Tag Archives: chromophores

Integrated artificial photosynthesis nanosystem, a first for Lawrence Berkeley National Laboratory

There’s such a thing as too much information and not enough knowledge, a condition I’m currently suffering from with regard to artificial photosynthesis. Before expanding on that theme, here’s the latest about artificial photosynthesis from a May 16, 2013 Lawrence Berkeley National Laboratory news release (also available on EurekAlert),

In the wake of the sobering news that atmospheric carbon dioxide is now at its highest level in at least three million years, an important advance in the race to develop carbon-neutral renewable energy sources has been achieved. Scientists with the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab) have reported the first fully integrated nanosystem for artificial photosynthesis. While “artificial leaf” is the popular term for such a system, the key to this success was an “artificial forest.”

Here’s a more detailed description of the system, from the news release,

“Similar to the chloroplasts in green plants that carry out photosynthesis, our artificial photosynthetic system is composed of two semiconductor light absorbers, an interfacial layer for charge transport, and spatially separated co-catalysts,” says Peidong Yang, a chemist with Berkeley Lab’s Materials Sciences Division, who led this research. “To facilitate solar water- splitting in our system, we synthesized tree-like nanowire  heterostructures, consisting of silicon trunks and titanium oxide branches. Visually, arrays of these nanostructures very much resemble an artificial forest.”

… Artificial photosynthesis, in which solar energy is directly converted into chemical fuels, is regarded as one of the most promising of solar technologies. A major challenge for artificial photosynthesis is to produce hydrogen cheaply enough to compete with fossil fuels. Meeting this challenge requires an integrated system that can efficiently absorb sunlight and produce charge-carriers to drive separate water reduction and oxidation half-reactions.

More specifically,

“In natural photosynthesis the energy of absorbed sunlight produces energized charge-carriers that execute chemical reactions in separate regions of the chloroplast,” Yang says. “We’ve integrated our nanowire nanoscale heterostructure into a functional system that mimics the integration in chloroplasts and provides a conceptual blueprint for better solar-to-fuel conversion efficiencies in the future.”

When sunlight is absorbed by pigment molecules in a chloroplast, an energized electron is generated that moves from molecule to molecule through a transport chain until ultimately it drives the conversion of carbon dioxide into carbohydrate sugars. This electron transport chain is called a “Z-scheme” because the pattern of movement resembles the letter Z on its side. Yang and his colleagues also use a Z-scheme in their system only they deploy two Earth abundant and stable semiconductors – silicon and titanium oxide – loaded with co-catalysts and with an ohmic contact inserted between them. Silicon was used for the hydrogen-generating photocathode and titanium oxide for the oxygen-generating photoanode. The tree-like architecture was used to maximize the system’s performance. Like trees in a real forest, the dense arrays of artificial nanowire trees suppress sunlight reflection and provide more surface area for fuel producing reactions.

“Upon illumination photo-excited electron−hole pairs are generated in silicon and titanium oxide, which absorb different regions of the solar spectrum,” Yang says. “The photo-generated electrons in the silicon nanowires migrate to the surface and reduce protons to generate hydrogen while the photo-generated holes in the titanium oxide nanowires oxidize water to evolve  oxygen molecules. The majority charge carriers from both semiconductors recombine at the ohmic contact, completing the relay of the Z-scheme, similar to that of natural photosynthesis.”

Under simulated sunlight, this integrated nanowire-based artificial photosynthesis system achieved a 0.12-percent solar-to-fuel conversion efficiency. Although comparable to some natural photosynthetic conversion efficiencies, this rate will have to be substantially improved for commercial use. [emphasis mine] However, the modular design of this system allows for newly discovered individual components to be readily incorporated to improve its performance. For example, Yang notes that the photocurrent output from the system’s silicon cathodes and titanium oxide anodes do not match, and that the lower photocurrent output from the anodes is limiting the system’s overall performance.

“We have some good ideas to develop stable photoanodes with better performance than titanium oxide,” Yang says. “We’re confident that we will be able to replace titanium oxide anodes in the near future and push the energy conversion efficiency up into single digit percentages.”

Now I can discuss my confusion, which stems from my May 24, 2013 posting about work done at the Argonne National Laboratory,

… Researchers still have a long way to go before they will be able to create devices that match the light harvesting efficiency of a plant.

One reason for this shortcoming, Tiede [Argonne biochemist David Tiede] explained, is that artificial photosynthesis experiments have not been able to replicate the molecular matrix that contains the chromophores. “The level that we are at with artificial photosynthesis is that we can make the pigments and stick them together, but we cannot duplicate any of the external environment,” he said.  “The next step is to build in this framework, and then these kinds of quantum effects may become more apparent.”

Because the moment when the quantum effect occurs is so short-lived – less than a trillionth of a second – scientists will have a hard time ascertaining biological and physical rationales for their existence in the first place. [emphasis mine]

It’s not clear to me whether or not the folks at the Berkeley Lab bypassed the ‘problem’ described by Tiede or solved it to achieve solar-to-fuel conversion rates comparable to natural photosynthesis conversions. As I noted, too much information/not enough knowledge.

The quantum mechanics of photosynthesis

Thankfully, Jared Sagoff included a description of photosynthesis (I’ve long since forgotten the mechanics of the process) in his May 21, 2012 article, Scientists uncover a photosynthetic puzzle, on the US Dept. of Energy’s Argonne National Laboratory website. From Sagoff’s article, here’s the photosynthesis  description along with a description of the quantum effect the scientists observed,

While different species of plants, algae and bacteria have evolved a variety of different mechanisms to harvest light energy, they all share a feature known as a photosynthetic reaction center. Pigments and proteins found in the reaction center help organisms perform the initial stage of energy conversion.

These pigment molecules, or chromophores, are responsible for absorbing the energy carried by incoming light. After a photon hits the cell, it excites one of the electrons inside the chromophore. As they observed the initial step of the process, Argonne scientists saw something no one had observed before: a single photon appeared to excite different chromophores simultaneously.

Here’s a gorgeous image of a leaf provided with the article,

I was aware that scientists are working at hard at duplicating photosynthesis but until reading this upcoming excerpt from Sagoff’s article, I had not appreciated the dimensions of the problem,

The result of the study could significantly influence efforts by chemists and nanoscientists to create artificial materials and devices that can imitate natural photosynthetic systems. Researchers still have a long way to go before they will be able to create devices that match the light harvesting efficiency of a plant.

One reason for this shortcoming, Tiede [Argonne biochemist David Tiede] explained, is that artificial photosynthesis experiments have not been able to replicate the molecular matrix that contains the chromophores. “The level that we are at with artificial photosynthesis is that we can make the pigments and stick them together, but we cannot duplicate any of the external environment,” he said.  “The next step is to build in this framework, and then these kinds of quantum effects may become more apparent.”

Because the moment when the quantum effect occurs is so short-lived – less than a trillionth of a second – scientists will have a hard time ascertaining biological and physical rationales for their existence in the first place. [emphasis mine] “It makes us wonder if they are really just there by accident, or if they are telling us something subtle and unique about these materials,” Tiede said. “Whatever the case, we’re getting at the fundamentals of the first step of energy conversion in photosynthesis.”

Thanks to Nanowerk for the May 24, 2012 news item which drew this article to my attention.