The case for better catalysts is straightforward. Water electrolysers split water into hydrogen and oxygen through two paired reactions: the hydrogen evolution reaction at the cathode and the oxygen evolution reaction at the anode. Platinum-based catalysts perform these transformations with exceptional efficiency, but their cost and scarcity limit any realistic path to large-scale deployment. Earlier alternatives built from metal oxides, sulfides, and nitrides brought their own problems, including toxicity and limited stability. That gap has pushed researchers toward organic polymer semiconductors whose delocalized pi-conjugated systems allow rapid charge transfer while remaining cheap, lightweight, and chemically robust.

What makes polymers so attractive is molecular-level design freedom. Chemists can tune pore structures, graft functional groups, and position active sites with a precision that is nearly impossible in conventional inorganic catalysts. The review catalogues the major classes now under investigation: polymers of intrinsic microporosity, hypercrosslinked polymers, conjugated microporous polymers, covalent organic frameworks, covalent triazine frameworks, and porous aromatic frameworks. Built from light elements joined by strong covalent bonds, these materials combine high specific surface areas with tunable pore architectures and, critically, long-term chemical stability in harsh electrolytic environments.

Covalent organic frameworks, or COFs, are the crystalline stars of this lineup. Their periodically ordered channels and predictable active-site distributions make them ideal platforms for hydrogen evolution. The most common preparation route is solvothermal synthesis, in which boronic acid or catechol derivatives condense in mixed solvents at around 120 degrees Celsius over several days, often with metalloporphyrin or bipyridine units incorporated as catalytic centers. A standout example is TpPAM, a metal-free porphyrin-based covalent organic polymer made by Schiff base condensation. It achieved a Faradaic efficiency of 98 percent and retained 91 percent of its initial current density after 1000 catalytic cycles—remarkable numbers for a catalyst containing no metal at all.

Alternative synthetic routes expand the toolbox further. Ionothermal synthesis, using molten zinc chloride as both solvent and catalyst at 400 to 600 degrees Celsius, produces highly stable triazine-based frameworks with strong hydrogen evolution activity. Mechanochemical ball milling offers a solvent-free route in under an hour, though at the cost of lower crystallinity. For conjugated microporous polymers, palladium-catalyzed Sonogashira-Hagihara coupling yields networks with pore sizes from 0.5 to 2 nanometers and surface areas up to 1000 square meters per gram, while Suzuki and Yamamoto couplings provide routes to heteroatom-doped, highly conjugated networks with excellent charge transport.

The classic conducting polymers—polyaniline, polypyrrole, and polythiophene—have also been revived for catalysis. Electrochemical polymerization can grow these films directly onto electrodes such as glassy carbon or carbon cloth, giving precise control over thickness and morphology, while chemical oxidative polymerization produces powders that can be coated onto electrode surfaces. Doping with nitrogen or sulfur during synthesis significantly boosts catalytic activity. Perhaps most impressive are the donor-acceptor polymers, whose alternating electron-rich and electron-poor units drive efficient intramolecular charge transfer, and which can be post-metalated with earth-abundant cobalt, nickel, or iron to introduce catalytic metal centers.

Metal-containing polymers are where performance numbers get dramatic. A bimetallic cobalt and nickel porphyrin two-dimensional polymer, synthesized by condensing metallated octahydroxyporphyrin with fumaric acid, delivered an overpotential of just 105 millivolts at 10 milliamperes per square centimeter, a Tafel slope of 74.1 millivolts per decade, and 97 percent Faradaic efficiency. The researchers attributed this to a polar porous structure that gives protons easy access to active sites, with nickel incorporation improving conductivity and lowering adsorption energy barriers. Even better, an imidazole-based porous organic polymer loaded with platinum nanoparticles of roughly 2.28 nanometers reached an overpotential of only 56 millivolts and stayed stable for 4000 cycles, because the polymer scaffold prevented the nanoparticles from clumping and aided electron transfer through pi-pi interactions.

The review also emphasizes that polymers can do far more than serve as catalysts in their own right. They can act as conductive supports, fixing agents, adsorption sites for reaction intermediates, proton trapping agents, hydrophilic surface modifiers, porous scaffolds, and even templates for synthesizing other catalysts. An efficient hydrogen evolution catalyst needs a large specific surface area, minimal overpotential, high exchange current density, and durability—and the review argues that conductive polymers, despite rigorous evaluation of their properties, remain underappreciated in the hydrogen evolution field relative to their potential.

Significant obstacles remain before polymer catalysts can graduate from laboratory glassware to industrial electrolyzers. Most high-performing systems still lean on platinum or ruthenium as active centers, undermining the cost argument. The relationship between polymer structure and active site density is poorly mapped, and the mechanistic link between porosity, conjugation length, heteroatom doping, and performance remains incompletely understood. Performance demonstrated on small three-electrode cells rarely survives translation to the high current densities, scalable electrode fabrication, and acidic or alkaline abuse of commercial membrane electrode assembly electrolyzers.

The path forward, according to the review, lies in designing donor-acceptor polymers to sharpen intramolecular charge transfer, engineering porosity and substituents to expose more active sites, and compositing polymers with carbon nanotubes, graphene, or carbon cloth to boost conductivity. Crosslinking and protective carbon coatings could extend durability, while in situ Raman, X-ray photoelectron, and X-ray absorption spectroscopies combined with density functional theory can reveal how hydrogen intermediates bind and how active sites evolve under operating conditions. If those strategies succeed, polymer cathodes could deliver the low-cost, durable hydrogen production that global carbon neutrality goals demand—and the same design principles may ripple outward into carbon dioxide, oxygen, and nitrate reduction catalysis.

Subject of Research: Polymer-based electrocatalysts for the hydrogen evolution reaction in water splitting

Article Title: Research progress on polymer electrochemical hydrogen evolution

Article References: Emin, A. (2026). Research progress on polymer electrochemical hydrogen evolution. Frontiers in Membrane Science and Technology, 5, Article 1823653. https://doi.org/10.3389/frmst.2026.1823653

Image Credits: AI Generated

DOI: 10.3389/frmst.2026.1823653

Keywords: hydrogen evolution reaction, electrocatalysis, covalent organic frameworks, conjugated polymers, water splitting, green hydrogen, porous organic polymers, donor-acceptor polymers, platinum-free catalysts, renewable energy, Faradaic efficiency, overpotential