The Reactor-STM: Watching Catalysts at Work, Atom by Atom

A powerful microscope that operates under industrial conditions is revolutionizing how we design the chemical processes that create fuels, fertilizers, and other essential products.

Have you ever wished you could shrink down to atomic size and watch a chemical reaction happen right before your eyes? Scientists who design catalysts—the materials that speed up chemical reactions in everything from car exhaust systems to massive fuel-producing plants—have long faced this limitation. They could study catalysts in a vacuum, but not under the high-pressure, high-temperature conditions of real factories. This frustrating difference is known as the "pressure gap."

Now, thanks to a remarkable instrument called the Reactor-STM, researchers are bridging this gap. This isn't just any microscope; it's a device that allows scientists to see surfaces with atomic resolution while chemical reactions are actively happening around them. This powerful approach, part of the field of operando catalysis, is providing an unprecedented, real-space view of the dynamic atomic world of working catalysts 1 5 .

The Pressure Gap: Why Laboratory Vacuums Aren't Enough

For decades, the most powerful microscopy tools required a near-perfect vacuum to function. However, industrial catalysis operates in a completely different world—one of intense pressure and heat.

The Laboratory Environment

Traditional scanning tunneling microscopes (STMs) work under ultra-high vacuum (UHV) conditions, at very low temperatures. This allows for beautiful atomic-scale images but tells us little about how a catalyst behaves when surrounded by gas molecules at several times atmospheric pressure and temperatures soaring beyond 1000 K 1 2 .

The Industrial Reality

In a real chemical plant, catalysts are exposed to pressures ranging from ambient to 100 bar and searing temperatures. Under these conditions, catalyst surfaces can change shape, form new structures, and behave in ways that are impossible to predict from vacuum-based studies 1 . This fundamental disconnect is the "pressure gap" 3 .

The Reactor-STM was invented to solve this problem, allowing scientists to finally "look" on the other side of the pressure gap and observe catalysts in action under realistic conditions 5 .

The Reactor-STM: A Microscope in a Miniature Reactor

So, what exactly is a Reactor-STM? Imagine a tiny, high-pressure flow reactor, small enough to hold just a few drops of liquid, built directly around the tip of a scanning tunneling microscope. This ingenious design allows the microscope to function perfectly while being engulfed by the very environment it is trying to study 8 .

How It Peers at the Atomic World

The instrument's operation is a marvel of engineering:

1
The Core Principle

A sharp metallic tip is brought extremely close to the catalyst surface. When a voltage is applied, electrons "tunnel" through the gap between the tip and the surface. The resulting current is exquisitely sensitive to distance, allowing the instrument to map the surface topography atom by atom 7 .

2
The Reactor Integration

The sample is sealed inside a miniature reactor cell, often with a volume as small as 300 microliters. The microscope's tip accesses the sample through a special seal. Reactant gases can be flowed through this cell, mimicking an industrial process, while the microscope below continues its work 1 8 .

3
Beyond Conductivity

Recent advancements have integrated qPlus sensor technology, combining the electronic insights of STM with the structural probing of Atomic Force Microscopy (AFM). This hybrid ReactorAFM/STM can study insulating materials, like the oxide supports used in many real-world catalysts, effectively bridging the "materials gap" as well 1 2 .

Key Features of the Reactor-STM and its Evolution
Feature Reactor-STM Advanced ReactorAFM/STM
Primary Technique Scanning Tunneling Microscopy (STM) Combined STM and Atomic Force Microscopy (AFM)
Operating Pressure Up to several bar Up to 20 bar
Operating Temperature Up to ~600 K Up to ~600 K (limited by seals/sensors)
What It Can Image Electrically conductive surfaces Both conductive and insulating surfaces
Key Advantage Closes the "pressure gap" Closes both the "pressure gap" and "materials gap"

A Landmark Experiment: The Fischer-Tropsch Synthesis in Action

To understand the power of the Reactor-STM, let's look at a key experiment studying the Fischer-Tropsch synthesis (FTS). This is a crucial industrial process that converts simple gases like carbon monoxide and hydrogen into liquid hydrocarbons—the building blocks for fuels and chemicals 1 .

The Experimental Setup

Researchers used the ReactorAFM/STM to study cobalt nanoparticle catalysts, the workhorses of FTS, supported on an aluminum oxide surface.

Preparation

The catalyst surface was prepared and its cleanliness verified in an ultra-high vacuum chamber.

Reaction Conditions

The sample was sealed in the reactor and exposed to a flow of CO and H₂ gas at a pressure of 2 bar and a temperature of 430 K—conditions that closely mimic the industrial process 1 2 .

Simultaneous Measurement

As the reaction proceeded, the ReactorAFM/STM captured images while a Quadrupole Mass Spectrometer (QMS) analyzed the gases being produced 1 .

The Revealing Results

The experiment provided a direct, atomic-scale correlation between the catalyst's structure and its function.

Visualizing the Catalyst

The microscope captured images of the cobalt nanoparticles on their support before, during, and after the reaction, revealing any structural changes induced by the harsh environment 1 .

Confirming the Reaction

The mass spectrometer detected a clear increase in the production of valuable hydrocarbons like ethane, propane, and hexane, as well as water as a byproduct, confirming that the FTS reaction was actively taking place 1 2 .

Products Detected During the Fischer-Tropsch Experiment
Product Chemical Formula Mass-to-Charge Ratio (m/z) Monitored
Water H₂O 18
Ethane C₂H₆ 30
Propane C₃H₈ 44
Hexane C₆H₁₄ 86

This experiment demonstrated the Reactor-STM's unique ability to directly link atomic-scale surface morphology with catalytic performance under realistic operating conditions 1 .

The Scientist's Toolkit: Essentials for Operando Analysis

Bringing atomic-scale imaging into high-pressure environments requires a suite of specialized tools and reagents. The following table details some of the key components that make these groundbreaking experiments possible.

Key Research Tools and Reagents in Reactor-STM Experiments
Tool or Material Function in the Experiment
qPlus Sensor The heart of the combined AFM/STM. A quartz tuning fork with a metallic tip that can simultaneously measure tunneling current and atomic forces 1 2 .
Pd(100) Single Crystal A model catalyst with a well-defined surface, often used to study fundamental processes like oxidation under controlled conditions 1 2 .
Cobalt Nanoparticles An industrially relevant catalyst, used in experiments on the Fischer-Tropsch synthesis to create liquid fuels 1 .
Aluminum Oxide Support A common, often insulating, material used to disperse metal catalyst nanoparticles, maximizing their surface area and efficiency 1 .
Quadrupole Mass Spectrometer (QMS) A "sniffer" at the reactor exhaust that identifies and quantifies gas-phase products in real-time, directly correlating surface structure with catalytic activity 1 .
Kalrez® Elastomer Seal A chemically resistant seal that can withstand high temperatures, crucial for isolating the high-pressure reactor volume from the vacuum of the main chamber 1 2 .

Beyond a Single Reaction: The Broader Impact

The insights from Reactor-STM studies are transforming our understanding of catalysis. For example, research on CO oxidation over platinum surfaces revealed that under high-pressure O₂, the metal surface can transform into a thin "surface oxide" 5 . This oxide layer often exhibits superior catalytic activity compared to the pure metal, a discovery that could only be made under operando conditions and which guides the design of more efficient catalysts .

Transforming Catalyst Design

The Reactor-STM provides direct visualization of active sites and surface transformations under working conditions, enabling rational design of next-generation catalysts with improved activity, selectivity, and stability.

Conclusion: A New Era of Catalyst Design

The Reactor-STM has moved the goalposts of surface science. It is no longer enough to know what a catalyst looks like at rest in a vacuum; we can now watch it dance under the heat and pressure of its actual job. By closing the pressure gap, this technology provides the interpretive framework needed to understand catalysts under industrial conditions 1 .

The ongoing development of these instruments, such as the combination with AFM, promises to unlock even more secrets of the atomic world. As we continue to peer directly at the active sites of chemical transformation, we gain the knowledge to design smarter, more efficient, and more selective catalysts—powering the sustainable chemical processes of the future.

References