Dukovic

Understanding light-driven production of hydrogen could unlock future insights for harnessing light for chemistry

Daniel Morton — Mon, 09 Jun 2025 16:27:04 +0000

Understanding light-driven production of hydrogen could unlock future insights for harnessing light for chemistry Daniel Morton Mon, 06/09/2025 - 10:27

Daniel Morton

Light to fuel: clean hydrogen production. Improved understanding of the light-driven production of hydrogen holds the promise not just to make the reaction more efficient in producing a fuel, but also to offer a framework to better understand future light-driven chemistries.

Many chemical reactions require the input of energy to activate the transformation. This can often be in the form of heat, or chemical energy. One of the most efficient ways of introducing energy into a reaction is by using light. If you don’t have to heat up a reaction, or add extra chemicals to it, and instead shine a light on it, you can save significant energy. However, it can be difficult to control and optimize light-driven reactions. This research, just published in Chem, is a collaboration between the Dukovic Group at the 91PORN (91PORN) and the King Group at the National Renewable Energy Lab (NREL) and provides a holistic understanding of the light-driven production of hydrogen gas using a nanocrystal-enzyme complex as the catalyst, and a computational framework that can be used more generally to understand other light-driven chemical reactions in the future. The code for this model is being made available in the supplementary documents of this article.

Chemical catalysis is a special type of reaction, one that increases the speed of a transformation and often reduces the amount of waste produced by the process. Think of it like an assembly line. The catalyst is like a station on the line, bringing together two or more components to create a new product that is then passed along. Without the catalyst the components might, by chance, bump together and form the desired product, but it will be much slower, and much less frequent. The catalyst remains unchanged in the process and can repeat the transformation many times.

Enzymes are Nature’s catalysts. On the cellular level, whenever a change needs to happen, an enzyme is usually involved. The speed of an enzyme, and its selectivity, that is its ability to only react with the desired molecules out of the soup of molecules present in a typical cell, is fantastic. Enzymes are often superior to catalysts we can make in a lab, and as such, much research has gone into finding ways to harness such enzymes to do reactions for us in the lab. Unfortunately, it is not as easy as just grabbing some enzyme out of a cell. Enzymes often require specific environments and partners to react with.

Redox enzymes are a special, and particularly attractive, class of enzymes. They are capable of adding, or removing, an electron from a chemical reaction, a key step in the production of hydrogen gas. Redox enzymes rarely exist by themselves. Returning to the assembly line analogy, to get a station that can add the electrons to the protons (H⁺) to make hydrogen gas, many other stations need to be added before in a specific order. In a cell there is a chain of enzymes that pass the electrons along before the reaction can take place.

This is where the artificial component comes in. The nanocrystal, which, when exposed to light, releases an electron, replaces the long chain of enzymes and can directly transfer an electron to the enzyme. So, you reduce your assembly line down from a chain of many stations to just two. “This work was really only possible through collaboration” explains Gordana Dukovic, the lead researcher at 91PORN. “The team at NREL have vast expertise in hydrogenase (the redox enzyme that creates hydrogen gas), and we have the expertise in making and tailoring the nanocrystals and studying what they do after they absorb light”. Getting the enzyme to work with the artificial electron donor took some work.

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This Research

Characterization of Photochemical Processes

Electron Transfer Kinetics

Competition between electron transfer processes

Activation Thermodynamics

Role of Surface-Capping Ligands

Quantum Efficiency of Charge Transfer

2020 Review of this research area

The two teams first started working together in 2011 and have invested a great deal of work in understanding many aspects of this nanocrystal-enzyme hybrid. “Working with the team at NREL has been really amazing” says Dukovic, “the opportunity to work with experts who really help you ask the important questions, and identify where our assumptions were wrong, was essential for this work.” For over more than a decade this collaboration has interrogated the different steps of this process, such as how the nanocrystal and enzyme fit together, how the nanocrystal generates an electron when exposed to light, how the nanocrystal transfers the electron to the enzyme, and how the enzyme uses those electrons to make hydrogen. It is only through building this comprehensive understanding of the steps that underpin this reaction that the team are in the position to provide a holistic picture of the whole transformation. Furthermore, the framework that they have built is robust enough to be applied in improving other light-driven reactions in the future.

This work describes an improved assembly line capable of converting light energy into hydrogen gas, a clean burning fuel that provides new, more efficient ways, to generate electricity. Perhaps more excitingly, it demonstrates the power of a new computational model and framework, built on over a decade of collaborative research, which has been made freely available, that provides insights into light-driven reactions and can be used by the scientific community to refine and optimize future light-driven chemistry. Helena Keller, the lead author is enthusiastic about the next steps “We are in a really exciting place now, where the capabilities of using computational methods to understand complex systems like this are becoming more and more accessible. The better we understand how to control processes at the smallest scales – like at the level of individual electron transfers – the closer we get to revolutionizing the way we produce energy and materials for the good of the world”.

June 2025

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Single-Molecule Fluorescence Microscopy Reveals Energy Transfer Active versus Inactive Nanocrystal/Dye Conjugate Pairs

Daniel Morton — Mon, 07 Apr 2025 21:56:48 +0000

Single-Molecule Fluorescence Microscopy Reveals Energy Transfer Active versus Inactive Nanocrystal/Dye Conjugate Pairs Daniel Morton Mon, 04/07/2025 - 15:56

CHEMICAL AND BIOMEDICAL IMAGING, 2025, ASAP

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Emissive Traps Lead to Asymmetric Photoluminescence Line Shape in Spheroidal CsPbBr3 Quantum Dots

Daniel Morton — Tue, 25 Mar 2025 19:36:09 +0000

Emissive Traps Lead to Asymmetric Photoluminescence Line Shape in Spheroidal CsPbBr3 Quantum Dots Daniel Morton Tue, 03/25/2025 - 13:36

NANO LETTERS, 2025, ASAP

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Revealing the Influence of Binding Motifs on Electron Transfer and Recombination Kinetics for CdSe Quantum Dots Functionalized with a Modified Viologen

Daniel Morton — Thu, 06 Mar 2025 20:27:26 +0000

Revealing the Influence of Binding Motifs on Electron Transfer and Recombination Kinetics for CdSe Quantum Dots Functionalized with a Modified Viologen Daniel Morton Thu, 03/06/2025 - 13:27

THE JOURNAL OF PHYSICAL CHEMISTRY C, 2025, 129, 11, 5556-5570

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Revealing the Phonon Bottleneck Limit in Negatively Charged CdS Quantum Dots

Daniel Morton — Thu, 13 Feb 2025 22:43:06 +0000

Revealing the Phonon Bottleneck Limit in Negatively Charged CdS Quantum Dots Daniel Morton Thu, 02/13/2025 - 15:43

ACS NANO, 2025, 19, 7, 7055-7063

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Synthesis and Characterization of [Ni(H2O)(7-PPh2NArSO3)2](NaBF4) for Light-Driven Quantum Dot-Catalyst Hydrogen Evolution

Daniel Morton — Tue, 14 Jan 2025 17:51:30 +0000

Synthesis and Characterization of [Ni(H2O)(7-PPh2NArSO3)2](NaBF4) for Light-Driven Quantum Dot-Catalyst Hydrogen Evolution Daniel Morton Tue, 01/14/2025 - 10:51

ENERGY FUELS, 2025, 39, 4, 2196-2202

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Intrinsically Slow Cooling of Hot Electrons in CdSe Nanocrystals Compared to CdS

Daniel Morton — Thu, 19 Dec 2024 03:43:53 +0000

Intrinsically Slow Cooling of Hot Electrons in CdSe Nanocrystals Compared to CdS Daniel Morton Wed, 12/18/2024 - 20:43

NANO LETTERS, 2024, ASAP

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Reductive pathways in molten inorganic salts enable colloidal synthesis of III-V semiconductor nanocrystals

Daniel Morton — Thu, 24 Oct 2024 19:58:51 +0000

Reductive pathways in molten inorganic salts enable colloidal synthesis of III-V semiconductor nanocrystals Daniel Morton Thu, 10/24/2024 - 13:58

SCIENCE, 2024, 386, 6720, 401-407

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RASEI Researchers unlock a 'new synthetic frontier' for quantum dots

Daniel Morton — Thu, 24 Oct 2024 19:50:17 +0000

RASEI Researchers unlock a 'new synthetic frontier' for quantum dots Daniel Morton Thu, 10/24/2024 - 13:50

Lauren Scholz

Read the Full Paper here

University of Chicago Press Release

In a breakthrough for nanotechnology, researchers have discovered a new way to synthesize quantum dot nanocrystals using molten salt as a medium. Traditional methods to create these materials required organic solvents, which cannot withstand the high temperatures needed for certain semiconductor materials, particularly those combining elements from groups III and V on the periodic table. By using superheated molten sodium chloride, scientists were able to synthesize these semiconductor nanocrystals, paving the way for improved applications in fields like quantum computing, LED lighting, and solar technology.

Led by a team from the University of Chicago and collaborating institutions, including RASEI Fellows Sadegh Yazdi and Gordana Dukovic, this novel method also opens new avenues for materials science by enabling the synthesis of previously inaccessible nanocrystal compositions. The technique addresses long-standing challenges by providing a high-temperature environment without degrading the materials. Researchers hope this advance will contribute to new types of devices and materials, marking a significant expansion in the range of accessible quantum dot technologies.

For a more information, please see the press release from The University of Chicago.

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Profile: Benjamin Hammel

Anonymous — Mon, 09 Sep 2024 06:00:00 +0000

Profile: Benjamin Hammel Anonymous (not verified) Mon, 09/09/2024 - 00:00

Daniel Morton

Ben Hammel is a graduate student in the Dukovic group at 91PORN, who is using advanced microscopic techniques with Sadegh Yazdi to provide insights into the relationships between materials structures and properties, specifically materials associated with renewable energy research. We caught up with Ben to find out more about what led him to this research area, what excites him about this field of study, and what he gets up to outside the lab.

Where did you grow up?

I am from Albuquerque, New Mexico. I grew up outside the city limits, on the southwest mesa. There are a lot of alfalfa farms and other agricultural industries around there. One of the really cool things about that part of New Mexico is the rich cultural heritage, there is a lot of cultures coming together, with such a long history. Some of the earliest settlements in the United States are in New Mexico!

What did you get up to as a kid?

I enjoyed exploring outside and hiking. Lots of great mountains near Albuquerque and good camping in northern New Mexico.

What drew you into science and research?

New Mexico is kind of this secret hub for scientific research. There is such a rich community of scientists and researchers there and a long history of amazing work. The Manhattan Project, Los Alamos and Sandia National Labs – they set up these huge institutions for research. These all have a trickle-down effect that has impacted a huge number of people and was definitely something that played a big part in my early thinking.

I started doing research at a really young age. As a freshman in high school, I wrote on my resume that my goal was to become a particle physicist! This got passed along to a retired Sandia National Labs scientist, Pace VanDevender, who then took me under his wing. I worked with him as a summer research assistant that year, and it made me think that my path would lead to working at Sandia.

When I was 16, I had the opportunity to work in a chemistry lab at Sandia National Labs – prior to that I had been all about physics and electrical engineering. I was very much interested in energy research and I was really into building projects and devices, such as a regenerative bicycle braking system. I didn’t really like chemistry and I started from basically nothing. On my first day, the researchers in the lab (LaRico Treadwell and Daniel Yonemoto) took me through my first reaction, how to calculate the amount of reagents and how to mix them – I didn’t even know how to do a mass balance! The support I got from that lab (Tim, Rico, Daniel, Jeremiah, Francesca, Diana, and Fernando to name a few) was fantastic and very rapidly chemistry became my main interest. My mentor, the venerable Timothy J. Boyle, said “Ben, learning chemistry in this lab is like learning how to drive in a Lamborghini!” I had a very flexible school schedule that enabled me to work at Sandia a lot. And I fell in love with chemistry.

So, you were hooked on research at a young age, how did this inform your decisions about university?

I really wanted to find a way to combine my early interest in building things and engineering with my passion for chemistry. The University of Pennsylvania has this program called the Vagelos Integrated Program in Energy Research, or VIPER, that gives you the chance to do 2 degrees and that really drew me in. I did chemistry plus materials science and engineering and I stuck with those all the way through.

I was looking for ways to combine making molecules with applications in nanoscience, and that led me to working in the lab of Christopher Murray. I was looking for paid work and my Mom said “You can either work as a dishwasher, or you can work in a chemistry lab”, so I was glad that I persuaded Chris to let me join his lab.

Later during my undergraduate degree, in 2019, I did an internship at NREL, and I ended up working on something completely different, microbubble insulation. This was much more a materials engineering project working with researchers Lin Simpson and Chaiwat Engtrakul. We were gluing bubbles together to form foam bricks for use in insulation. The aim was to try and make something that was cheap, had high performance, and robust to damage and defects.

Coming out of that internship I realized that what really fascinated me was the fundamental chemistry I was doing more than the engineering aspects. I became very interested in the fundamentals of what was happening at the surfaces of these microbubbles, much more than the engineering challenges, and that is what steered me more toward chemistry and materials science.

I really enjoyed my time at NREL, both the research and the opportunities to spend time outdoors, it was one of the big draws when I was looking into graduate school.

Describe the research that you are involved in now

I work on the fundamental end of materials and energy research. We aim to learn how we can make nanomaterials that are better catalysts, which involves fabricating these nanomaterials in an extremely precise fashion, so that we have clear understanding about the materials structure and properties. Of specific interest is the electronic structure, since this impacts how it absorbs light. Armed with this fundamental understanding we can better guide the design of the next generation of materials for energy harvesting, storage, and transport. Working out how the structure of a material influences its properties is what really interests me at the moment.

Your research involves a great deal of collaboration, how has that impacted your work?

I think my experience of working in both engineering and chemistry has helped me connect with folks from different disciplines. I have learned that there are many ways in which teams are forming in the energy sciences, and it’s these teams that are doing the really cool science. It’s also interesting to consider some of the social and economic impacts of doing research and thinking about cost and other factors that are going to dictate which technologies get commercialized.

Early on I wanted to be involved in every part of the research spectrum, from discovery to application. But you can’t do it all. And as I have specialized, I have really enjoyed working as an integral part of bigger research teams, where I can be aware of the big picture, make meaningful contributions through my specialty, and engage and learn from others.

What do you enjoy doing outside of the lab?

I do really enjoy spending time outdoors, but my main hobby is gaming. I play a game called League of Legends, and at one point I was in the top 0.1% of players online. It got pretty competitive and required a ton of work. I entertained the idea of playing professionally. But when I ended up playing against some professional players, I quickly realized there was no chance I could ever go pro! I play a lot more casually now.

What would you say to someone considering a research path?

For me I found that scientists and engineers operate in quite different ways, and when you start taking both sets of classes you rapidly pick up on this. If someone is trying to do the same kind of dual pathway, it is hard at first, but it really is worth persevering. Having expertise in one area is important but having a more general perspective can come in very useful and gives you a broad skillset. You can think at a bunch of different scales, and from different perspectives, which I found challenging at first but have found to be very useful.

What are the future impacts of your research that you are excited about?

I think virtual reality displays are going to bring huge benefits. The most expensive part of these at the moment is the display. Engineering new materials that are super small and super bright will make these really high-resolution. We are going to get this amazing technology that is going to have a lot of great practical applications, I think VR will be a game changer.

Microscopy is also blowing up right now. It is now almost routine to look at atoms, which really changes how you think about and make materials. We are reaching higher and higher levels of precision, which I think is going to open the door to new applications. I don’t know what those are going to be!

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