Advancing hydrogen energy through enzyme-mimetic electrocatalysis

The global transition to a hydrogen-based clean energy economy faces a critical bottleneck: current proton exchange membrane (PEM) fuel cells and water electrolyzers rely almost exclusively on scarce platinum group metals (PGMs) like platinum and iridium oxide. With platinum reserves accounting for only 5% of gold reserves worldwide, this dependency presents a major barrier to large-scale deployment. Nature, however, offers a compelling solution. Over billions of years, evolution has engineered highly efficient enzymes using only earth-abundant elements to manage energy metabolism. These biological catalysts achieve maximum metal atom utilization—where every atom participates in catalysis—unlike conventional nanoparticles where only surface atoms are active. They also demonstrate exceptional activity and operate in aqueous environments under mild conditions. Columbia University and Tsinghua University researchers argue that translating these enzyme design principles into synthetic electrocatalysts could revolutionize hydrogen energy technologies.

The perspective article advocates for a functional approach to enzyme mimicry—replicating catalytic behavior rather than precisely copying structural architecture. By selectively integrating nature's design principles with synthetic chemistry and advanced materials science, the researchers outline strategies for developing high-performance, economically viable electrocatalysts. The study systematically examines key hydrogen energy reactions: the hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR), and oxygen evolution reaction (OER). For each reaction, the team analyzes natural enzymatic active sites—from the iron-sulfur clusters of hydrogenases to the manganese-calcium clusters of photosystem II—and demonstrates how their core principles can be adapted for harsh technological conditions. The research emphasizes that successful translation requires re-engineering entire systems, including polymer electrolytes and electrode architectures, rather than simply substituting catalyst materials.

The review highlights several breakthrough achievements in functional enzyme mimicry:

• Reversible Hydrogen Catalysis: Nickel complexes incorporating amine proton relays from [FeFe]-hydrogenase active sites demonstrated reversible HER/HOR behavior near thermodynamic equilibrium potential (0V vs. RHE) in acidic conditions—previously exclusive to platinum. When supported on conductive carbon and structured in three-dimensional electrodes, these PGM-free catalysts achieved performance comparable to commercial Pt/C and were successfully integrated into the first completely PGM-free hydrogen fuel cell.
• Oxygen Reduction Advances: Metal-nitrogen-doped carbon (M-N-C) materials were found to preserve porphyrin motifs (MN₄ moieties) even after pyrolysis at 1000°C, serving as highly stable active sites for the four-electron ORR in acidic PEM environments. Covalently linking cobalt porphyrin arrays to carbon nanotubes significantly improved selectivity for water formation over hydrogen peroxide production.
• Oxygen Evolution Innovation: Synthetic analogs of the natural Mn₄CaOₓ cluster from photosystem II, incorporated into amorphous manganese oxide phases, showed high OER activity under neutral conditions suitable for anion exchange membrane electrolyzers. Co-phosphate materials featuring polynuclear molecular motifs also demonstrated enhanced catalytic performance beyond what surface area alone could provide.
• System-Level Integration: Embedding molecular motifs within conductive carbonaceous matrices was shown to stabilize catalysts in acidic environments and under technologically relevant electrochemical potentials, mirroring how enzymes use protein backbones and iron-sulfur clusters for electron/proton transport.

This functional enzyme-mimetic approach provides a clear pathway to overcome the critical material scarcity crisis limiting hydrogen technology scale-up. By demonstrating how earth-abundant elements can achieve platinum-like performance, the research opens the door to cost-effective, sustainable fuel cells and electrolyzers essential for grid-scale energy storage and heavy-duty transportation. The perspective shifts the field from trial-and-error material screening to rational design based on billions of years of evolutionary optimization. It also emphasizes that realizing these benefits requires holistic system innovation—developing new polymer electrolytes, electrode architectures, and interpenetrating transport networks tailored specifically for enzyme-mimetic catalysts. As the hydrogen economy accelerates globally, these advances could fundamentally transform energy conversion efficiency while ensuring resource sustainability.

JOURNAL: Frontiers in Energy

DOI: 10.1007/s11708-025-0975-7

ARTICLE TITLE: Advancing hydrogen energy through enzyme-mimetic electrocatalysis

Article Link: https://doi.org/10.1007/s11708-025-0975-7