited, and the gas evolution
terminates because the formate supply is restricted. In our
study, the molar concentration of FA can decrease to 0.2 mol
L−1 under FA6PF4 conditions before the gas evolution stops
(Table S1).
However, when formate is in the same or a larger proportion
than FA (i.e., FA5PF5, FA4PF6, FA3PF7), the TP was
observed; the increased molar ratio of H2:CO2 observed in the
GC analysis at the final stage of the reaction indicated that the
FMD route took place after TP. At the pH where FMD occurs,
the proton concentration remains relatively low (ca. [H+] <
10−7); therefore, the molar concentration ratio between
formate and FA in should remain high. Hence, the gas
evolution is eventually terminated because the allowed
quantity of formate that can be consumed via the FMD
route is limited to retain the chemical equilibrium of eq 14.
Scheme 1A summarizes the two key effects of the
coexistence of FA and formate. It should be noted that the
hydrogen release (FAD and FMD) is initiated by the
adsorption of formate ions on Pd.16,30 Thereafter, the existence
of both FA and formate during the reaction has positive effects
on dehydrogenation through the synergetic ef fect and the
common ion ef fect. As mentioned above, the synergetic effect
was suggested by a DFT simulation of the surface reaction;19
FA in the aqueous solution could stabilize the formate-derived
intermediates on Pd via H-bonding. In this study, we
experimentally revisit this phenomenon and demonstrate the
enhancement of the gas generation rate under MIX conditions
compared to that under pure FA and formate conditions. The
other key effect is the common ion effect, explained by the
concept of the FA−formate buffer system.35−37 Our operando
pH analyses revealed that the conjugate acid−base pair in this
system ensures reaction continuity while maintaining the pH of
the system via the common ion effect. In addition, a dramatic
pH increase at specific points, defined as the TP in this study,
demonstrates that the relative ratio of FA to formate changes
suddenly at the TP, which indicates a change in the reaction
route from the FAD route to the FMD route (Scheme 1B).
Specifically, the proton source for dehydrogenation changes
from FA to H2O.
With insights into the gas evolution mechanisms and the
triggers for the suspension of the gas evolution, we suggest two
rational strategies that can maximize the H2 yield at 65 °C.
This is crucial for devising an H2 generator from FA and
formate with high dehydrogenation efficiency. First, to
generate H2 via the FMD route, the initial FA molar ratio
should be lower than PF to ensure the FA molar concentration
can decrease to 5.7 × 10−2 mol L−1 (i.e., to the TP), while
retaining the chemical equilibrium of eq 14 (Figure S5).
Second, for the FAD route in which the synergetic effect
boosts the reaction rate of the MIX dehydrogenation at the
initial stage, the initial FA molar concentration should be
sufficiently high. This trade-off between the synergetic effect
and additional H2 generation via the FMD route is illustrated
in Scheme 2. There is an optimal point that entails the benefits
of both the FAD and FMD routes. In our experimental
conditions, based on operando pH analysis (Figure 1A), an
initial pH between 3.7 (FA5PF5), 3.9 (FA4PF6), and 4.1
(FA3PF7) is required for dehydrogenation via the FMD route
after the TP. Moreover, the quantity of formate that can be
dehydrogenated with the synergetic effect due to FA was
maximized in FA5PF5 and FA4PF6. Among the initial FA:PF
molar ratios examined, FA4PF6, with an initial pH of 3.9,
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Scheme 2. Trade-Off between FAD Route with Synergetic
Effect Boosting Reaction Rate and FMD Route Allowing
Additional H2 Generationa
a
The FA4PF6 reaction conditions can maximize the total H2 yield by
optimizing both effects. The iTOF and H2 yields corresponding to
each case are tabulated in Table S1.
exhibited the optimal reaction conditions that provided the
maximum H2 yield (70%) (Figure 1C).
Determination of Reaction Pathway via Chemical
Equilibrium of FA−Formate System. To further discover a
determinant for the dehydrogenation reaction pathway, that is,
the FAD vs FMD routes, we purposely altered the
dehydrogenation path from FMD to FAD by adjusting the
proton concentration of the FA−formate system during the
reaction. Initially, when 10 mmol of PF was dehydrogenated at
65 °C, similar to the PF10 condition described in the first
section of the Results and Discussion, the H2:CO2 molar ratio
obtained at a reaction time of 5 min was 93:7 (Figure 2B).
After the first injection of HCl (1 mmol, 10 M) in PF10 at 5
min, a sudden increase in the volume of evolved gas was
observed (Figure 2A) at an average gas evolution rate of 4.0
mL min−1 (Figure 2C); this was defined by the rate of the
volume of additional gas evolved between the first injection of
HCl and the second. The injection of additional protons into
the proton-depleted reaction environment facilitated the gas-
evolving reaction via the FAD route with the synergetic effect.
The effect was supported by the marked change in the H2:CO2
composition ratio to 77:23 at 20 min when the gas evolution
almost stopped. The second injection of HCl (1 mmol, 10 M)
was performed when the gas evolution stopped after the first
injection (20 min). The evolved gas volume increased
markedly (average gas evolution rate of 2.0 mL min−1); the
gas composition of H2:CO2 was 59:41 at the end of the
reaction (30 min) (Figure 2B). The change in the gas
composition indicates that the dehydrogenation after the HCl
injection followed the FAD route. The constant pH value
observed at the initial stage of dehydrogenation of MIX in the
first section of the Results and Discussion indicates that the
reaction rate of both the forward and reverse reactions of eq 14
is faster than that of eq 1 (the common ion effect). Therefore,
the injected proton first reacts with the formate ion to generate
FA. The generation of FA allows formate to be dehydro-
genated via the FAD route via a synergetic effect, as evidenced
by the marked increase in gas evolution. Moreover, the
increase in gas evolution immediately after the second
injection clearly demonstrates that the gas evolution stops
when chemical equilibrium is reached, not by the deactivation
of the Pd/C catalyst. To demonstrate that the effect of
deactivation of Pd/C on the cessation of gas evolution might
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Figure 2. (A) Accumulated volume of released gas (top) and the operando pH measurement (bottom) depending on sequential HCl (10 M)
solution injection to a PF solution at 65 °C at 5 and 20 min. (B) Gas composition (H2:CO2) variation depending on HCl (10 M) solution
injection; HCl 1, HCl 2, HCl 3, and KCl 1 correspond to the injection of 1, 2, and 3 mmol HCl and 1 mmol KCl, respectively, at injection times of
5 and 20 min. (C) Average gas generation rate (mL/min) after injecting the HCl (10 M) or KCl (5 M) solution.

not be the sole factor involved, we injected HCl (3 mmol) into
the PF10 solution after 2 days at 65 °C when the gas evolution
had stopped fully. The results are displayed in Figure S6.
Moreover, the recyclability of the Pd/C catalyst was
thoroughly tested, and we found that the catalyst deactivation
by either CO poisoning or metal nanoparticle sintering is a
negligible factor for the suspension of gas evolution (see the
Supporting Information, Figure S7). The noticeable increase in
gas evolution (73 mL) after the HCl injection clearly
demonstrates that additional gas evolution can be triggered
by the common ion effect. In addition, the negligible impact of
chlorine ions on the reaction kinetics was confirmed by the
negligible perturbations of both the composition and volume
of the produced gas (Figure 2A, B) after injecting KCl (1
mmol, 5 M, the solubility limit of KCl in pure water at 65 °C)
twice at 5 and 25 min.
The corresponding operando pH analyses after injecting HCl
(1 mmol), displayed in Figure 2A (red), clearly indicate that
the pH of the reaction system is not the sole determinant of
the dehydrogenation reaction path. This is because the pH
value is retained above the TP, although dehydrogenation
takes place via the FAD route, as evidenced by the achieved
H2:CO2 (77:23) molar ratio after the HCl (1 mmol) injection.
Instead, the quantity of FA coexisting with formate is a decisive
factor for the dehydrogenation of MIX to occur via the FAD
route. Regardless of the pH in the reaction system, the FA
dehydrogenation path is preferred when FA (concentration
higher than 5.7 × 10−2 mol L−1) coexists with formate. On the
894
basis of the change in the reaction path observed after the TP
(mentioned in the first section of the Results and Discussion),
we presumed that 5.7 × 10−2 mol L−1 is the concentration of
FA at which the quantity of protons that can be supplied by FA
is comparable with that supplied by water molecules under our
experimental conditions (65 °C, 1 bar).
Moreover, the gas evolution rate could be tuned by
controlling the quantity of protons injected. At the first
injection, the average rate of additional gas evolution increased
when 2 and 3 mmol of HCl (10 M) were injected (to 5.7 and
6.7 mL min−1, respectively), compared to that when 1 mmol of
HCl was injected (an additional 4.0 mL min−1 of gas evolution
was observed) (Figure 2A, top). More FA is formed by the
reverse reaction of eq 14 after the addition of more protons.
Therefore, immediately after the first injection, the coexistence
of FA and formate enhances the gas evolution rate, while the
formate adsorbed on Pd is dehydrogenated via the FAD route,
as evidenced by the increased molar ratio of H2:CO2 (74:26
and 51:49, for HCl 2 and HCl 3, respectively) (Figure 2B).
The impact of the proton injection on the molar concentration
ratio of FA:formate was determined from operando pH
monitoring (Figure S8). The recovery of the initial pH after
injecting HCl (2 mmol) indicates that the initial molar ratio of
FA:formate (ca., 1:104) had been restored. However, injecting
excessive HCl (3 mmol) resulted in the loss of the pH buffer
capacity of the system. This was confirmed by the system not
reverting to the initial pH (8) during the 15 min waiting time
after the first injection. Furthermore, additional FA was
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Figure 3. (A) Cation effect on volume of gas released (solid line) and pH variation (dotted line). (B) Gas composition (H2:CO2) and H2 yield
with different ratios of FAxSFy.

Figure 4. (A) Volume of released gas during periodic FA injection (every 30 min, indicated as ↓) in each buffer solution (initial pH indicated). The
operando pH results of other cases are presented in Figure S12. (B) Comparison of the volume of gas released (solid line) and pH measurement
(dotted line) with pH control (obtained with the average volume of gas released values at pH 4.3, 5.4, and 6.6 in panel A where total FA7PF1 was
added every 30 min, indicated as ↓) and without pH control (FA7PF1 was added once initially). (C) Comparison of the volume of gas released
(solid line) during periodic FA injection (every 30 min, indicated as ↓) and operando pH measurement (dotted line) between pH 5.4 buffer (green
line) and without buffering (red line). (D) Comparison of the volume of gas released with buffer control (total FA5PF5 was added every 15 min,
indicated as ↓) and without buffer control (FA5PF5 was added once initially); both solutions did not utilize the external buffer solutions.

generated from residual formate by the second injection of 2
mmol of HCl after the first injection; however, a negligible
amount of gas was generated after the second injection of 3
mmol of HCl because the allowed number of FA molecules
which can be dissociated was limited while the molar
concentration of FA was larger than that of formate (Figure
S8). Therefore, the synergetic effect promoted additional gas
evolution after the second injection of HCl (2 mmol) (Figure
2B). However, because the pH of the reaction system was too
low to produce formate by the dissociation of FA, negligible
gas evolution was observed after the second injection of HCl
(3 mmol); this is also the reason for the suspended gas
895
evolution under the FA10 and FA6PF4 conditions, described
in the first section of the Results and Discussion.
Effects of Cations in MIX Dehydrogenation. Thus, far,
the dehydrogenation characteristics of PF have only been
discussed from the perspective of formate. However, previous
studies have proposed that potassium enhances the dehydro-
genation rate by increasing the surface formate concentra-
tion.38−41 Therefore, we investigated the effect of cations on
the dehydrogenation yield. Figure 3A illustrates the volume of
gas released and the corresponding pH variation when a
mixture of FA (4 mmol) and SF (NaHCO2, 6 mmol) is
dehydrogenated (the results for different ratios of FAx SFy are
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ACS Sustainable Chemistry & Engineering
illustrated in Figure S9). The total volume of evolved gas from
the FA4SF6 mixture was comparable to that evolved from
FA4PF6. Moreover, the pH variation within the reaction
systems exhibited similar trends. The only noticeable differ-
ence was the dehydrogenation rate due to the promoting effect
of potassium. However, a maximum H2 yield of 61% was
obtained under the FA4SF6 condition, similar to MIX
dehydrogenation with PF, further supporting our assumption
that the chemical equilibrium between FA and formate dictates
the overall dehydrogenation efficiency.
■ PERSPECTIVE AND POTENTIAL APPLICATIONS
Our findings imply that the gas evolution stops when the
chemical equilibrium between FA and formate is reached, prior
to catalyst deactivation. Moreover, the pH of the reaction
system plays a crucial role in determining the quantity of FA
that decomposes to formate and protons and replenishes the
reactants for the FAD route with a synergetic effect. On the
basis of this understanding that the dehydrogenation
mechanism is governed mainly by the system pH, we propose
a simple method for increasing the quantity of gas evolved by
maintaining the pH of the reaction system using a prepared
buffer solution and periodically injecting FA.
The volumes of gas released during periodic injections of FA
(2 mmol) were recorded for all buffer solutions (prepared with
citric acid (0.25 M) and K2HPO4 (0.5 M)) with different
initial pH values (Figure 4A). While slightly more gas was
generated when the pH 5.4 buffer was used, a comparable
quantity of gas evolved when the pH of the buffer solution
remained near the neutral region (pH 4.3−6.4). However, a
reduced (1.8 times less) quantity of gas was observed at the
reaction end (120 min) when the reaction took place at pH
3.1. As indicated by the previous discussions, the proton
concentration at pH 3.1 is high enough to impede the
dissociation of FA into formate and protons, thereby lowering
the concentration of formate to below that required to initiate
both the FAD and FMD routes. Moreover, as evidenced by the
gas evolution rate after each FA injection (slope of Figure 4A),
the promoter effect of the coexistence of formate and FA on
the dehydrogenation rate decreases under the pH 3.1
condition because the formate replenishment from FA
dissociation is hindered by the high proton concentration.
Interestingly, the gas evolution trends in the buffer having the
same pH condition are comparable since the initial molar ratio
of FA and formate is fixed due to the external buffer solution
by following the Henderson−Hasselbalch equation (see Figure
S10 in Supporting Information for details).
Finally, our findings indicate that a greater quantity of gas
can be obtained from the same quantity of reagent by
controlling the pH. Figure 4B illustrates the effect of pH
control (obtained with the average volume of gas released at
pH 4.3, 5.4, and 6.6 shown in Figure 4A) on the total gas
generation. By using the same quantities of FA (7 mmol) and
PF (1 mmol), an approximately 1.9 times larger quantity of gas
can be produced by periodically injecting FA and maintaining
the pH of the system compared to no pH control (FA7PF1
was added once initially). Because excess protons can be
consumed by an external buffer solution, FA decomposition
can occur continuously and replenish formate; the dehydro-
genation will occur via the FAD route. The dehydrogenation
reaction takes place continuously via the FAD route since the
periodic injection of FA maintains the molar concentration of
FA higher than 5.7 × 10−2 mol L−1. Figure 4C illustrates that a
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pubs.acs.org/journal/ascecg Research Article
comparable quantity of gas can continuously evolve unless the
proton concentration (represented as the pH value in the
figure) is too high for the dissociation of FA. Moreover, we
found that the same rationale can be extended to explain the
dehydrogenation mechanism of MIX under the pH condition
higher than 7 (pH 8) (see the details in the Supporting
Information, Figure S11). Furthermore, it should be noted that
the presence of citric acid, which contains a carboxyl group,
does not disturb the MIX dehydrogenation because a
comparable total volume of gas is observed when using the
potassium phosphate buffer (1 M) having the same pH (pH
5.4) (Figure S12 E).
We designed a facile strategy to enhance the overall
hydrogen yield based on our findings with the external buffer
solutions and the understanding that MIX is itself a buffer
system. By periodically injecting FA5PF5 and maintaining the
pH of the reaction system at a near-neutral value (pH 4−8)
without utilizing the external buffer solutions, additional gas
can be generated. Upon injecting 1, 2, 3, and 4 mL of FA5PF5
sequentially, the total accumulated volume of gas increased (to
232 mL) compared to that when 1 mL of FA5PF5 was injected
(201 mL of gas evolution). In addition, the H2:CO2 molar
ratio obtained at a reaction time of 60 min was 60:40 in each
condition. A 16% increase in the hydrogen yield (58%) was
observed compared to that obtained under pristine FA5PF5
conditions (50%) (i.e., directly using 10 mL of FA5PF5
solution for dehydrogenation) (Figure 4D).
■
CONCLUSION
Our quantitative studies explain the manner in which the
proton concentration and FA concentration change the
dehydrogenation pathway of mixtures of FA and formate.
The study was based on previous research suggesting that the
coexistence of formate is beneficial for FA dehydrogenation,
but there was insufficient mechanistic insight (the results of
previous research are tabulated in Table S3). The determinants
of the reaction pathway were clarified because the operando
analysis of pH allowed the monitoring of the marked variation
of the pH; the analysis of the gas composition before and after
the TP also helped clarify the determinants of the reaction
path. Moreover, we demonstrate that the dehydrogenation
reaction first stops because of the chemical equilibrium
between FA and formate and not because of the deactivation
of the Pd/C catalyst, which contrasts with the results from
previous studies.42−44 We confirmed that the suspensions of
the dehydrogenation of both FA and PF do not necessarily
indicate the deterioration of the catalyst; that is, the
equilibrium for the FA dissociation could be the “on−off
switch” for the continuation of the dehydrogenation. There-
fore, by integrating the operando measurement capability with
H2 generators from both FA and formate, the regeneration or
replacement process for the catalyst can be applied at the
appropriate time to enhance the system efficiency and H2
production rate. The feasibility of this concept is under
investigation and will be addressed in detail in a future study.
We suggest a facile method to increase the conversion
efficiency from the same quantity of reagent by maintaining
the pH in the buffer based on the reaction mechanism. By
maintaining the pH in a relatively neutral region, the hindrance
of FA dissociation is eliminated. Therefore, the continuous
replenishment of formate and protons takes place via the
periodic injection of FA; consequently, the quantity of gas
evolved increases by approximately 1.9 times compared with
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ACS Sustainable Chemistry & Engineering
that in the reaction conditions without buffering and the
periodic injection of FA.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.1c06603.
Method for determination of appropriate amount of
catalyst, calculation methods, mathematical modeling of
operando pH change based on chemical equilibrium,
schematic drawings of the reactor, volume of gas
released and pH changes, relationship between pH and
residual FA concentration in different FA:PF initial
ratios of the reactant, TEM image of fresh and recycled
catalysts, comparison of palladium contents by ICP
analysis, evolution of pH and accumulated volume of gas
released using multiple buffer solutions, dehydrogen-
ation data with varied ratios of FAxPFy, and optimum
reaction conditions conducted from previous researches
utilizing formic acid and formate salts (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Yongmin Kim − Center for Hydrogen and Fuel Cell Research,
Korea Institute of Science and Technology (KIST), Seongbuk-
gu, Seoul 02792, Republic of Korea; orcid.org/0000-
0003-3152-3405; Email: yongminkim@kist.re.kr
Hyangsoo Jeong − KHU-KIST Department of Converging
Science and Technology, Kyung Hee University,
Dongdaemun-gu, Seoul 02447, Republic of Korea; Center for
Hydrogen and Fuel Cell Research, Korea Institute of Science
and Technology (KIST), Seongbuk-gu, Seoul 02792, Republic
of Korea; Divison of Energy and Environment Technology,
KIST School, Korea University of Science and Technology,
Seongbuk-gu, Seoul 02792, Republic of Korea; orcid.org/
0000-0002-0101-5699; Email: hsjeong@kist.re.kr
Authors
Chan Kim − KHU-KIST Department of Converging Science
and Technology, Kyung Hee University, Dongdaemun-gu,
Seoul 02447, Republic of Korea
Kimoon Lee − Center for Hydrogen and Fuel Cell Research,
Korea Institute of Science and Technology (KIST), Seongbuk-
gu, Seoul 02792, Republic of Korea; orcid.org/0000-
0003-4839-1592
Il-Han Yoo − Center for Hydrogen and Fuel Cell Research,
Korea Institute of Science and Technology (KIST), Seongbuk-
gu, Seoul 02792, Republic of Korea
Yu-Jin Lee − Center for Hydrogen and Fuel Cell Research,
Korea Institute of Science and Technology (KIST), Seongbuk-
gu, Seoul 02792, Republic of Korea
Safira Ramadhani − Center for Hydrogen and Fuel Cell
Research, Korea Institute of Science and Technology (KIST),
Seongbuk-gu, Seoul 02792, Republic of Korea; Divison of
Energy and Environment Technology, KIST School, Korea
University of Science and Technology, Seongbuk-gu, Seoul
02792, Republic of Korea
Hyuntae Sohn − Center for Hydrogen and Fuel Cell Research,
Korea Institute of Science and Technology (KIST), Seongbuk-
gu, Seoul 02792, Republic of Korea; Divison of Energy and
Environment Technology, KIST School, Korea University of
897
pubs.acs.org/journal/ascecg Research Article
Science and Technology, Seongbuk-gu, Seoul 02792, Republic
of Korea
Suk Woo Nam − Center for Hydrogen and Fuel Cell Research,
Korea Institute of Science and Technology (KIST), Seongbuk-
gu, Seoul 02792, Republic of Korea
Joohoon Kim − KHU-KIST Department of Converging
Science and Technology and Department of Chemistry,
Research Institute for Basic Sciences, Kyung Hee University,
Dongdaemun-gu, Seoul 02447, Republic of Korea;
orcid.org/0000-0003-1481-2440
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.1c06603
Author Contributions
⊥
C. Kim and K. Lee contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Research
Foundation of Korea (NRF) grant funded by the Korean
government (MSIT) (No. NRF-2020M1A2A2080881) and
the KIST Institutional Program (No. 2E30993).
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