Electrochemical Synthesis of Hydrogen Peroxide
1. Introduction
Hydrogen peroxide H₂O₂, which is a green oxidant widely used in water treatment,
bleaching, and disinfection. However, its conventional production via the anthraquinone process
relies on large centralized facilities, therefore, electrochemical synthesis through the two-electron
oxygen reduction reaction (2e- ORR) offers a more sustainable alternative and enable using
renewable electricity, eventually reducing safety risks and costs.
2. The electrochemical principles behind hydrogen peroxide formation
Hydrogen peroxide formation in electrochemical systems is governed by electron-transfer
reactions occurring at the electrode–electrolyte interface. During these processes, reactant
molecules such as oxygen or water undergo oxidation or reduction through controlled electron
transfer driven by an applied potential. The formation of H₂O₂ typically involves selective two-
electron transfer reactions in which the O-O bond is preserved rather than fully broken.
The development of catalysts for the electrosynthesis of hydrogen peroxide (H₂O₂) is
particularly challenging because many commonly used electrode materials tend to promote
competing electrochemical reactions. In particular, the four-electron reduction of oxygen (the
oxygen reduction reaction, ORR) and the four-electron oxidation of water (the oxygen evolution
reaction, OER) are unfavorable for H₂O₂ production. For efficient H₂O₂ generation, the
reaction must proceed through the two-electron reduction of O₂ or the two-electron oxidation of
H₂O, which preserves the O-O bond and leads to peroxide formation [1].
Electrochemical synthesis of H₂O₂ is relatively complex compared with many other
electrochemical processes because it involves reversible redox transformations of reactants,
intermediates, and products. This reversibility introduces additional challenges in maintaining
high selectivity toward H₂O₂. Much of the existing research on electrocatalytic oxygen
reduction and water oxidation has been driven by renewable energy technologies, such as fuel
cells, where the complete four-electron reduction of oxygen to water is preferred due to its higher
energy efficiency. Consequently, catalysts that produce H₂O₂ are often considered undesirable
for fuel cell applications. However, such catalysts are highly valuable for the green and
decentralized production of hydrogen peroxide, an important industrial chemical [1].
Current research therefore focuses on developing catalysts that selectively promote the
two-electron pathway while suppressing further reduction to water or oxidation back to oxygen.
Combining experimental studies with theoretical modeling has become an effective strategy for
guiding catalyst design and improving selectivity toward H₂O₂ formation. In addition,
electrochemical cell design plays an important role, particularly the separation of anode and
cathode compartments, which helps prevent the decomposition of H₂O₂ after it is produced.
Based on these fundamental principles, the detailed reaction mechanisms involved in
electrochemical H₂O₂ synthesis are discussed in the following section.
3. Electrochemical pathways for H₂O₂ synthesis
3.1. Mechanism of the water oxidation reaction
The 2e- oxidation of 2H2O can proceed electrochemically to give H₂O₂. All standard
electrode potentials cited in this review are referenced from the Atkins' Physical Chemistry [2]
and are reported versus the standard hydrogen electrode (SHE)
2H2O → H₂O₂ + 2H+ + 2e- E0 = 1.78 V
The arising problem is the desired produced H2O2 can undergo further oxidation:
H2O2 → O2 + 2H+ + 2e- E0 = 0.67 V
The standard potential of the formation of H 2O2 is more positive than that for the further
oxidation of H2O2 to O2, so that any H2O2 formed can be easily oxidized, resulting in lowering
the utility. Many electrochemical cells are optimized for the oxygen evolution reaction , either
via H2O2 or by direct 4e- oxidation of 2H2O [1]:
2H2O → O2 + 4H+ + 4e- E0 = 1.23 V
3.2. Mechanism of the oxygen reduction reaction
The mechanism of hydrogen peroxide electrosynthesis via the two-electron oxygen
reduction reaction (2e- ORR) has been widely investigated in previous studies. This section
summarizes the key reaction steps involved in this pathway [3].
The mechanism of the electrochemical ORR is presented in Fig. 1. Generally, the ORR
(Oxygen Reduction Reaction) involves either a four-electron transfer pathway, which reduces O 2
to H2O.
O2 + 4H+ + 4e- → 2H2O
Figure 1. Schematic of unified two and four-electron oxygen reduction reaction pathways [3].
3.2.1. The selective 2e- Pathway
This is the desired process to obtain hydrogen peroxide. This process retains the O-O
bond the throughout all steps:
Step 1, in this step, molecular oxygen is adsorbed onto the active (*) sites on the electrode
surface. Prior to the formation of H₂O₂, the catalyst must facilitate oxygen adsorption in a
configuration where the O₂ molecule binds to the surface without complete dissociation. This
adsorption mode weakens the O-O bond while maintaining its integrity, thereby favoring the
selective formation of hydrogen peroxide.
Step 2, absorbed oxygen received first electron and proton to form intermediate
Hydroperoxyl (HOO*). The stability of HOO* decides all the reaction rates.
O2 + * + H+ + e- → HOO* (1)
Step 3, intermediate HOO* receive 1 more proton and electron to form H 2O2 molecules
which link to the surface.
HOO* + H+ + e- → H2O2 + * (2)
Step 4, H2O2 molecules release from the electrode surface and move to the liquid phase.
The desorption rate must be fast enough to avoid product retention and deeper reduction.
H2O2 Desorption
→
H2O2 (l) (3)
Where ∗ denotes an unoccupied active site, and HOO ∗, HO∗, O∗ represent the single
adsorbed intermediates on the catalyst surface [4].
3.2.2. Competition with 4e- Pathway
Overall, the direct four electron ORR involves multiple steps and intermediates (HOO*,
HO*, O*), which can be divided into the dissociative and associative way, depending on the
oxygen dissociation barrier on the catalyst surface (Eqs. (4)-(11)) [5,6].
Dissociative pathway: the cleavage of the O-O bond leads to the formation of two
adsorbed oxygen atoms (O*), which subsequently undergo further reduction to produce H2O as
the terminal product.
O2 + 2* → 2O* (4)
2O* + 2H+ + 2e- → 2HO* (5)
2HO* + 2H+ + 2e- → 2H2O + 2* (6)
Associative pathway: In this specific 4e⁻ route, the initially activated O 2 molecule
undergoes a single-proton and single-electron coupling to form a HOO* intermediate; however,
the subsequent cleavage of the O-O bond within this HOO* species leads to its complete
reduction into H2O.
O2 + * + H+ + e- → HOO* (7)
HOO* + H+ + e- → O* + H2O (8)
O* + H + e- → HO* (9)
HO* + H+ + e- → H2O + * (10)
HOO* + * → O* + HO* (11)
From the above reactions and the schematic diagram shown in Fig. 1, it is observed that
breaking the O–O bond (Eqs. (4) and (8)) is a necessary step in both dissociative and associative
four-electron pathways. Therefore, preventing the O-O bond from dissociation is critical in the
selective catalysis for H2O2 synthesis [7].
Moreover, the obtained H2O2 could be further reduced to H 2O, making the process an
indirect four-electron ORR to reduce the H2O2 production (Eqs. (12)-(15)).
H2O2 + * + H + e- → HO* + H2O (12)
HO* + H + e- → H2O + * (13)
H2O2 + 2* → 2HO* (14)
2HO* + 2H+ + 2e- → 2H2O + 2* (15)
Consequently, shortening the H2O2 residence time on the catalyst surface is also critical to
maintaining the stability of H2O2 during electro-synthesis. In summary, the ideal electrocatalyst
with high activity and high selectivity toward twoelectron ORR should have the property of
minimizing the kinetic barriers for Eqs. 2 and 3 and maximizing the barrier for H 2O2 reduction
and HOO* dissociation to HO* and O* [4].
In conclusion, although both the water oxidation reaction (WOR) and the oxygen
reduction reaction (ORR) may promote further oxidation pathways that lead to undesired
products rather than the selective formation of H₂O₂, the electrosynthesis of hydrogen peroxide
via the two-electron oxygen reduction reaction (2e- ORR) is generally considered the more
promising approach. This pathway is particularly attractive because it can operate under
relatively mild conditions and allows for higher selectivity toward H₂O₂ when appropriate
catalysts are employed. In contrast, competing reactions such as the four-electron ORR pathway,
which produces water, or further oxidation reactions that decompose H₂O₂, often reduce the
overall efficiency of peroxide generation. Therefore, significant research has focused on
developing catalysts that favor the two-electron ORR pathway by stabilizing the *OOH
intermediate while preventing O-O bond cleavage, thereby enhancing both the selectivity and
yield of hydrogen peroxide during electrochemical synthesis.
4. Electrochemical production with traditional industrial processes
4.1. Definition
4.1.1. Traditional Industrial Process
It is noticeable that this method currently accounts for over 95% of global H₂O₂
production [8]. The traditional industrial production of hydrogen peroxide is based on the
anthraquinone process, a cyclic chemical method involving the hydrogenation and oxidation of
anthraquinone derivatives. Therefore, initially, anthraquinone is reduced by hydrogen gas to
generate anthrahydroquinone, and then oxidized by molecular oxygen to rebuild anthraquinone,
while producing H₂O₂ as the result.
4.1.2 Electrochemical Production
Unlike traditional processes, electrochemical production of H₂O₂ is concerned with the
synthesis of H₂O₂ through the electrochemical reduction of molecular oxygen in an
electrochemical cell. This process occurs via the 2e - oxygen reduction reaction at the cathode,
where oxygen is selectively reduced to H₂O₂ instead of water. Meanwhile, depending on the
electrolyte conditions, it may form either H₂O₂ or its conjugate base (HO₂-) [8].
4.2. Mechanisms
4.2.1. Mechanisms of traditional Industrial Process (or Anthraquinone process)
The AO process is a multi-stage method that relies on the reversible hydrogenation and
oxidation of anthraquinone derivatives (typically 2-ethylanthraquinone). The process consists of
two main steps: hydrogenation and oxidation, occurring in separate reactors.
Firstly, in the hydrogenation step, anthraquinone is reduced by hydrogen gas to form
anthrahydroquinone (AHQ):
AQ + H₂ → AHQ (catalyst)
Subsequently, in the oxidation step, anthrahydroquinone reacts with molecular oxygen to
reform anthraquinone while producing H₂O₂:
AHQ + O₂ → AQ + H₂O₂
Therefore, the overall process does not involve direct synthesis of H₂O₂ from hydrogen
and oxygen in a single step for avoiding explosives [9]. Notice that the separation of
hydrogenation and oxidation steps can enhance process safety and controllability [10].
However, the mechanism is accompanied by several side reactions, including the
degradation of anthraquinone derivatives and the formation of by-products, which can reduce
efficiency over time.
4.2.2. Mechanisms of Electrochemical Process
The electrochemical processes of H₂O₂ is governed by the oxygen reduction reaction
(ORR) at the cathode, which can proceed via two competing pathways, one is a two-electron
(2e-) pathway and one is a four-electron (4e-) pathway.
In acidic environment, the reaction can be expressed as:
O₂ + 2H⁺ + 2e- → H₂O₂
The mechanism involves the adsorption of O₂ onto the catalyst surface for forming
intermediate species. The adsorption strength of these intermediates plays a critical role in
determining the reaction pathway. If from weak to moderate adsorption, it will increase the
release of H₂O₂, while strong adsorption tends to reduce the intermediates [11], leading to water
formation:
O₂ + 4H⁺ + 4e- → 2H₂O
Although the mechanism described below is characterized by coupling with protons (H⁺),
typical of acidic environments, associative and dissociative pathways also occur in alkaline
media:
O₂ + H₂O + 2e- → HO₂- + OH-
Therefore, factors such as applied potential, pH, and mass transport conditions
significantly influence the kinetics and Faradaic efficiency of the reaction [12].
4.3. Limitations of each processes
The traditional process is really complex and energy-intensive, involving multiple steps
such as hydrogenation, oxidation, and product separation. Furthermore, the use of organic
solvents and hydrogen gas can affect environmental and safety concerns. Moreover, the gradual
degradation of anthraquinone derivatives surprisingly can decrease process efficiency.
On the other hand, electrochemical production is limited by insufficient selectivity,
catalyst stability and durability under long-term operation [13]. Additionally, the production
rates are still quite low, along with mass transport limitations and scale-up challenges.
5. Conclusions
In conclusion, the traditional process remains the main industrial method due to its
efficiency and maturity, despite its complexity and environmental concerns. Meanwhile,
electrochemical production appears as a more sustainable alternative with mild operating
conditions and on-site potential.
References
[1] Perry, S. C., Pangotra, D., Vieira, L., Csepei, L. I., Sieber, V., Wang, L., ... & Walsh, F. C.
(2019). Electrochemical synthesis of hydrogen peroxide from water and oxygen. Nature Reviews
Chemistry, 3(7), 442-458.
[2] Atkins, P. W., De Paula, J., & Keeler, J. (2018, Table 6D.1, pp. 881-882). Atkins' physical
chemistry. Oxford university press.
[3] An, J., Feng, Y., Zhao, Q., Wang, X., Liu, J., & Li, N. (2022). Electrosynthesis of H2O2
through a two-electron oxygen reduction reaction by carbon based catalysts: From mechanism,
catalyst design to electrode fabrication. Environmental science and ecotechnology, 11, 100170.
[4] Siahrostami, S., Verdaguer-Casadevall, A., Karamad, M., Deiana, D., Malacrida, P.,
Wickman, B., ... & Rossmeisl, J. (2013). Enabling direct H2O2 production through rational
electrocatalyst design. Nature materials, 12(12), 1137-1143.
[5] Seh, Z. W., Kibsgaard, J., Dickens, C. F., Chorkendorff, I. B., Nørskov, J. K., & Jaramillo, T.
F. (2017). Combining theory and experiment in electrocatalysis: Insights into materials
design. Science, 355(6321), eaad4998.
[6] Jiao, Y., Zheng, Y., Jaroniec, M., & Qiao, S. Z. (2015). Design of electrocatalysts for
oxygen-and hydrogen-involving energy conversion reactions. Chemical Society Reviews, 44(8),
2060-2086.
[7] Zhang, J., Zhang, H., Cheng, M. J., & Lu, Q. (2020). Tailoring the electrochemical
production of H2O2: strategies for the rational design of high‐performance
electrocatalysts. Small, 16(15), 1902845.
[8] Yang, S., et al. (2023). Strategies for enhancing the electrosynthesis of hydrogen peroxide.
Nature Reviews Materials, 8(3), 156–174.
[9] Sargent, E. H., et al. (2022). Electrified pathways for a sustainable chemical industry.
Science, 376(6589), eabj3069.
[10] Xia, Y., et al. (2024). Advances in carbon-based electrocatalysts for the two-electron oxygen
reduction reaction. Journal of the American Chemical Society, 146(5), 10234–10255.
[11] Viswanathan, V., et al. (2024). Scaling relations in electrosynthesis: Beyond the volcano plot
for H₂O₂. ACS Catalysis, 14(2), 1105–1120.
[12] Koper, M. T. M., et al. (2023). pH-dependent kinetics of the oxygen reduction reaction on
noble and non-noble metal electrodes. Nature Chemistry, 15(4), 488–497.
[13] Gao, J., et al. (2024). Single-atom catalysts for the electrosynthesis of H₂O₂. Advanced
Materials, 36(12), 2304512.