Heterogeneous Electrocatalysis

Note: This post introduces heterogeneous electrocatalysis — the problem setting that motivates large-scale catalyst design efforts like the Open Catalyst project. The first half follows Zitnick et al. (2020), which covers the energy storage problem, the Sabatier principle, and the idealized metal-surface picture. The second half draws on Tran et al. (2023) and Shuaibi et al. (2025) to explain why real catalysts — oxides, disordered materials, surfaces in liquid — are far more complex. I wrote this as a bridge between my previous posts on DFT and equivariant GNNs, and the application domain where these methods have the most impact. Corrections are welcome.

Introduction

The design problem is to find a catalyst¹ material that achieves a target adsorption energy² for a given chemical reaction.

This matters because the Sabatier principle says the best catalyst binds intermediates³ at a specific strength: not too strongly, not too weakly. Scaling relations reduce the problem further. In many reaction families, one number, the adsorption energy of a key intermediate, largely determines catalyst performance. Theory identifies the optimal value; the open question is which material achieves it.

The search space is enormous. Catalyst surfaces are built from ~40 candidate metals in alloys of 1–3 elements, cut along different crystal facets,⁴ with multiple binding sites⁵ per surface. Combined with 82 relevant adsorbate⁶ molecules, the number of candidate configurations runs into the billions. Evaluating each one requires a DFT relaxation⁷ — an iterative quantum-mechanical simulation costing hours to days per candidate. Exhaustive evaluation is infeasible.

This is a natural ML problem: learn a surrogate that maps material structure to adsorption energy, then search or generate candidates that hit the target. The rest of this post explains where the target comes from, why the search space has this structure, and why the problem matters scientifically.

The Energy Storage Problem

Renewable electricity from solar and wind is intermittent. Solar output peaks at midday, while demand often peaks in the evening, creating the mismatch known as the duck curve.⁸ Grid-scale energy storage is the missing piece for full renewable adoption.

California hourly energy demand. The green area shows wind and solar generation peaking midday while total demand (black) peaks in the evening — the 'duck curve.' The gap must be filled by other sources or storage. Adapted from Zitnick et al. (2020).

Several storage technologies exist, each with trade-offs:

Pumped-storage hydropower (PSH): 70–80% round-trip efficiency, but requires specific geography (two reservoirs at different elevations). Already accounts for 95% of grid storage worldwide — and most good sites are taken.
Batteries: 60–95% round-trip efficiency, but cost-prohibitive at the scale needed for multi-day or seasonal storage. Lithium-ion costs have fallen dramatically, yet storing a full day of U.S. electricity demand (~11 TWh) in batteries remains economically impractical.
Hydrogen energy storage (HES): Use excess electricity to split water (electrolysis),⁹ store the hydrogen, and convert it back to electricity in a fuel cell¹⁰ when needed. Round-trip efficiency is lower (~35%), but hydrogen can be stored in bulk at low cost — underground caverns, pressurized tanks, or converted to methane for existing natural gas infrastructure.

The efficiency gap is real: HES wastes roughly two-thirds of the input energy.¹¹ But efficiency is not the only constraint. At grid scale, the relevant quantity is the total cost of stored energy. Zitnick et al. (2020) estimate HES at $113/MWh, competitive with batteries for multi-day storage because cheap bulk hydrogen storage can offset the efficiency loss.

The bottleneck is not storage capacity. It is the catalyst. Both the electrolyzer (splitting water) and the fuel cell (recombining hydrogen with oxygen) require electrocatalysts¹² to drive their reactions at practical rates. The dominant catalyst is platinum, which is scarce and expensive. Reducing or replacing platinum is the key to making HES economically viable.

The hydrogen energy storage cycle. Renewable electricity powers an electrolyzer that splits water into hydrogen. The hydrogen can be stored directly or converted to methane via methanation with captured CO2. Fuel cells convert stored fuel back to electricity for the grid. Adapted from Zitnick et al. (2020).

Fuel Cells and Electrolyzers

The previous section identified catalysts as the bottleneck for hydrogen energy storage. The catalysis occurs inside two devices: the electrolyzer, which converts electricity into hydrogen, and the fuel cell, which converts hydrogen back into electricity. Their internal structure reveals the specific reactions a catalyst must accelerate, and why those reactions are hard.

A proton exchange membrane (PEM) fuel cell converts hydrogen and oxygen into electricity and water. It has three layers:

Anode:¹³ Hydrogen gas arrives and is split into protons and electrons: $\text{H}_2 \rightarrow 2\text{H}^+ + 2e^-$.
Membrane: A polymer electrolyte¹⁴ that conducts protons (H$^+$) but blocks electrons, forcing them through an external circuit — producing useful electrical current.
Cathode: Oxygen combines with the protons and electrons to form water: $\tfrac{1}{2}\text{O}_2 + 2\text{H}^+ + 2e^- \rightarrow \text{H}_2\text{O}$.

An electrolyzer runs the same reactions in reverse: apply a voltage to split water into hydrogen and oxygen. Both devices need a catalyst at each electrode¹⁵ to make the reactions proceed fast enough to be practical.

Schematic of a PEM fuel cell. Hydrogen enters at the anode (left, red), is split into protons and electrons. Protons pass through the membrane (gold center), electrons flow through an external circuit (top) to power a load. At the cathode (right, blue), oxygen combines with protons and electrons to form water. Adapted from Zitnick et al. (2020).

The Platinum Problem

Platinum is the best-known catalyst for both the hydrogen oxidation reaction at the anode and the oxygen reduction reaction¹⁶ at the cathode. It sits near the peak of the activity volcano, explained below: it binds reactants strongly enough to catalyze the reaction, but weakly enough to release products.

The problem is cost and scarcity:

Platinum accounts for over 40% of fuel cell capital costs when including the support structures needed for adequate power density (Zitnick et al., 2020).
To supply 35 TWh/day of electricity via HES would require ~2,000 metric tons of platinum. Known world reserves are ~70,000 metric tons.¹⁷
A survey of automotive fuel cell experts found that 76% identified platinum cost as the primary barrier to reducing fuel cell costs.

Research suggests a 90% reduction in platinum loading may be achievable, and platinum-free catalysts are an active research area. Finding them requires searching an enormous materials space, where each candidate is expensive to evaluate.

Electrocatalysis

Heterogeneous catalysis¹⁸ involves a reaction between a solid surface, the catalyst, and gas- or liquid-phase reactants. The catalyst is not consumed; it provides a surface where reactants can adsorb,¹⁹ react, and desorb as products.

Potential energy as a function of distance between an adsorbate and a surface. Physisorption (gold) is a weak van der Waals attraction. Chemisorption (blue) involves forming a chemical bond — the deeper well corresponds to the adsorption energy that determines catalytic activity. Adapted from Zitnick et al. (2020).

The Oxygen Reduction Reaction

The cathode reaction in a fuel cell, the oxygen reduction reaction (ORR), is the harder half to catalyze and the primary target for improvement. Consider the dissociative pathway²⁰ on a metal surface, where $*$ denotes a binding site on the catalyst:

\[\tfrac{1}{2}\text{O}_2 + * \;\longrightarrow\; *\text{O}\] \[*\text{O} + \text{H}^+ + e^- \;\longrightarrow\; *\text{OH}\] \[*\text{OH} + \text{H}^+ + e^- \;\longrightarrow\; \text{H}_2\text{O} + *\]

Each step involves an adsorbate ($*$O or $*$OH) bound to the catalyst surface. The reaction proceeds through these intermediate states, and the catalyst is regenerated at the end — the binding site $*$ is freed.

Gibbs Free Energy and Reaction Barriers

Each step has a Gibbs free energy change $\Delta G$, which determines whether the step is thermodynamically favorable ($\Delta G < 0$) or requires energy input ($\Delta G > 0$). Gibbs free energy is:

\[G = H - TS\]

where $H$ is enthalpy,²¹ $T$ is temperature, and $S$ is entropy.²²

A catalyst works by lowering the activation energy²³ barriers between steps — not by changing the overall thermodynamics (the total $\Delta G$ from reactants to products is fixed), but by providing an alternative pathway with lower barriers.

Energy diagram for a single reaction step: O2 dissociating on a surface. The activation energy (0.62 eV) is the barrier the system must overcome. The reaction free energy (−1.5 eV) is the net energy change. A catalyst lowers the activation energy without changing the net free energy. Adapted from Zitnick et al. (2020).

The key screening quantity is the adsorption energy: how strongly each intermediate binds to the surface. If binding is too strong, the intermediate cannot desorb and the catalyst is “poisoned.” If binding is too weak, the intermediate never forms.

Gibbs free energy diagram for the dissociative ORR pathway on Pt(111) (blue) and Ni(111) (green). Pt has moderate energy barriers at each step — close to ideal. Ni binds oxygen too strongly: the initial steps drop much further, but the activation barriers between steps are correspondingly larger. Adapted from Zitnick et al. (2020).

The Sabatier Principle

The Sabatier principle. The optimal catalyst binds reaction intermediates neither too strongly nor too weakly. Too strong, and products cannot desorb. Too weak, and reactants cannot adsorb. Maximum activity occurs at an intermediate binding strength.

This qualitative principle becomes quantitative through the Brønsted-Evans-Polanyi (BEP) relations: across a family of catalysts, the activation energy $E_a$ for a given elementary step is linearly related to the reaction energy $\Delta E$:

\[E_a = \alpha \, \Delta E + \beta\]

where $\alpha$ and $\beta$ are constants specific to the reaction step.²⁴ The reaction rate follows the Arrhenius equation:²⁵

\[r \propto \exp\!\left(-\frac{E_a}{k_B T}\right)\]

Combining these: as adsorption energy becomes more negative (stronger binding), $E_a$ decreases for adsorption steps but increases for desorption steps. The overall rate is limited by the slowest step. On the strong-binding side, desorption is rate-limiting — the rate decreases as binding strengthens. On the weak-binding side, adsorption is rate-limiting — the rate decreases as binding weakens. The result is a volcano plot: reaction rate versus adsorption energy traces an inverted-V shape, with the optimum at the peak.

Volcano plot for the ORR. Catalytic activity (log scale) vs. oxygen adsorption energy. Platinum and palladium sit near the peak. Metals to the left (Fe, W, Ni) bind too strongly; metals to the right (Ag, Au) bind too weakly. The two branches correspond to different rate-limiting steps. Adapted from Nørskov et al. (2004), as presented in Zitnick et al. (2020).

The volcano plot is the central organizing principle of electrocatalysis. It reduces catalyst discovery to a one-dimensional search: find a material whose adsorption energy places it at the volcano peak. Theory gives the optimal value; materials discovery asks which structure achieves it.

Scaling Relations and the Search Space

Why One Binding Energy Suffices

The ORR involves multiple intermediates ($*$O, $*$OH, $*$OOH), each with its own binding energy. In principle, optimizing the catalyst requires tuning all of them independently. In practice, they are correlated.

The $*$OH and $*$OOH binding energies are linearly correlated across all known catalysts, with a constant offset of ~3.2 eV:

\[\Delta G_{*\text{OOH}} \approx \Delta G_{*\text{OH}} + 3.2 \;\text{eV}\]

This scaling relation arises because both $*$OH and $*$OOH bond to the surface through oxygen, so the catalyst surface “sees” similar binding chemistry. The hydrogen atoms point away and contribute little to the interaction.

The consequence is that a single descriptor, such as $\Delta G_{*\text{OH}}$, determines a catalyst’s position on the volcano. This makes screening tractable despite the high-dimensional space of possible materials.

2D volcano plot showing catalytic activity (color, red = highest) as a function of OH and OOH binding free energies. The dashed red line is the scaling relation — all known catalysts (dots) cluster along it. The activity peak (red region) sits slightly off the line, meaning the scaling relation itself limits achievable performance. Pt(111) is labeled near the peak. Adapted from Zitnick et al. (2020).

The Constraint — and the Open Challenge

The scaling relation is both a gift and a curse. It simplifies the search to one dimension, but also imposes a fundamental limit: because known catalysts lie on or near the scaling line, they share the same trade-off. The ideal catalyst would bind $*$OH at the volcano peak while also binding $*$OOH at its independently optimal value, which requires breaking the scaling relation. Strategies include nanostructured surfaces, alloys with specific local environments, and single-atom catalysts, but none has definitively broken the linear scaling.

The Design Space

Even with the simplification to a single descriptor, the space of candidate catalyst configurations is vast:

~40 metals can appear in a catalyst, in combinations of 1–3 elements (yielding over 10,000 compositions before considering ratios).
Each composition can be cut along multiple crystal facets — (100), (110), (111), and others — exposing different surface arrangements.
Each surface has multiple binding sites: an adsorbate can bond to 1 atom (atop), 2 atoms (bridge), or 3 atoms (hollow).
82 adsorbate molecules are relevant intermediates of reactions important for renewable energy.

3D rendering of a catalyst surface with adsorbate molecules (red and white atoms) bound at different sites on a close-packed metal surface (gray). The adsorbates are small compared to the surface — their binding energy depends on the local arrangement of surface atoms. Adapted from Zitnick et al. (2020).

Types of catalyst materials in the OC20 search space. From left: pure metal, multi-metallic alloy, intermetallic compound (ordered), overlayer (thin film on bulk), and high-entropy alloy (5+ elements, disordered). Each type has different surface chemistry. Adapted from Zitnick et al. (2020).

Crystal facets exposed by cutting along different planes (Miller indices). Top: the (100), (110), and (111) cutting planes through a cubic unit cell. Bottom: the resulting surface arrangements — (111) is the most densely packed. Different facets expose different binding site geometries. Adapted from Zitnick et al. (2020).

The 82 adsorbate molecules in the OC20 dataset, grouped by composition: O and H (top), small molecules with one carbon (C1), larger molecules with two or more carbons (C2), and nitrogen-containing molecules (N). These are intermediates of reactions relevant to renewable energy storage. Adapted from Zitnick et al. (2020).

Combining these factors gives on the order of 1,000 candidate configurations per catalyst composition, and billions of total (composition, facet, site, adsorbate) combinations. Each evaluation requires a DFT relaxation, an $O(n^3)$ iterative simulation that takes hours to days. This is the search problem that motivates ML approaches to catalyst design.

Why Oxides Matter

The previous sections focused on the fuel-cell cathode (ORR) and used pure metals, especially platinum, as running examples. The other half of the hydrogen energy cycle is water splitting, where the bottleneck is a different reaction: the oxygen evolution reaction (OER).²⁶

\[2\text{H}_2\text{O} \;\longrightarrow\; \text{O}_2 + 4\text{H}^+ + 4e^-\]

The OER is kinetically sluggish because it forms an O–O bond through four proton-coupled electron transfers, each with its own energy barrier. It is the primary source of efficiency loss in electrolyzers and the main target for catalyst improvement on the water-splitting side.

Metal oxides are the dominant catalyst class for the OER. The reason is stability: in PEM electrolyzers, water splitting operates under strongly acidic conditions with a proton-conducting membrane. Under these conditions, most pure metals dissolve. Oxides survive. The best-known stable and active OER catalyst is iridium oxide (IrO$_2$) — but iridium is rarer and more expensive than platinum (Tran et al., 2023). Finding cheaper multi-component oxide catalysts that match IrO$_2$ in both activity and acid stability is a central goal of electrocatalysis research.

The OER catalyst discovery workflow. (a) Select a bulk oxide structure. (b) Enumerate surface terminations and identify the most stable one via surface Pourbaix diagrams. (c) Place adsorbate intermediates. (d) Relax the structure and compute adsorption energy. Steps (a)–(b) are unique to oxides — on metals, the surface is determined by the facet alone. Adapted from Tran et al. (2023).

Why Oxides Are Harder Than Metals

Oxide electrocatalysts introduce at least five layers of complexity absent from pure metal surfaces (Tran et al., 2023):

Multiple polymorphs. A given oxide composition (e.g., TiO$_2$) can crystallize in several distinct structures (rutile, anatase, brookite), each with different surface chemistry. All must be screened.
Surface terminations. Cutting a crystal along a given plane can expose different atomic layers. A rutile (110) surface has at least three possible terminations,²⁷ each presenting different atoms to the adsorbate. On metals, the facet determines the surface; on oxides, the termination adds another degree of freedom.
Oxygen vacancies. Surface oxygen atoms can be removed — by thermal treatment, electrochemical reduction, or solvent dissolution — leaving behind vacancy defects that serve as active sites. The number and arrangement of vacancies affects both activity and selectivity.
Active site ambiguity. It is often unclear which surface site is catalytically active, and multiple competing reaction mechanisms may operate simultaneously.
Stronger electron correlation. Standard DFT functionals (GGA) are less accurate for oxides because of strong electron–electron interactions in transition metal d-orbitals. Hubbard U corrections²⁸ or more expensive hybrid functionals are needed.

Surface terminations of rutile (110). (a) Three possible terminations (T1, T2, T3) obtained by cutting at different depths. The dashed blue box marks the surface unit cell. (b) Labeled surface oxygen sites — removing any subset of these creates vacancy defects, each configuration with different catalytic properties. Adapted from Tran et al. (2023).

Adsorbate Binding on Oxides

On a metal surface, adsorbates bind to metal atoms at well-defined sites (atop, bridge, hollow). Oxides add a second class of binding interactions: adsorbates can bind to surface oxygen atoms rather than to metal atoms. This enables reactions that have no analogue on metals.

The Mars-van Krevelen (MvK) mechanism²⁹ is the most important example. In MvK, an incoming adsorbate reacts with a lattice oxygen atom on the surface, forming a new intermediate that desorbs and leaves behind an oxygen vacancy. The vacancy is later replenished by oxygen from the next adsorbate. The catalyst surface itself participates as a reactant, cycling between oxidized and reduced states.

Adsorbate placement strategies on oxide surfaces. Top row: adsorbates bind to undercoordinated surface metals at lattice oxygen positions (including vacancy sites). Bottom row: adsorbates bind to existing surface oxygen to form new intermediates — e.g., CO on surface O forms CO2, monatomic O on surface O forms a dimer. This second class of binding is unique to oxides. Adapted from Tran et al. (2023).

Beyond Ideal Surfaces

The picture so far, with volcano plots, scaling relations, and well-defined crystal facets, applies to idealized single-crystal surfaces in vacuum. Real electrocatalysts operate under conditions that break these simplifications.

The Solid-Liquid Interface

Real electrocatalysis happens in liquid, not vacuum. The catalyst surface is immersed in an electrolyte, typically water with dissolved ions. This changes the physics in ways gas-phase models cannot capture (Shuaibi et al., 2025):

Solvent stabilization. Water molecules form hydrogen bonds with adsorbed intermediates, shifting their binding energies. An intermediate that binds too weakly in vacuum may be stabilized enough by the solvent to become catalytically relevant.
The electrical double layer. At an electrified interface, ions in the electrolyte rearrange to screen the surface charge, forming a structured layer whose properties govern charge transfer kinetics. The structure of this double layer depends on applied potential, ion concentration, and solvent identity.
Specific ion adsorption. Ions from the electrolyte can adsorb directly on the catalyst surface, blocking active sites or modifying the local electronic environment.

The solvation energy captures these effects: it is the difference between a species’ adsorption energy in the solvated environment and in vacuum. A catalyst that looks optimal in gas-phase DFT may perform differently once solvent shifts binding energies by tenths of an eV, comparable to the width of the volcano peak.

The OC25 dataset models catalysis at solid-liquid interfaces: catalyst surfaces with explicit solvent molecules and ions, spanning 88 elements and multiple solvent types. Adapted from Shuaibi et al. (2025).

Compositional Complexity

The design space grows dramatically beyond pure metals and binary alloys.

Heteroatom doping. Introducing foreign atoms — nitrogen, sulfur, phosphorus, boron — into a host material modifies the electronic structure of nearby active sites. Nitrogen-doped carbon catalysts are a well-known example. Dopant concentration, spatial distribution, and the specific coordination environment all affect activity. Even for a single host material, this creates a large combinatorial space.

High-entropy materials. These contain five or more principal elements in near-equimolar ratios, as in high-entropy alloys (HEAs) or high-entropy oxides. The vast configurational space produces local electronic environments not achievable in simpler compositions. Properties emerge from collective interactions among elements (the “cocktail effect”), not from individual elemental contributions. This makes decomposition-based reasoning, such as “element A contributes property X,” unreliable.

Structural Disorder and Dynamic Surfaces

Many high-performing electrocatalysts lack long-range crystalline order. Amorphous metal oxides and hydroxides used for oxygen evolution have no single repeating unit cell. Instead, they present a distribution of local coordination environments, each with potentially different catalytic activity. Standard DFT assumes periodic boundary conditions and a well-defined slab; modeling amorphous surfaces requires large supercells or ensemble sampling to capture this structural diversity.

The problem is compounded by surface reconstruction under operating conditions. Atoms migrate, oxidation states change, and the electrochemically active phase may differ from the as-synthesized material. Oxide surfaces are particularly prone to reconstruction: partial dissolution by the solvent creates vacancy defects, and applied potential can rearrange the surface. The structure being modeled is not necessarily the structure that catalyzes.

Oxides also exhibit magnetic polymorphism — the same crystal structure can have different magnetic configurations (ferromagnetic, antiferromagnetic, nonmagnetic), each with different surface energies and adsorption properties (Tran et al., 2023). In semiconducting oxides, a further complication arises from charge self-compensation: when vacancies or dopants perturb the electron count, the surface can thermodynamically prefer to reconstruct — breaking or forming bonds — rather than promote electrons into the conduction band. This means a vacancy on one side of a slab can trigger geometric rearrangement on the other side, an effect that is long-ranged and difficult to capture with local models.

Scaling Relations on Complex Materials

The linear scaling relations that simplify catalyst screening on metals (the $\Delta G_{*\text{OOH}} \approx \Delta G_{*\text{OH}} + 3.2 \;\text{eV}$ relation from the Scaling Relations section) were established on close-packed metal surfaces with uniform binding sites. On oxide surfaces with diverse site types, the picture is noisier.

Scaling relations on oxide surfaces. (A) OOH* vs OH* binding energies. (B) O* vs OH* binding energies. Red points: OC22 dataset (oxides). Blue points: literature values. The linear correlations still exist but with larger scatter (R² ≈ 0.6–0.8) and higher MAE compared to metals. On materials with diverse site types — high-entropy alloys, doped carbons, amorphous oxides — the correlations weaken further. Adapted from Tran et al. (2023).

Tran et al. (2023) find that the linear correlations persist on oxides, with slopes within 0.15 eV of literature values for metals, but with substantially more scatter (R$^2$ ≈ 0.6 for $*$OOH vs. $*$OH, compared to >0.9 on metals). The increased scatter makes the one-dimensional volcano picture less predictive: two oxides with similar $\Delta G_{*\text{OH}}$ can have meaningfully different $\Delta G_{*\text{OOH}}$ values. On more disordered materials, such as high-entropy alloys and amorphous oxides, the correlations are expected to weaken further, making single-descriptor screening unreliable.

When scaling relations break down, the full multidimensional binding-energy space re-emerges. Each intermediate must be evaluated independently, and the tractable one-dimensional search becomes a high-dimensional optimization problem: precisely the setting where learned surrogates have the most to contribute.

Machine Learning for Catalyst Discovery

The previous sections establish the problem: find a catalyst whose adsorption energy sits at the volcano peak, within a search space of billions of candidates, where each evaluation costs hours of DFT compute. ML makes this search tractable in two ways: surrogate energy models accelerate evaluation, and generative models propose candidates directly.

Surrogate Energy Models

The first generation of ML models for catalysis predicts DFT energies and forces from atomic structure, replacing the expensive quantum-mechanical calculation with a fast forward pass. These machine learning interatomic potentials (MLIPs)³⁰ take an atomic configuration as input and predict total energy plus per-atom forces, enabling structure relaxation at a fraction of the DFT cost.

The key architectural insight is that catalyst systems are inherently three-dimensional and obey physical symmetries: rotating or translating the entire system should not change the predicted energy. This motivates equivariant graph neural networks (covered in a previous post), which build these symmetries into the model architecture rather than learning them from data.

The progression of models on the OC20 benchmark illustrates how architectural advances translate to accuracy gains:

SchNet (Schütt et al., 2018) and DimeNet++ (Gasteiger et al., 2020) established the invariant GNN baseline — message-passing networks that use interatomic distances (and angles, for DimeNet++) as features.
GemNet-OC (Gasteiger et al., 2022) introduced two-hop message passing with dihedral angle information, achieving strong performance on both energy and force prediction.
EquiformerV2 (Liao & Smidt, 2024) combined equivariant Transformers with higher-order spherical harmonics representations, achieving state-of-the-art results on OC20 — energy MAE of 0.21 eV and force MAE of 0.013 eV/Å.

From Prediction to Screening: AdsorbML

A trained MLIP does not directly solve the catalyst design problem — it accelerates a single energy evaluation. The AdsorbML pipeline (Lan et al., 2023) connects the surrogate model to the actual screening workflow:

For a given (surface, adsorbate) pair, generate many candidate initial configurations by random placement.
Relax each configuration using the ML surrogate instead of DFT.
Rank by predicted energy and run DFT only on the top-$k$ lowest-energy candidates to validate.

This reduces DFT cost by orders of magnitude while maintaining high success rates: AdsorbML identifies the correct lowest-energy configuration ~84% of the time on OC20 (Lan et al., 2023). The pipeline has screened thousands of bimetallic alloy surfaces for the hydrogen evolution reaction, with a validated adsorption energy MAE of 0.12 eV across the screened space.

Generative Catalyst Design

Surrogate models accelerate evaluation but still require candidate proposals. The workflow remains enumerate-then-filter: list configurations, predict energies, pick the best. An alternative is to generate promising candidates directly by learning a model that, given a target adsorption energy or reaction intermediate, outputs a catalyst structure likely to achieve it.

This is harder. A catalyst structure is a coupled system: the surface slab, a periodic crystal cut along a specific facet, and the adsorbate, a molecule at a specific position and orientation on that surface. The two are not independent. The adsorbate’s preferred binding site depends on surface geometry, and the surface may reconstruct in response to the adsorbate.

CatFlow (Kim et al., 2026) addresses this coupling through a flow matching framework that co-generates the slab and adsorbate jointly. The key idea is a factorized primitive-cell representation: rather than generating the full slab (which may contain hundreds of atoms in a repeated pattern), CatFlow generates only the primitive cell and encodes the surface orientation explicitly. This reduces the number of learnable variables by ~9x on average while preserving the interface geometry that determines catalytic activity. Generated structures show accurate adsorption energy distributions and sit closer to DFT-relaxed local minima compared to autoregressive and sequential baselines.

Open Challenges

Several gaps remain between current ML capabilities and practical catalyst discovery:

Out-of-distribution generalization. Models trained on OC20 (metals) transfer imperfectly to oxides (OC22) or solvated interfaces (OC25). Fine-tuning helps, but the chemical diversity of real catalyst spaces — high-entropy alloys, amorphous oxides, doped carbons — remains undersampled.
Long-range interactions. Local message-passing GNNs struggle with the long-range electrostatics and magnetic interactions that dominate in semiconducting oxides (see Beyond Ideal Surfaces). Extending effective interaction ranges without prohibitive cost is an active research direction.
Beyond adsorption energy. Current screening pipelines optimize a single thermodynamic descriptor. Real catalyst selection requires stability under operating conditions (Pourbaix analysis), synthesis feasibility, cost, and selectivity — none of which are captured by adsorption energy alone.

References

Zitnick, C. L., Chanussot, L., Das, A., Goyal, S., Heras-Domingo, J., Ho, C., … & Ulissi, Z. W. (2020). An introduction to electrocatalyst design using machine learning for renewable energy storage. arXiv preprint arXiv:2010.09435.
Chanussot, L., Das, A., Goyal, S., Lavril, T., Shuaibi, M., Riviere, M., … & Zitnick, C. L. (2021). Open Catalyst 2020 (OC20) dataset and community challenges. ACS Catalysis, 11(10), 6059-6072.
Nørskov, J. K., Rossmeisl, J., Logadottir, A., Lindqvist, L., Kitchin, J. R., Bligaard, T., & Jónsson, H. (2004). Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B, 108(46), 17886-17892.
Nørskov, J. K., Bligaard, T., Rossmeisl, J., & Christensen, C. H. (2009). Towards the computational design of solid catalysts. Nature Chemistry, 1, 37-46.
Tran, R., Lan, J., Shuaibi, M., Wood, B. M., Goyal, S., Das, A., … & Zitnick, C. L. (2023). The Open Catalyst 2022 (OC22) dataset and challenges for oxide electrocatalysts. ACS Catalysis, 13(5), 3066-3084.
Shuaibi, M., Choubisa, H., Engel, M., Wood, B. M., Musielewicz, J., Comer, B., … & Zitnick, C. L. (2025). Open Catalyst 2025 (OC25): dataset and models for the solid-liquid interface. arXiv preprint arXiv:2509.17862.
Gasteiger, J., Becker, F., & Günnemann, S. (2022). GemNet-OC: developing graph neural networks for large and diverse molecular simulation datasets. Transactions on Machine Learning Research.
Liao, Y.-L., & Smidt, T. (2024). EquiformerV2: improved equivariant Transformer for scaling to higher-degree representations. ICLR 2024.
Lan, J., Palizhati, A., Shuaibi, M., Wood, B. M., Wander, B., Das, A., … & Zitnick, C. L. (2023). AdsorbML: a leap in efficiency for adsorption energy calculations using generalizable machine learning potentials. npj Computational Materials, 9, 172.
Kim, M., Kim, N., Kim, H., & Ahn, S. (2026). CatFlow: co-generation of slab-adsorbate systems via flow matching. arXiv preprint arXiv:2602.05372.

A catalyst is a substance that increases the rate of a chemical reaction without being consumed. It works by lowering the energy barrier (activation energy) that reactants must overcome, providing an alternative reaction pathway. The catalyst participates in intermediate steps but is regenerated at the end. ↩
The adsorption energy (or binding energy) measures how strongly a molecule sticks to a surface. More negative values mean stronger binding. It is computed as the energy difference between the combined system (molecule on surface) and the separated components (clean surface + isolated molecule). ↩
A reaction intermediate is a molecule that is produced in one step of a multi-step reaction and consumed in a subsequent step. It exists transiently on the catalyst surface. For the oxygen reduction reaction, the intermediates are $*$O and $*$OH, where $*$ denotes binding to the surface. ↩
A crystal facet is the flat surface exposed when a crystal is cut along a specific plane. Different cuts expose different arrangements of atoms. Facets are labeled by Miller indices — e.g., (111), (110), (100) — which describe the orientation of the cutting plane relative to the crystal lattice. ↩
A binding site is a specific location on the catalyst surface where an adsorbate molecule can attach. On a close-packed metal surface, common sites include: atop (directly above one atom), bridge (between two atoms), and hollow (in the center of three atoms). Each site type produces a different adsorption energy. ↩
An adsorbate is a molecule or atom that has adhered to a surface. In electrocatalysis, adsorbates are the reaction intermediates sitting on the catalyst surface — for example, an oxygen atom ($*$O) or a hydroxyl group ($*$OH) bonded to a metal surface. ↩
A DFT relaxation (or geometry optimization) is an iterative simulation that finds the lowest-energy arrangement of atoms. Starting from an initial guess, each step computes quantum-mechanical forces on every atom using density functional theory (see previous post), then nudges the atoms downhill. This repeats for 50–400 steps until the forces converge to near zero. ↩
The “duck curve” refers to the shape of net electricity demand (demand minus solar generation) over a day: it dips at midday when solar peaks, then rises sharply in the evening. First identified by the California Independent System Operator (CAISO). ↩
Electrolysis is the process of using electrical energy to drive a non-spontaneous chemical reaction. In water electrolysis, an applied voltage splits water into hydrogen and oxygen: $2\text{H}_2\text{O} \rightarrow 2\text{H}_2 + \text{O}_2$. ↩
A fuel cell is an electrochemical device that converts chemical energy (from a fuel like hydrogen) directly into electrical energy, without combustion. Unlike a battery, it does not store energy internally — it produces electricity continuously as long as fuel is supplied. ↩
Zitnick et al. (2020) estimate HES round-trip efficiency at ~35% (AC to AC), compared to 70–80% for pumped hydro and 60–95% for batteries. The losses occur in both the electrolyzer (~70% efficient) and the fuel cell (~60% efficient): 0.7 × 0.6 ≈ 0.42, minus additional transmission and conversion losses. ↩
An electrocatalyst is a catalyst that operates at an electrode surface in an electrochemical cell. It accelerates reactions involving electron transfer — such as the splitting of water or the reduction of oxygen. The “electro-“ prefix distinguishes it from catalysts for purely thermal or gas-phase reactions. ↩
The anode is the electrode where oxidation occurs (loss of electrons); the cathode is where reduction occurs (gain of electrons). A mnemonic: anode = away (electrons flow away from it). ↩
An electrolyte is a substance that conducts ions but not electrons. In a PEM fuel cell, the polymer membrane serves as the electrolyte — it allows protons (H$^+$) to pass through while forcing electrons to travel through the external circuit. ↩
An electrode is a conductor through which electric current enters or leaves an electrochemical cell. In a fuel cell, the two electrodes are the anode (fuel side) and cathode (oxygen side). ↩
The oxygen reduction reaction (ORR) is the cathode half-reaction in a fuel cell: $\text{O}_2 + 4\text{H}^+ + 4e^- \rightarrow 2\text{H}_2\text{O}$. It is kinetically sluggish — the main source of efficiency loss in fuel cells — and the primary motivation for catalyst research. ↩
As of 2020. South Africa holds approximately 80% of known platinum reserves. ↩
Heterogeneous catalysis means the catalyst and reactants are in different phases — typically a solid catalyst with gas- or liquid-phase reactants. This is in contrast to homogeneous catalysis, where catalyst and reactants are in the same phase (e.g., both dissolved in solution). ↩
Adsorption is the adhesion of atoms or molecules to a surface (not to be confused with absorption, which is uptake into the bulk). In chemisorption, the adsorbate forms a chemical bond with the surface. In physisorption, the interaction is weaker (van der Waals forces only). ↩
In a dissociative pathway, a molecule breaks apart as it adsorbs — e.g., O$_2$ splits into two separate O atoms on the surface. The alternative is an associative pathway, where the molecule adsorbs intact and breaks apart in a later step. ↩
Enthalpy ($H$) is the total heat content of a system at constant pressure: $H = U + PV$, where $U$ is internal energy, $P$ is pressure, and $V$ is volume. Changes in enthalpy ($\Delta H$) measure the heat released or absorbed by a reaction. ↩
The Gibbs free energy ($G = H - TS$) determines the direction of spontaneous processes at constant temperature and pressure. A reaction with $\Delta G < 0$ is thermodynamically favorable (exergonic); $\Delta G > 0$ requires energy input (endergonic). ↩
The activation energy ($E_a$) is the minimum energy that reactants must have to undergo a reaction. Even thermodynamically favorable reactions ($\Delta G < 0$) may proceed slowly if the activation energy is high. A catalyst provides an alternative pathway with a lower $E_a$. ↩
The BEP relation is an empirical observation: across a family of related catalysts, activation energy is linearly related to reaction energy. Proposed independently by Brønsted (1928) and Evans & Polanyi (1938). The slope $\alpha$ is typically between 0 and 1. ↩
The Arrhenius equation says that reaction rate increases exponentially as the activation energy decreases or temperature increases. $k_B$ is Boltzmann’s constant. At room temperature ($k_B T \approx 0.025$ eV), even small changes in $E_a$ (tenths of an eV) cause large changes in rate. ↩
The oxygen evolution reaction (OER) is the anode half-reaction in water splitting: $2\text{H}_2\text{O} \rightarrow \text{O}_2 + 4\text{H}^+ + 4e^-$. It is the reverse of the ORR and is kinetically even more demanding — forming the O–O bond requires coordinating four electron transfers. ↩
A surface termination is the specific atomic layer exposed when a crystal is cut. On a binary oxide like TiO$_2$, cutting along the (110) plane can expose a Ti-rich, O-rich, or mixed layer depending on where the cut is made. Each termination has different catalytic properties. ↩
The Hubbard U correction adds an empirical on-site Coulomb repulsion to specific orbitals (usually transition metal d-orbitals) to compensate for the tendency of standard DFT functionals to over-delocalize electrons. Typical U values range from 3–6 eV depending on the metal. ↩
The Mars-van Krevelen (MvK) mechanism is a catalytic cycle in which lattice atoms from the catalyst surface participate directly in the reaction. An adsorbate reacts with a surface oxygen, the product desorbs (creating a vacancy), and the vacancy is replenished by oxygen from a subsequent reactant. Common in oxide and carbide catalysts. ↩
A machine learning interatomic potential (MLIP) is a model that predicts the potential energy surface of an atomic system — total energy as a function of atomic positions — learned from quantum-mechanical (typically DFT) training data. Once trained, it can compute energies and forces orders of magnitude faster than DFT, enabling rapid structure relaxation and molecular dynamics. ↩