Membranes and Membrane Technologies

, Volume 1, Issue 3, pp 137–144 | Cite as

Interfaces in Materials for Hydrogen Power Engineering

  • I. A. Stenina
  • A. B. YaroslavtsevEmail author


Hydrogen power engineering is based on the production of hydrogen and subsequent oxidation of it to generate electrical energy. Using the example of ion-exchange membranes, catalysts for low-temperature fuel cells, and catalysts for alcohol steam reforming, the features of the transfer, catalysis, and electrocatalysis in hydrogen power engineering are discussed. Particular attention is paid to the role of interfaces. The occurrence of transport processes in ion-exchange membranes is determined by a system of pores and channels that are formed in the membranes owing to self-organization processes. The main selective transport of counterions occurs in a thin Debye layer at the interface between the polymer and the water solution that fills the pores. The transport of gases in these systems occurs through an electrically neutral solution localized in the center of the pores; it can be controlled by introducing nanoparticles into the pores. Catalytic processes in fuel cells occur at the interface between three phases, namely, the catalyst, the support, and the proton-conducting component. The role of the support in the stabilization and enhancement of the power of fuel cells is discussed. Despite the significant difference, the laws governing the catalytic processes of alcohol steam reforming are similar to those of fuel cells in many respects. The nature of metal catalysts is responsible for the preferred direction of the process, whereas the nature of the support largely determines the catalyst performance.


interfaces proton conductivity membranes steam reforming catalysis supports 


Modern civilization cannot exist without the use of energy, which is in ever-increasing demand. According to the International Energy Agency, the primary energy production increases approximately twofold within 30–40 years. However, electrical energy production is generally associated with environmental degradation. The combustion of crude oil, coal, and gas leads to the emission of huge amounts of carbon, sulfur, and nitrogen oxides and products of their incomplete combustion into the atmospheric. In addition, there is a threat of oil reserve depletion, and oil is currently the main energy source. There is an opinion that, at the end of the 21st century, crude oil will mostly be used for chemical synthesis [1]. Therefore, an intensive search for new alternative energy sources is being conducted. It is believed that the use of so-called renewable energy sources, which are replenished through natural processes, is the most appropriate. Of greatest interest are solar cells, the use of which in Russia is fairly promising [2]. In addition, a significant contribution is expected from a number of other renewable sources, such as wind energy, river power, tidal energy, and biomass processing. At present, a significant disadvantage of all these sources is a relatively low efficiency; significant efforts are being made to increase this parameter. An even greater problem is a periodic behavior of power generation from solar, wind, and other sources. In this context, it is necessary to design complex systems comprising energy storage units. To date, the best-known energy storage units are lithium-ion batteries. However, their use for large-scale power engineering is problematic because of the limited lithium reserves. It is assumed that sodium-ion batteries will be used for these purposes [3], because the sodium content in the earth’s crust is three orders of magnitude higher than the lithium content. However, any battery is inappropriate for damping the annual fluctuations of solar energy, the intensity of which in summer is an order of magnitude higher than that in winter, while the energy consumption, conversely, is 2 times higher in winter [1]. It is believed that the most promising solution of this problem is the use of a complex based on steam electrolyzers and fuel cells (FCs) using the energy of hydrogen oxidation [4].

In addition, FCs can be thought of as an independent energy source in using hydrogen generated from natural gas [5]. In recent years, considerable attention has been paid to hydrogen production from biomass [6] or alcohols resulting from biomass processing [7]. These sources of hydrogen can also be used as renewable sources. Therefore, hydrogen power engineering is thought of as one of the most promising directions of future power engineering and can be widely used for autonomous power supply. This problem is highly relevant for Russia, where a significant portion of the territory has not yet been covered with electrical networks [8].

Thus, the design and improvement of FCs and reformers for hydrogen production are important tasks for the advancement of hydrogen power engineering. Despite all the differences in the processes that occur in these decides, the materials used in them have much in common. This review is focused on the role of surface phenomena and interfaces in catalysts and membranes used for hydrogen power engineering.


Membranes that are most commonly used in FCs are macromolecular sulfonated cation-exchange membranes of the Nafion type [9]. The flexibility of the macromolecular chains constituting the membrane provides the occurrence of self-organization processes in them. The hydrophilic functional –SO3H groups are agglomerated into clusters and absorb water molecules from the surrounding space to form a system of pores and channels [10]. This system is responsible for the unique transport properties of these membranes. The functional groups of the materials, which are fragments of a strong acid (–SO3H), undergo almost complete dissociation. Negatively charged fixed \(--{\text{SO}}_{{\text{3}}}^{ - }\) ions cover the membrane pore walls. The protons pass into the aqueous solution; however, most of them remain localized near the pore walls owing to the electrostatic interaction and form an electrical double layer with them. The protons are localized in a Debye layer with a thickness of about 1 nm. It is this layer through which almost all the protons are transported; a nearly electroneutral solution is localized in the center of the pore; the composition of this solution is close to that of the solution contacting with the membrane. In FCs, the membrane contacts only with steam and gases. In this case, the electroneutral solution is represented by almost pure water, as shown in [11]. However, it is this water in which gases and methanol are dissolved. This feature is responsible for their crossover [12], which leads to a decrease in the power and efficiency of the FC. Since the water solubility of methanol is significantly higher than that of gases, crossover is most critical for methanol FCs.

The most effective way to prevent this undesirable phenomenon is the design of hybrid membranes containing nanoparticles of various inorganic substances, primarily, oxides and salts. Therefore, there is intense interest in the use of hybrid membranes in methanol FCs [12, 13]. The effect is associated with the fact that nanoparticles are incorporated into the pore to displace primarily the electroneutral solution from it [14]; as a consequence, the solubility and crossover of methanol decrease. It should be noted that this modification is particularly effective in the case of introduction of particles whose surface contains groups capable of dissociating by the acid mechanism, in particular, acid salts of heteropoly acids, oxides, and carbon with a sulfonated surface [15, 16, 17, 18, 19, 20, 21]. In this case, nanoparticles with a negatively charged surface should be located in the center of the pore. In addition, an electrical double layer is also formed near the surface of the particles; this process leads to an even more significant displacement of gases and methanol from the membrane [14]. Fuel cells based on these membranes are characterized by a high power, in particular, at low temperatures [22].


In the presence of hydrogen–air FC catalysts, fairly trivial processes—hydrogen and oxygen sorption—occur. Protons arising from the dissociative sorption of hydrogen at the anode (reaction (1)) and the subsequent electrooxidation of it are transported across a proton-conducting membrane owing to the chemical potential gradient and react with the sorbed oxygen to form water [23]. Multistage oxygen electroreduction (reaction (2)) occurs much more slowly because of the necessity to break the strong double bond and limits the FC power [24]:
$${{{\text{H}}}_{2}}-2{\text{e}} \to 2{{{\text{H}}}^{ + }},$$
$${{{\text{O}}}_{2}} + 4{{{\text{H}}}^{ + }} + 4{\text{e}} \to 2{{{\text{H}}}_{2}}{\text{O}}.$$
Note that almost all of commercial FC catalysts are based on platinum, in the presence of which both the cathodic and anodic processes occur much more rapidly than in the presence of other metals.

Fuel cell catalysts, in addition to performing their main function, i.e., sorption and electrochemical conversion of fuel and oxygen, should provide the arrival of protons and electrons to the chemical reaction zone (or their removal), a rapid supply of gases, and the removal of the resulting water. Therefore, platinum is most commonly deposited on a fine electron-conducting support, which is typically prepared of carbon [23]. Proton conductivity is provided by the addition of a small amount of a proton-conducting polymer, such as the above-mentioned Nafion. In this case, the electrocatalytic process always occurs near the interface between the three above phases (Fig. 1a).

Fig. 1.

Schematic of degradation of the platinum/carbon/polymer three-phase contact during fuel cell operation.

It is obvious that the catalyst activity is primarily determined by the surface area of platinum at the three-phase interface. Therefore, the rate of electrochemical processes generally increases with decreasing particle size. On the other hand, catalysts with a small particle size rapidly undergo degradation. Most researchers agree that for methanol electrooxidation and/or oxygen electroreduction, the optimum size of Pt particles is 2.5–5 nm [25, 26, 27]. For the oxygen electroreduction reaction, the optimum particle size is 2–4 nm [28, 29, 30, 31]. However, catalysts with a large particle size exhibit a more stable on-stream behavior [32]. The typical size of platinum nanoparticles in commercial catalysts is 2.5–5 nm [33].

Hydrogen produced by hydrocarbon reforming always contains a certain amount of CO, which, at a temperature below 120°C, is irreversibly sorbed on platinum and thereby hinders the sorption of hydrogen. The anode potential of FCs is insufficient to provide CO oxidation. Therefore, even a low CO concentration in the fuel abruptly decreases the current density [34]. A similar picture is observed in methanol FCs. During methanol chemisorption on Pt, the same CO groups are formed [35], and the degree of binding of the catalyst surface can achieve 90%. The use of alloys of platinum with other metals makes it possible to decrease the formation of CO [35] and reduce the consumption of this expensive metal [36, 37].

It is obvious that the main catalytic activity is attributed to platinum. In addition, the localization of the second metal on the surface of bimetallic nanoparticles leads to a more intense dissolution of it owing to the formation of a galvanic pair. This factor inevitably leads to membrane degradation due to a decrease in proton conductivity. Therefore, it is more advantageous to form bimetallic core–shell nanoparticles with the outer layer represented by platinum [38, 39]. In this case, the shift of the electron density to less active platinum leads to the stabilization of this parameter. A promising approach is the preparation of alloys and subsequent acid treatment of them to remove more active metals from the surface [40]. Despite the structure heterogeneity, these particles are commonly referred to as alloys. Typically, they are prepared by adding group 8 metals (Ru, Pd, Os, Fe, Co, Ni), copper, silver, and some other metals to platinum [41, 42]. It is believed that the most efficient anodic electrocatalyst is a PtRu alloy [43, 44, 45, 46]. An important characteristic of PtRu and a number of other platinum alloys is a high tolerance to CO [47, 48, 49]. Optimum catalytic properties in the oxygen reduction reaction are achieved at a Pt : metal ratio of about 7 : 3 [50, 51, 52].

It is assumed that CO sorbed on Pt is oxidized by water sorbed on the second metal [53, 54, 55]. However, in view of the advantages of core–shell alloys, this hypothesis is not so obvious. It is more logical to assume that the formation of an alloy leads to an increase in the Fermi level of platinum and an improvement in the chemisorption of CO and water [56, 57, 58].


The role of the support is of no less importance. As noted above, porous materials based on carbon, typically conventional carbon black, are most commonly used as supports. Much attention is paid to carbon nanotubes and fullerenes. Thus, it is believed that switching to carbon nanofibers or nanotubes provides a decrease in the catalyst sensitivity to carbon monoxide [59]. A significant problem for carbon supports is their degradation due to oxidation at the cathode [60]. This process is most efficient at the Pt/C interface [23, 61]. It leads to the degradation of the three-phase contract (Fig. 1b) and a decrease in the FC efficiency.

There is an opinion that the use of carbon nanofibers or nanotubes can increase the service life of catalysts [62, 63]. However, this approach does not solve the problem of catalyst degradation. In this context, it is of interest to replace carbon supports with more stable materials, among which oxide systems are particularly worth noting. They can quite easily be obtained in a nanodispersed state. In addition, some oxides exhibit a fairly high electronic conductivity. The choice of the support commonly determines the direction of the reaction. Thus, gold deposited on tin oxide catalyzes the conversion of oxygen to water in accordance with reaction (2); in the case of a support made of carbon black, the formation of hydrogen peroxide is the dominant process [64]. It was found that some other oxides—titania [65], manganese oxide [66], vanadia [67], and some other [68, 69, 70, 71]—also contribute to an increase in the efficiency of process (2).

It was shown that some oxides used as a support contribute to an increase in the efficiency of oxidation of methanol and CO [72, 73, 74, 75]. Thus, it was shown that platinum catalysts supported on titania are highly active in these processes [76, 77, 78, 79, 80]. It is obvious that the conductivity of TiO2 is low. To improve it, titania should be coated with carbon [81]. A more commonly used approach is doping [82]. Thus, it was found that, upon switching from a carbon support to a nanosized Ti0.9Nb0.1O2 material, the activity of the platinum–ruthenium alloy increases [83]. The activity of platinum catalysts supported on sulfur-doped titania was reported [84, 85].

A promising support is tin oxide. The active chemisorption of water on the surface of SnO2 contributes to the electrooxidation of CO [86], methanol, and ethanol [87, 88]. Doping with antimony leads to a few orders of magnitude increase in the conductivity of this oxide [89]. This factor provides an increase in the catalytic activity in the alcohol electrooxidation processes [90, 91, 92, 93]. The catalytic activity of platinum in oxygen reduction and methanol oxidation increases owing to doping with indium [94, 95, 96] and ruthenium [92, 97, 98]. Similar properties are exhibited by catalysts supported on tungsten oxide [99, 100, 101], cerium–zirconium mixed oxides, and sulfonated zirconia [102, 103, 104]. Supports exhibiting not only electronic conductivity, but also proton conductivity, such as tungsten bronzes HxWO3, are even more promising [105]. Finally, of purely theoretical interest is the use of supports based on oxides of some noble metals, particularly ruthenium [106, 107, 108] and iridium [109, 110, 111], which also contribute to CO electrooxidation.

Significantly less attention is paid to the use of supports made of other (nonoxide) materials, which primarily include carbides of transition metals, such as titanium, tungsten, and tantalum [112, 113, 114]. It can be assumed that their surface layers undergo oxidation and, therefore, can act as water chemisorption sites. The resulting layers are apparently the product of incomplete oxidation. For example, in the case of tungsten, oxide WOx exhibiting both electronic and ionic conductivity should be formed. As a consequence, catalysts supported on WC exhibit a high catalytic activity in the electrooxidation of methanol and hydrogen in the presence of CO [115, 116]. To improve the electronic conductivity, some authors mixed tungsten carbide with carbon nanotubes [117, 118]. It was reported that doping with tantalum leads to an increase in the activity of WC [119].


A relatively simple approach for hydrogen production is steam reforming of alcohols, in particular, methanol and ethanol (alcohol steam reforming (ASR)), which has been recently described in [120]:

This process is run at high temperatures and accompanied by methanol decomposition to form CO. Typically, the aim of the researchers is the selection of active catalysts that provide a high methanol conversion at a relatively low temperature and, thereby, a high process selectivity.

The ASR processes are most commonly mediated by copper-based catalysts; in this case, the most important parameter is apparently the degree of dispersion of copper [121, 122]. However, catalysts based on copper nanoparticles gradually undergo sintering, which decreases the catalyst activity. In this respect, catalysts based on noble metals, primarily palladium [123, 124], rhodium [125], and ruthenium [126, 127, 128], are much more stable. In addition, they are highly active. However, the dominant reaction on copper is the single-site adsorption of alcohols through oxygen, whereas on the surface of group 8 metals, alcohols are sorbed simultaneously through oxygen and carbon atoms. In this case, the existing carbon–carbon and carbon–hydrogen bonds are broken much more readily and the contribution from alcohol decomposition accompanied by the formation of CO is much more significant [129]. As in the case of FCs, the activity and selectivity of the catalysts can be increased by switching to bimetallic alloys [129, 130].

Supports that are most commonly used for ASR catalysts are prepared of alumina, zinc oxide, and silica. Transition metal oxides are used less commonly. Various nanostructured forms of oxides, such as mesoporous silicas [131, 132] and mesoporous titania [133, 134, 135], are frequently used. There is an opinion that catalyst activity significantly depends on the degree of dispersion of the support [136, 137]; in particular, it is believed that the use of fine supports hinders the agglomeration of metal nanoparticles [138, 139]. In recent years, fine mixed oxides have been increasingly used. For example, the use of catalysts supported on layered magnesium–aluminum hydroxide provides a high conversion and selectivity [140].

In the case of ethanol reforming, a significant problem is catalyst coking, which leads to the blocking of the catalytic sites and a loss of activity. This problem can be overcome by selecting the support. Thus, satisfactory results are obtained in the case of using ceria [141, 142]. The assumption that the presence of mobile oxygen contributes to the occurrence of reforming is confirmed by studies of catalysts supported on various forms of zirconia. Methanol reforming occurs most intensively in the presence of catalysts based on a cubic modification of ZrO2, which is characterized by high oxygen mobility. Catalyst activity also increases upon switching from ZrO2 to YxZr1 – xO2 – (x/2), LaxZr1 – xO2 – (x/2), and CexZr1 – xO2 – δ [129, 143]. The substitution of a portion of zirconium contributes to the formation of a highly symmetric cubic modification of zirconia with high oxygen mobility. In addition, the introduction of cerium provides the intrinsic activity of the catalyst in the redox conversion of alcohols.

Another fairly interesting solution is the use of some specific carbon supports, such as carbon black, graphene, nanotubes, and detonation nanodiamonds [144, 145, 146, 147]. Catalysts supported on these materials are less prone to coking. This feature is apparently attributed to the fact that, in this case, carbon is formed only on the support surface or is not formed at all. Among various carbon materials, the best results are provided by the use of detonation nanodiamonds, the surface of which comprises the largest number of oxygen-containing functional groups. Using IR spectroscopy, it was shown that it is these groups that are responsible for the sorption of water; in addition, they are involved in the sorption of alcohols; this feature provides the intrinsic catalytic activity of detonation nanodiamonds [148, 149].

Comparison of the above results shows that the choice of the metal determines the selectivity of ASR processes; the nature of the support has a significant effect on the catalyst activity. This finding indicates a bifunctional mechanism of ASR processes, in which alcohol sorption occurs on the metal particles, while water is sorbed on the support surface. Therefore, the ASR process takes place exclusively at the interfaces of these phases (Fig. 2) [129].

Fig. 2.

Schematized methanol steam reforming on the catalyst surface [128].

The highest efficiency of ASR can be achieved by implementing the process in a membrane reactor. The use of membranes based on palladium alloys provides the production of high-purity hydrogen and an increase in the yield of this product owing to a shift of the thermodynamic equilibrium [130, 146, 150, 151].


Hydrogen power engineering is thought of as a promising component of future power engineering, primarily for uninterruptible power systems, vehicle power supply systems, and remote area power supply systems. Components of hydrogen power engineering are FCs and devices for hydrogen production from both water and other materials, for example, bioalcohols. Interfaces play an important role in providing an efficient operation of all these devices. The dissociation of functional groups localized on the membrane pore walls is responsible for a high current carrier concentration. The formation of an electrical double layer determines the occurrence of proton transfer in the vicinity of these walls. Conversely, the nonspecific transfer of anions, gases, and low-polarity molecules, particularly alcohols, mostly occurs through the electrically neutral solution localized in the center of the pores. The displacement of this solution owing to the incorporation of nanoparticles into the pores can lead to the suppression of methanol and gas crossover and an increase in the FC efficiency.

Catalysts used in FCs are based on platinum. In this case, electrocatalytic reactions occur at the three-phase interfaces (metal/support/ion-conducting polymer). Carbon used as a support undergoes degradation owing to oxidation at the interface with platinum. In this context, close attention is paid to more stable supports—primarily those exhibiting electronic conductivity—based on various oxides and carbides.

The most effective method to produce hydrogen from alcohols is steam reforming. Catalysts for this process are typically represented by a combination of a metal and an oxide or carbon support. In this case, both the efficiency and selectivity of the process significantly depend on the nature of the two components. This feature is attributed to the bifunctional mechanism of the catalytic process owing to the simultaneous sorption of alcohols and water at the metal/support interface.


This work was supported by the Russian Science Foundation, project no. 17-79-30054.



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Copyright information

© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  1. 1.Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of SciencesMoscowRussia
  2. 2.Institute of Problems of Chemical Physics, Russian Academy of SciencesChernogolovkaRussia
  3. 3.Higher School of Economics (National Research University)MoscowRussia

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