Tag Archives: Peidong Yang

Unusual appetite for gold

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This bacterium (bacteria being the plural) loves gold, which is lucky for anyone trying to develop artificial photosynthesis.From an October 9, 2018 news item on ScienceDaily,

A bacterium named Moorella thermoacetica won’t work for free. But UC Berkeley [University of California at Berkeley] researchers have figured out it has an appetite for gold. And in exchange for this special treat, the bacterium has revealed a more efficient path to producing solar fuels through artificial photosynthesis.

An October 5, 2018 UC Berkeley news release by Theresa Duque (also on EurekAlert but published on October 9, 2018), which originated the news item, expands on the theme,

M. thermoacetica first made its debut as the first non-photosensitive bacterium to carry out artificial photosynthesis (link is external) in a study led by Peidong Yang, a professor in UC Berkeley’s College of Chemistry. By attaching light-absorbing nanoparticles made of cadmium sulfide (CdS) to the bacterial membrane exterior, the researchers turned M. thermoacetica into a tiny photosynthesis machine, converting sunlight and carbon dioxide into useful chemicals.

Now Yang and his team of researchers have found a better way to entice this CO2-hungry bacterium into being even more productive. By placing light-absorbing gold nanoclusters inside the bacterium, they have created a biohybrid system that produces a higher yield of chemical products than previously demonstrated. The research, funded by the National Institutes of Health, was published on Oct. 1 in Nature Nanotechnology (link is external).

For the first hybrid model, M. thermoacetica-CdS, the researchers chose cadmium sulfide as the semiconductor for its ability to absorb visible light. But because cadmium sulfide is toxic to bacteria, the nanoparticles had to be attached to the cell membrane “extracellularly,” or outside the M. thermoacetica-CdS system. Sunlight excites each cadmium-sulfide nanoparticle into generating a charged particle known as an electron. As these light-generated electrons travel through the bacterium, they interact with multiple enzymes in a process known as “CO2 reduction,” triggering a cascade of reactions that eventually turns CO2 into acetate, a valuable chemical for making solar fuels.

But within the extracellular model, the electrons end up interacting with other chemicals that have no part in turning CO2 into acetate. And as a result, some electrons are lost and never reach the enzymes. So to improve what’s known as “quantum efficiency,” or the bacterium’s ability to produce acetate each time it gains an electron, the researchers found another semiconductor: nanoclusters made of 22 gold atoms (Au22), a material that M. thermoacetica took a surprising shine to.

A single nanocluster of 22 gold atoms

Figure: A single nanocluster of 22 gold atoms – Au22 – is only 1 nanometer in diameter, allowing it to easily slip through the bacterial cell wall.

“We selected Au22 because it’s ideal for absorbing visible light and has the potential for driving the CO2 reduction process, but we weren’t sure whether it would be compatible with the bacteria,” Yang said. “When we inspected them under the microscope, we discovered that the bacteria were loaded with these Au22 clusters – and were still happily alive.”

Imaging of the M. thermoacetica-Au22 system was done at UC Berkeley’s Molecular Imaging Center (link is external).

The researchers also selected Au22 ­– dubbed by the researchers as “magic” gold nanoclusters – for its ultrasmall size: A single Au22nanocluster is only 1 nanometer in diameter, allowing each nanocluster to easily slip through the bacterial cell wall.

“By feeding bacteria with Au22 nanoclusters, we’ve effectively streamlined the electron transfer process for the CO2 reduction pathway inside the bacteria, as evidenced by a 2.86 percent quantum efficiency – or 33 percent more acetate produced within the M. thermoacetica-Au22 system than the CdS model,” Yang said.

The magic gold nanocluster is the latest discovery coming out of Yang’s lab, which for the past six years has focused on using biohybrid nanostructures to convert CO2 into useful chemicals as part of an ongoing effort to find affordable, abundant resources for renewable fuels, and potential solutions to thwart the effects of climate change.

“Next, we’d like to find a way to reduce costs, improve the lifetimes for these biohybrid systems, and improve quantum efficiency,” Yang said. “By continuing to look at the fundamental aspect of how gold nanoclusters are being photoactivated, and by following the electron transfer process within the CO2 reduction pathway, we hope to find even better solutions.”

Co-authors with Yang are UC Berkeley graduate student Hao Zhang and former postdoctoral fellow Hao Liu, now at Donghua University in Shanghai, China.

Here’s a link to and a citation for the paper,

Bacteria photosensitized by intracellular gold nanoclusters for solar fuel production by Hao Zhang, Hao Liu, Zhiquan Tian, Dylan Lu, Yi Yu, Stefano Cestellos-Blanco, Kelsey K. Sakimoto, & Peidong Yang. Nature Nanotechnologyvolume 13, pages900–905 (2018). DOI: https://doi.org/10.1038/s41565-018-0267-z Published: 01 October 2018

This paper is behind a paywall.

For lovers of animation, the folks at UC Berkeley have produced this piece about the ‘gold-loving’ bacterium,

Mixing the unmixable for all new nanoparticles

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This news comes out of the University of Maryland and the discovery could led to nanoparticles that have never before been imagined. From a March 29, 2018 news item on ScienceDaily,

Making a giant leap in the ‘tiny’ field of nanoscience, a multi-institutional team of researchers is the first to create nanoscale particles composed of up to eight distinct elements generally known to be immiscible, or incapable of being mixed or blended together. The blending of multiple, unmixable elements into a unified, homogenous nanostructure, called a high entropy alloy nanoparticle, greatly expands the landscape of nanomaterials — and what we can do with them.

This research makes a significant advance on previous efforts that have typically produced nanoparticles limited to only three different elements and to structures that do not mix evenly. Essentially, it is extremely difficult to squeeze and blend different elements into individual particles at the nanoscale. The team, which includes lead researchers at University of Maryland, College Park (UMD)’s A. James Clark School of Engineering, published a peer-reviewed paper based on the research featured on the March 30 [2018] cover of Science.

A March 29, 2018 University of Maryland press release (also on EurekAlert), which originated the news item, delves further (Note: Links have been removed),

“Imagine the elements that combine to make nanoparticles as Lego building blocks. If you have only one to three colors and sizes, then you are limited by what combinations you can use and what structures you can assemble,” explains Liangbing Hu, associate professor of materials science and engineering at UMD and one of the corresponding authors of the paper. “What our team has done is essentially enlarged the toy chest in nanoparticle synthesis; now, we are able to build nanomaterials with nearly all metallic and semiconductor elements.”

The researchers say this advance in nanoscience opens vast opportunities for a wide range of applications that includes catalysis (the acceleration of a chemical reaction by a catalyst), energy storage (batteries or supercapacitors), and bio/plasmonic imaging, among others.

To create the high entropy alloy nanoparticles, the researchers employed a two-step method of flash heating followed by flash cooling. Metallic elements such as platinum, nickel, iron, cobalt, gold, copper, and others were exposed to a rapid thermal shock of approximately 3,000 degrees Fahrenheit, or about half the temperature of the sun, for 0.055 seconds. The extremely high temperature resulted in uniform mixtures of the multiple elements. The subsequent rapid cooling (more than 100,000 degrees Fahrenheit per second) stabilized the newly mixed elements into the uniform nanomaterial.

“Our method is simple, but one that nobody else has applied to the creation of nanoparticles. By using a physical science approach, rather than a traditional chemistry approach, we have achieved something unprecedented,” says Yonggang Yao, a Ph.D. student at UMD and one of the lead authors of the paper.

To demonstrate one potential use of the nanoparticles, the research team used them as advanced catalysts for ammonia oxidation, which is a key step in the production of nitric acid (a liquid acid that is used in the production of ammonium nitrate for fertilizers, making plastics, and in the manufacturing of dyes). They were able to achieve 100 percent oxidation of ammonia and 99 percent selectivity toward desired products with the high entropy alloy nanoparticles, proving their ability as highly efficient catalysts.

Yao says another potential use of the nanoparticles as catalysts could be the generation of chemicals or fuels from carbon dioxide.

“The potential applications for high entropy alloy nanoparticles are not limited to the field of catalysis. With cross-discipline curiosity, the demonstrated applications of these particles will become even more widespread,” says Steven D. Lacey, a Ph.D. student at UMD and also one of the lead authors of the paper.

This research was performed through a multi-institutional collaboration of Prof. Liangbing Hu’s group at the University of Maryland, College Park; Prof. Reza Shahbazian-Yassar’s group at University of Illinois at Chicago; Prof. Ju Li’s group at the Massachusetts Institute of Technology; Prof. Chao Wang’s group at Johns Hopkins University; and Prof. Michael Zachariah’s group at the University of Maryland, College Park.

What outside experts are saying about this research:

“This is quite amazing; Dr. Hu creatively came up with this powerful technique, carbo-thermal shock synthesis, to produce high entropy alloys of up to eight different elements in a single nanoparticle. This is indeed unthinkable for bulk materials synthesis. This is yet another beautiful example of nanoscience!,” says Peidong Yang, the S.K. and Angela Chan Distinguished Professor of Energy and professor of chemistry at the University of California, Berkeley and member of the American Academy of Arts and Sciences.

“This discovery opens many new directions. There are simulation opportunities to understand the electronic structure of the various compositions and phases that are important for the next generation of catalyst design. Also, finding correlations among synthesis routes, composition, and phase structure and performance enables a paradigm shift toward guided synthesis,” says George Crabtree, Argonne Distinguished Fellow and director of the Joint Center for Energy Storage Research at Argonne National Laboratory.

More from the research coauthors:

“Understanding the atomic order and crystalline structure in these multi-element nanoparticles reveals how the synthesis can be tuned to optimize their performance. It would be quite interesting to further explore the underlying atomistic mechanisms of the nucleation and growth of high entropy alloy nanoparticle,” says Reza Shahbazian-Yassar, associate professor at the University of Illinois at Chicago and a corresponding author of the paper.

“Carbon metabolism drives ‘living’ metal catalysts that frequently move around, split, or merge, resulting in a nanoparticle size distribution that’s far from the ordinary, and highly tunable,” says Ju Li, professor at the Massachusetts Institute of Technology and a corresponding author of the paper.

“This method enables new combinations of metals that do not exist in nature and do not otherwise go together. It enables robust tuning of the composition of catalytic materials to optimize the activity, selectivity, and stability, and the application will be very broad in energy conversions and chemical transformations,” says Chao Wang, assistant professor of chemical and biomolecular engineering at Johns Hopkins University and one of the study’s authors.

Here’s a link to and a citation for the paper,

Carbothermal shock synthesis of high-entropy-alloy nanoparticles by Yonggang Yao, Zhennan Huang, Pengfei Xie, Steven D. Lacey, Rohit Jiji Jacob, Hua Xie, Fengjuan Chen, Anmin Nie, Tiancheng Pu, Miles Rehwoldt, Daiwei Yu, Michael R. Zachariah, Chao Wang, Reza Shahbazian-Yassar, Ju Li, Liangbing Hu. Science 30 Mar 2018: Vol. 359, Issue 6383, pp. 1489-1494 DOI: 10.1126/science.aan5412

This paper is behind a paywall.

Cyborg bacteria to reduce carbon dioxide

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This video is a bit technical but then it is about work being presented to chemists at the American Chemical Society’s (ACS) at the 254th National Meeting & Exposition Aug. 20 -24, 2017,

For a more plain language explanation, there’s an August 22, 2017 ACS news release (also on EurekAlert),

Photosynthesis provides energy for the vast majority of life on Earth. But chlorophyll, the green pigment that plants use to harvest sunlight, is relatively inefficient. To enable humans to capture more of the sun’s energy than natural photosynthesis can, scientists have taught bacteria to cover themselves in tiny, highly efficient solar panels to produce useful compounds.

…

“Rather than rely on inefficient chlorophyll to harvest sunlight, I’ve taught bacteria how to grow and cover their bodies with tiny semiconductor nanocrystals,” says Kelsey K. Sakimoto, Ph.D., who carried out the research in the lab of Peidong Yang, Ph.D. “These nanocrystals are much more efficient than chlorophyll and can be grown at a fraction of the cost of manufactured solar panels.”

Humans increasingly are looking to find alternatives to fossil fuels as sources of energy and feedstocks for chemical production. Many scientists have worked to create artificial photosynthetic systems to generate renewable energy and simple organic chemicals using sunlight. Progress has been made, but the systems are not efficient enough for commercial production of fuels and feedstocks.

Research in Yang’s lab at the University of California, Berkeley, where Sakimoto earned his Ph.D., focuses on harnessing inorganic semiconductors that can capture sunlight to organisms such as bacteria that can then use the energy to produce useful chemicals from carbon dioxide and water. “The thrust of research in my lab is to essentially ‘supercharge’ nonphotosynthetic bacteria by providing them energy in the form of electrons from inorganic semiconductors, like cadmium sulfide, that are efficient light absorbers,” Yang says. “We are now looking for more benign light absorbers than cadmium sulfide to provide bacteria with energy from light.”

Sakimoto worked with a naturally occurring, nonphotosynthetic bacterium, Moorella thermoacetica, which, as part of its normal respiration, produces acetic acid from carbon dioxide (CO2). Acetic acid is a versatile chemical that can be readily upgraded to a number of fuels, polymers, pharmaceuticals and commodity chemicals through complementary, genetically engineered bacteria.

When Sakimoto fed cadmium and the amino acid cysteine, which contains a sulfur atom, to the bacteria, they synthesized cadmium sulfide (CdS) nanoparticles, which function as solar panels on their surfaces. The hybrid organism, M. thermoacetica-CdS, produces acetic acid from CO2, water and light. “Once covered with these tiny solar panels, the bacteria can synthesize food, fuels and plastics, all using solar energy,” Sakimoto says. “These bacteria outperform natural photosynthesis.”

The bacteria operate at an efficiency of more than 80 percent, and the process is self-replicating and self-regenerating, making this a zero-waste technology. “Synthetic biology and the ability to expand the product scope of CO2 reduction will be crucial to poising this technology as a replacement, or one of many replacements, for the petrochemical industry,” Sakimoto says.

So, do the inorganic-biological hybrids have commercial potential? “I sure hope so!” he says. “Many current systems in artificial photosynthesis require solid electrodes, which is a huge cost. Our algal biofuels are much more attractive, as the whole CO2-to-chemical apparatus is self-contained and only requires a big vat out in the sun.” But he points out that the system still requires some tweaking to tune both the semiconductor and the bacteria. He also suggests that it is possible that the hybrid bacteria he created may have some naturally occurring analog. “A future direction, if this phenomenon exists in nature, would be to bioprospect for these organisms and put them to use,” he says.

For more insight into the work, check out Dexter Johnson’s Aug. 22, 2017 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website),

“It’s actually a natural, overlooked feature of their biology,” explains Sakimoto in an e-mail interview with IEEE Spectrum. “This bacterium has a detoxification pathway, meaning if it encounters a toxic metal, like cadmium, it will try to precipitate it out, thereby detoxifying it. So when we introduce cadmium ions into the growth medium in which M. thermoacetica is hanging out, it will convert the amino acid cysteine into sulfide, which precipitates out cadmium as cadmium sulfide. The crystals then assemble and stick onto the bacterium through normal electrostatic interactions.”

I’ve just excerpted one bit, there’s more in Dexter’s posting.

Training your bacterium to perform photosynthesis

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A Jan. 4, 2016 news item on Nanotechnology Now announces a rather distinctive approach to artificial photosynthesis,

Trainers of dogs, horses, and other animal performers take note: a bacterium named Moorella thermoacetica has been induced to perform only a single trick, but it’s a doozy. Berkeley Lab researchers are using M. thermoacetica to perform photosynthesis – despite being non-photosynthetic – and also to synthesize semiconductor nanoparticles in a hybrid artificial photosynthesis system for converting sunlight into valuable chemical products.

“We’ve demonstrated the first self-photosensitization of a non-photosynthetic bacterium, M. thermoacetica, with cadmium sulfide nanoparticles to produce acetic acid from carbon dioxide at efficiencies and yield that are comparable to or may even exceed the capabilities of natural photosynthesis,” says Peidong Yang, a chemist with Berkeley Lab’s Materials Sciences Division, who led this work.

“The bacteria/inorganic-semiconductor hybrid artificial photosynthesis system we’ve created is self-replicating through the bio-precipitation of cadmium sulfide nanoparticles, which serve as the light harvester to sustain cellular metabolism,” Yang says. “Demonstrating this cyborgian ability to self-augment the functionality of biological systems through inorganic chemistry opens up the integration of biotic and abiotic components for the next generation of advanced solar-to-chemical conversion technologies.”

A Jan. 1, 2016 Berkeley Lab news release, which originated the news item, provides a little more detail,

Photosynthesis is the process by which nature harvests sunlight and uses the solar energy to synthesize carbohydrates from carbon dioxide and water. Artificial versions of photosynthesis are being explored for the clean, green and sustainable production of chemical products now made from petroleum, primarily fuels and plastics. Yang and his research group have been at the forefront of developing artificial photosynthetic technologies that can realize the full potential of solar-to-chemical synthesis.

“In our latest study, we combined the highly efficient light harvesting of an inorganic semiconductor with the high specificity, low cost, and self-replication and self-repair of a biocatalyst,” Yang says. “By inducing the self-photosensitization of M. thermoacetica with cadmium sulfide nanoparticles, we enabled the photosynthesis of acetic acid from carbon dioxide over several days of light-dark cycles at relatively high quantum yields, demonstrating a self-replicating route toward solar-to-chemical carbon dioxide reduction.”

Cadmium sulfide is a well-studied semiconductor with a band structure and that is well-suited for photosynthesis. As both an “electrograph” (meaning it can undergo direct electron transfers from an electrode), and an “acetogen” (meaning it can direct nearly 90-percent of its photosynthetic products towards acetic acid), M. thermoacetica serves as the ideal model organism for demonstrating the capabilities of this hybrid artificial photosynthesis system.

“Our hybrid system combines the best of both worlds: the light-harvesting capabilities of semiconductors with the catalytic power of biology,” Yang says. “In this study, we’ve demonstrated not only that biomaterials can be of sufficient quality to carry out useful photochemistry, but that in some ways they may be even more advantageous in biological applications.”

Here’s a link to and a citation for the paper,

Self-photosensitization of nonphotosynthetic bacteria for solar-to-chemical production by Kelsey K. Sakimoto, Andrew Barnabas Wong, Peidong Yang. Science 1 January 2016: Vol. 351 no. 6268 pp. 74-77 DOI: 10.1126/science.aad3317

This paper is behind a paywall.

Not the same old gold: there’s a brand new phase

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A Dec. 7, 2015 news item on ScienceDaily announces a new phase for gold has been identified,

A new and stable phase of gold with different physical and optical properties from those of conventional gold has been synthesized by Agency for Science, Technology and Research (A*STAR) researchers [1], Singapore, and promises to be useful for a wide range of applications, including plasmonics and catalysis.

Many materials exist in a variety of crystal structures, known as phases or polymorphs. These different phases have the same chemical composition but different physical structures, which give rise to different properties. For example, two well-known polymorphs of carbon, graphite and diamond, arranged differently, have radically different physical properties, despite being the same element.

Gold has been used for many purposes throughout history, including jewelry, electronics and catalysis. Until now it has always been produced in one phase ― a face-centered cubic structure in which atoms are located at the corners and the center of each face of the constituent cubes.

Now, Lin Wu and colleagues at the Institute of the A*STAR Institute of High Performance Computing have modeled the optical and plasmonic properties of nanoscale ribbons of a new phase of gold — the 4H hexagonal phase (…) — produced and characterized by collaborators at other institutes in Singapore, China and the USA. The team synthesized nanoribbons of the new phase by simply heating the gold (III) chloride hydrate (HAuCl4) with a mixture of three organic solvents and then centrifuging and washing the product. This gave a high yield of about 60 per cent.

Here’s an image supplied by the researchers,

The atomic structure of the new phase of gold synthesized by A*STAR researchers. Reproduced from Ref. 1 and licensed under CC BY 4.0 © 2015 Z. Fan et al.

The atomic structure of the new phase of gold synthesized by A*STAR researchers. Reproduced from Ref. 1 and licensed under CC BY 4.0 © 2015 Z. Fan et al.

A Dec. 2, 2015 A*STAR news release, which originated the news item, provides more details,

The researchers also produced 4H hexagonal phases of the precious metals silver, platinum and palladium by growing them on top of the gold 4H hexagonal phase.

The cubic phase looks identical when viewed front on, from one side or from above. In contrast, the new 4H hexagonal phase lacks this cubic symmetry and hence varies more with direction — a property known as anisotropy. This lower symmetry gives it more directionally varying optical properties, which may make it useful for plasmonic applications. “Our finding is not only is of fundamental interest, but it also provides a new avenue for unconventional applications of plasmonic devices,” says Wu.

The team is keen to explore the potential of their new phase. “In the future, we hope to leverage the unconventional anisotropic properties of the new gold phase and design new devices with excellent performances not achievable with conventional face-centered-cubic gold,” says Wu. The synthesis method also gives rise to the potential for new strategies for controlling the crystalline phase of nanomaterials made from the noble metals.

Here’s a link to and a citation for the paper,

Stabilization of 4H hexagonal phase in gold nanoribbons by Zhanxi Fan, Michel Bosman, Xiao Huang, Ding Huang, Yi Yu, Khuong P. Ong, Yuriy A. Akimov, Lin Wu, Bing Li, Jumiati Wu, Ying Huang, Qing Liu, Ching Eng Png, Chee Lip Gan, Peidong Yang & Hua Zhang. Nature Communications 6, Article number: 7684 doi:10.1038/ncomms8684 Published 28 July 2015

This is an open access paper.

Kavli Foundation roundtable on artificial synthesis as a means to produce clean fuel

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A Sept. 9, 2015 news item on Azonano features a recent roundtable discussion about artificial photosynthesis and clean fuel held by the Kavli Foundation,

Imagine creating artificial plants that make gasoline and natural gas using only sunlight. And imagine using those fuels to heat our homes or run our cars without adding any greenhouse gases to the atmosphere. By combining nanoscience and biology, researchers led by scientists at University of California, Berkeley, have taken a big step in that direction.

Peidong Yang, a professor of chemistry at Berkeley and co-director of the school’s Kavli Energy NanoSciences Institute, leads a team that has created an artificial leaf that produces methane, the primary component of natural gas, using a combination of semiconducting nanowires and bacteria. The research, detailed in the online edition of Proceedings of the National Academy of Sciences in August, builds on a similar hybrid system, also recently devised by Yang and his colleagues, that yielded butanol, a component in gasoline, and a variety of biochemical building blocks.

The research is a major advance toward synthetic photosynthesis, a type of solar power based on the ability of plants to transform sunlight, carbon dioxide and water into sugars. Instead of sugars, however, synthetic photosynthesis seeks to produce liquid fuels that can be stored for months or years and distributed through existing energy infrastructure.

In a [Kavli Foundation] roundtable discussion on his recent breakthroughs and the future of synthetic photosynthesis, Yang said his hybrid inorganic/biological systems give researchers new tools to study photosynthesis — and learn its secrets.

There is a list of the participants and an edited transcript of the roundtable, which took place sometime during summer 2015, on the Kavli Foundation’s Fueling up: How nanoscience is creating a new type of solar power webpage (Note: Links have been removed),

The participants were:

PEIDONG YANG – is professor of chemistry and Chan Distinguished Professor of Energy at University of California, Berkeley, and co-director of the Kavli Energy NanoScience Institute at Berkeley National Laboratory and UC Berkeley. He serves as director of the California Research Alliance by BASF, and was a founding member of the U.S. Department of Energy (DOE) Joint Center for Artificial Photosynthesis (JCAP).
THOMAS MOORE – is Regents’ Professor of Chemistry and Biochemistry and past director of the Center for Bioenergy & Photosynthesis at Arizona State University. He is a past president of the American Society for Photobiology, and a team leader at the Center for Bio-Inspired Solar Fuel Production.
TED SARGENT – is a University Professor of Electrical and Computer Engineering at the University of Toronto where he is vice-dean for research for the Faculty of Applied Science and Engineering. He holds the Canada Research Chair in Nanotechnology and is a founder of two companies, InVisage Technologies and Xagenic.

…

THE KAVLI FOUNDATION (TKF): Solar cells do a good job of converting sunlight into electricity. Converting light into fuel seems far more complicated. Why go through the bother?

THOMAS MOORE: That’s a good question. In order to create sustainable, solar-driven societies, we need a way to store solar energy. With solar cells, we can make electricity efficiently, but we cannot conveniently store that electricity to use when it is cloudy or at night. If we want to stockpile large quantities of energy, we have to store it as chemical energy, the way it is locked up in coal, oil, natural gas, hydrogen and biomass.

PEIDONG YANG: I agree. Perhaps, one day, researchers will come up with an effective battery to store photoelectric energy produced by solar cells. But photosynthesis can solve the energy conversion and storage problem in one step. It converts and stores solar energy in the chemical bonds of organic molecules.

TED SARGENT: Much of the globe’s power infrastructure, from automobiles, trucks and planes to gas-fired electrical generators, is built upon carbon-based fossil fuels. So creating a new technology that can generate liquid fuels that can use this infrastructure is a very powerful competitive advantage for a renewable energy technology.

…

For someone who’s interested in solar energy and fuel issues, this discussion provide a good introduction to some of what’s driving the research and, happily, none of these scientists are proselytizing.

One final comment. Ted Sargent has been mentioned here several times in connection with his work on solar cells and/or quantum dots.

Platinum catalysts and their shortcomings

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The problem boils down to the fact that platinum isn’t cheap and so US Dept. of Energy research laboratories are looking for alternatives to or ways of making more efficient use of platinum according to a June 16, 2015 news item on Nanowerk,

Visions of dazzling engagement rings may pop to mind when platinum is mentioned, but a significant share of the nearly half a million pounds of the rare metalExternal link [sic] mined each year ends up in vehicle emission systems and chemical manufacturing plants. The silvery white metal speeds up or enhances reactions, a role scientists call serving as a catalyst, and platinum is fast and efficient performing this function.

Because of its outstanding performance as a catalyst, platinum plays a major role in fuel cells. Inside a fuel cell, tiny platinum particles break apart hydrogen fuel to create electricity. Leftover protons are combined with oxygen ions to create pure water.

Fuel cells could let scientists turn wind into fuel. Right now, electricity generated by wind turbines is not stored. If that energy could be converted into hydrogen to power fuel cells, it would turn a sporadic source into a continuous one.

The problem is the platinum – a scarce and costly metal. Scientists funded by the U.S. Department of Energy’s Office of Science are seeing if something more readily available, such as iron or nickel, could catalyze the reaction.

But, earth-abundant metals cannot simply be used in place of platinum and other rare metals. Each metal works differently at the atomic level. It takes basic research to understand the interactions and use that knowledge to create the right catalysts.

A June 15, 2015 US Department of Energy Office of Science news release, which originated the news item, describes various efforts,

At the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, scientists are gaining new understanding of catalysts based on common metals and how they move protons, the positively charged, oft-ignored counterpart to the electron.

Center Director Morris Bullock and his colleagues showed that protons’ ability to move through the catalyst greatly influences the catalyst’s speed and efficiency. Protons move via relays — clusters of atoms that convey protons to or from the active site of catalysts, where the reaction of interest occurs. The constitution, placement, and number of relays can let a reaction zip along or grind to a halt. Bullock and his colleagues are creating “design guidelines” for building relays.

Further, the team is expanding the guidelines to examine proton movement related to the solutions and surfaces where the catalyst resides. For example, matching the proton-donating abilityExternal link [sic] of a nickel-based catalyst to that of the surrounding liquid, much like matching your clothing choice with the event you’re attending, eases protons’ travels. The benefit? Speed. A coordinated catalyst pumped out 96,000 hydrogen molecules a second — compared to just 27,000 molecules a second without the adjustment.

This and other research at the Energy Frontier Research Center is funded by the DOE Office of Science’s Office of Basic Energy Sciences. The Center is led by Pacific Northwest National Laboratory.

At two other labs, research shows how changing the catalyst’s superstructure, which contains the proton relays and wraps around the active site, can also increase the speed of the reaction. Led by Argonne National Lab’s Vojislav Stamenkovic and Berkeley Lab’s Peidong Yang, researchers created hollow platinum and nickel nanoparticles, a thousand times smaller in diameter than a human hair. The 12-sided particles split oxygen molecules into charged oxygen ions, a reaction that’s needed in fuel cells. The new catalyst is far more active and uses far less platinum than conventional platinum-carbon catalysts.

Building the catalysts begins with tiny structures made of platinum and nickel held in solution. Oxygen from the air dissolves into the liquid and selectively etches away some of the nickel atoms. The result is a hollow framework with a highly active platinum skin over the surface. The open design of the catalyst allows the oxygen to easily access the platinum. The new catalyst has a 36-fold increase in activity compared to traditional platinum–carbon catalysts. Further, the new hollow structure continues to work far longer in operating fuel cells than traditional catalysts.

I think we’re entering the ‘slow’ season newswise so there are likely to be more of these ’roundup’ pieces being circulated in the online nanosciencesphere and, consequently, here. too.

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

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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.