Searching for Photocathodes that Convert CO2 into Fuels

Figure
Six-step selection criteria used in the search for photocathodes for CO2 reduction. The search began with 68,860 inorganic compounds. The number of materials that satisfied the requirements of each step are shown in red, with 52 meeting all the requirements.

Carbon dioxide (CO2) has a bad reputation due to its pivotal role in the greenhouse gas effect at the Earth’s surface. But scientists at the Joint Center for Artificial Photosynthesis (JCAP), a U.S. Department of Energy (DOE) Innovation Hub, view CO2 as a promising solution to clean, low-cost, renewable energy.

JCAP is a team led by the California Institute of Technology (Caltech) that brings together more than 100 world-class scientists and engineers, primarily from Caltech and its lead partner, Lawrence Berkeley National Laboratory (Berkeley Lab).

The JCAP team is developing new ways to produce transportation fuels from CO2, sunlight, and water using a process called artificial photosynthesis, which harvests solar energy and stores it in chemical bonds. If successful, they’ll be able to produce fuels while also eliminating some CO2 — a “win-win,” according to Arunima Singh, an assistant professor of physics at Arizona State University and a former member of the JCAP team.

Singh became involved in the research as a postdoctoral associate at Berkeley Lab, where she searched for new photocathodes to efficiently convert CO2 to chemical fuels — a major hurtle to realizing scalable artificial photosynthesis.

“There is a dire need to find new materials to enable the photocatalytic conversion of CO2. The existing photocathodes have very low efficiencies and product selectivity, which means the CO2 produces many products that are expensive to distill,” said Singh. “Previous experimental attempts found new photocatalytic materials by trial and error, but we wanted to do a more directed search.”

Searching for Needles in a Materials Project Haystack

Using supercomputing resources at the National Energy Research Scientific Computing Center (NERSC), the Berkeley Lab team performed a massive photocathode search, starting with 68,860 materials and screening them for specific intrinsic properties. Their results were published in the January issue of Nature Communications.

“The candidate materials need to be thermodynamically stable so they can be synthesized in the lab. They need to absorb visible light. And they need to be stable in water under the highly reducing conditions of CO2 reduction, ” said first author Singh. “These three key properties were already available through the Materials Project.”

The Materials Project is a DOE-funded database of materials properties calculated based on predictive quantum-mechanical simulations using supercomputing clusters at NERSC, which is a DOE Office of Science User Facility. The database includes both experimentally known materials and hypothetical structures predicted by machine learning algorithms or various other procedures. Of the 68,860 candidate materials screened in the Nature Communications study, about half had already been experimentally synthesized, while the remaining were hypothetical.

The researchers screened these materials in six steps. First they used the Materials Project to identify the materials that were thermodynamically stable, able to absorb visible light, stable in water, and electrochemically stable. This strategy reduced the candidate pool to 235 materials — dramatically narrowing the list for the final two steps, which required computationally intensive calculations.

“By leveraging a large amount of data already available in the Materials Project, we were able to cut the computational cost of the project by several millions of CPU hours,” said Kristin Persson, a faculty scientist in Berkeley Lab’s Energy Technologies Area and senior author on the paper.

Additional Screening with First-Principles Calculations

However, the Materials Project database did not have all the necessary data. So the final screening required new first-principles simulations of materials properties based on quantum mechanics to accurately estimate the electronic structures and understand the energy of the excited electrons. These calculations were computed at NERSC and the Texas Advanced Computing Center (TACC) for the remaining 235 candidate materials.

“NERSC is the backbone of the Materials Project computation and database. But we also used about two million NERSC core hours to do the step 5 and 6 calculations,” said Singh. “Without NERSC, we would have been running our simulations on 250 cores for 24 hours a day for a year, versus being able to do these calculations in parallel on NERSC in a matter of a few months.”

The team also used about half a million core hours for these calculations at TACC, which were allocated through the National Science Foundation’s Extreme Science and Engineering Discovery Environment (XSEDE).

These theoretical calculations showed that 52 materials met all of the stringent requirements of the screening process, but that only nine of these had been previously studied for CO2 reduction. Among the 43 newly identified photocathodes, 35 have previously been synthesized and eight are hypothetical materials.

“We performed the largest exploratory search for CO2 reduction photocathodes to date, covering 68,860 materials and identifying 43 new photocathode materials exhibiting promising properties,” Persson said.

Finally, the researchers narrowed the list down to 39 promising candidates by looking at the vibrational properties of the eight hypothetical materials and ruling out the four predicted to be unstable by themselves.

However, more work is needed before artificial photosynthesis becomes are reality, including working with their experimental colleagues like Caltech’s John Gregoire (a leader of JCAPS’s high-throughput experimentation laboratory) to validate their computational results.

“We have collaborators at Berkeley Lab and Caltech who are actively trying to grow these materials and test them,” Singh said. “I’m excited to see our study opening up new avenues of research.”

This is a reposting of my Computing Sciences news feature, courtesy of Berkeley Lab.

Sick people are worse for the environment, a study shows

Photo by ryan harvey

Environmental degradation is widely recognized to contribute to human illness. However, little research has been done to investigate the impact of human illness on the environment. This is a critical question particularly for the millions of people around the world who depend on natural resources for food and income while coping with high burdens of infectious diseases.

When people are sick, they often alter their use of natural resources in ways that harm the environment, according to a new study reported in the Proceedings of the National Academy of Sciences.

Specifically, the researchers examined how illness influenced fishing practices in the community around Lake Victoria, Kenya, which has high rates of HIV and other illnesses. They interviewed about 300 households several times over 16 months, collecting and analyzing data about household fishing habits and mental and physical health. They found that healthy people are better for the environment.

“Studies suggest that people will spend less time on their livelihoods when they are sick, but we didn’t see that trend in our study. Instead, we saw a shift toward more destructive fishing methods when people were ill,” said lead author Kathryn Fiorella, PhD, a postdoctoral scholar at Cornell University, in a recent news release.

The study found that sick fishermen were less likely to legally fish in deep waters or overnight to target the more sustainable mature fish. Instead, they used destructive fishing methods that were concentrated along the shoreline — such as using a beach dragnet that captures a high proportion of juvenile fish and disturbs shallow fish breeding habits.

Basically, sick fishermen just wanted to get their catch quickly with less energy. They were focused on their short-term goal and not worried about depleting the fish stock.

In light of this study, the authors suggest that institutions and organizations focused on protecting the environment may need to more deeply consider the health of communities. The paper concludes, “Our study emphasizes the importance of considering health, governance, and ecosystems through an integrative lens.”

This is a reposting of my Scope blog story, courtesy of Stanford School of Medicine.

Berkeley Lab Tackles Vaccine Delivery Problem with Portable Solar-Powered Vaccine Fridge

LBNL Institute for Globally Transformative Technologies research team with prototype vaccine fridge and backpack for developing countries. (Berkeley Lab / Roy Kaltschmidt)
LBNL Institute for Globally Transformative Technologies research team with prototype vaccine fridge and backpack for developing countries. (Berkeley Lab / Roy Kaltschmidt)

Vaccines are arguably one of the most important inventions of mankind. Unfortunately, vaccines must be produced and stored in an environment with very tight temperature regulation – between 36 °F and 46 °F – to keep the vaccine bugs alive. So vaccine delivery is a major problem due to the absence of reliable refrigeration in many remote countries.

Approximately 30 million children worldwide – roughly one in five – do not receive immunizations, leaving them at significant risk of disease. As a result, 1.5 million children under the age of five die annually from vaccine-preventable diseases, such as pneumonia and diarrhea. Perhaps more surprising, almost half of the vaccines in developing countries are thrown away because they get too warm during delivery so they are no longer viable. Some administered vaccines are also ineffective because they froze during transport, but there is no easy way to test this.

Scientists at Lawrence Berkeley National Laboratory (LBNL) are trying to solve this vaccine delivery problem by developing a portable solar-powered fridge. Fabricated entirely at LBNL, their portable solar-powered vaccine fridge will be transported by bicycle or motorcycle in remote areas of the developing world. Zach Friedman and Reshma Singh are leading the project as part of the LBNL Institute for Globally Transformative Technologies, which seeks to bring scientific and technological breakthroughs to address global poverty and related social ills.

The team’s first prototype portable fridge uses a thermoelectric heat pump, rather than a traditional vapor compression heat pump that relies on a circulating liquid refrigerant to absorb and remove heat. The thermoelectric chips were initially developed to keep laptops cool, so laptops could be made thinner without fans. The technology was adapted for this global application to reduce the size and weight of the fridge.

Their portable units have a one to three-liter capacity, much smaller than standard solar fridges that are typically 50 liters or more. Once the fridge cools down to the right temperature (36 °F – 46 °F), it is designed to run within that temperature range for at least five days without any power, at an ambient outside temperature as hot as 110 °F.

Before the researchers can field test their first prototype fridge in Africa, they need to pass the World Health Organization’s Performance, Quality and Safety testing protocol for products used in immunization programs. They are currently busy performing in-house testing at LBNL to ensure that they pass the formal tests, which will be conducted by an independent laboratory in the UK.

“We aren’t in the process of field testing yet, but we have established field testing agreements in both Kenya and Nigeria and have locations identified,” said Friedman. “We expect to start testing this coming year.”

Meanwhile, they are continuing their portable fridge development. “Currently, we are pursuing both thermoelectric and vapor compression heat pumps, even for these smaller devices,” explained Jonathan Slack, lead engineer. “It is not clear which will win out in terms of manufacturability and affordability.”

They are also developing a backpack version of the vaccine fridge. However, human-carried devices have to meet stricter World Health Organization standards, so they are focusing at this stage on the small portable fridge instead.

Ultimately their goal is to make it easy for health care workers to deliver viable vaccines to children in remote areas, solving the “last miles” of vaccine delivery.

This is a repost of my KQED Science blog.

Time to Invest in Delta Levees

US Army Corp of Engineers inspect a Sacramento river levee ( U.S. Army photo by Chris Gray-Garcia, Flickr).
US Army Corp of Engineers inspect a Sacramento river levee ( U.S. Army photo by Chris Gray-Garcia, Flickr).

Two hundred years ago most of the Sacramento-San Joaquin Delta (Delta) was a vast wetland. Early settlers built an intricate levee system to create dry “islands” suitable for farming.

Today, these levees help protect people, property, natural resources, and infrastructure of statewide importance. The Delta is home to more than 515,000 people and 750 animal and plant species; supplies drinking water to 25 million Californians and irrigation water for the majority of California’s agricultural industry; and attracts 12 million recreational visits annually.

Unfortunately the Delta levees are vulnerable to damage caused by floods, wave action, seepage, subsidence, earthquakes, and sea-level rise. While the occasional levee break is a fact of Delta life, a catastrophic levee failure could cause injury to people or loss of life. It could also damage property, highways, energy utilities, water supply systems, and the environment —all with regional and statewide consequences.

A variety of actions can be used to reduce flood risk in the Delta. The Delta Levees Council is developing a strategy to evaluate and guide future California investments to reduce the likelihood and consequences of levee failures. Interested? Learn more about this project and get involved by attending public meetings.

Prescription Drug Take-Back Day

prescription bottles
Photograph courtesy of joguldi via a Creative Commons license.

Do you have expired or unused prescription drugs stacked up in your medicine cabinet? It’s not safe to flush them down the toilet or throw them out with the trash. But you can get rid of them safely, easily and for free at sites across the US tomorrow. Yep, it is National Prescription Drug Take-Back Day on Saturday October 26 from 10 am – 2 pm. Drop them off at a local collection site.

The Threat of Terrestrial Carbon

Dr. Margaret Torn at an NGEE field test site near Council, Alaska. Lawrence Berkeley National Laboratory – Roy Kaltschmidt, photographer.
Dr. Margaret Torn at an NGEE field site near Council, Alaska. Photo: Lawrence Berkeley National Laboratory – Roy Kaltschmidt, photographer.

In the northernmost city of the United States – Barrow, Alaska – the treeless flat tundra looks stark and forbidding to many people. The permanently frozen soil (permafrost) is only capable of supporting plants like moss, heather and lichen and the temperatures can drop as low as -60 °F.

However, this tundra is a mecca for climate scientists like Dr. Margaret Torn, co-lead of the Climate and Carbon Sciences Program at Lawrence Berkeley National Laboratory (Berkeley Lab). Torn just returned from performing field experiments near Barrow. She is part of the 10-year Next-Generation Ecosystem Experiment, a large collaboration of scientists and engineers who are trying to better understand the Arctic terrestrial ecosystem so they can improve vital climate predictions. These scientists are finding new ways to study the complex ecosystem of the Arctic landscape, including looking deep into the soil.

“Soil is a big mystery,” explained Torn. “We don’t understand why soil holds so much carbon. And we don’t understand how a warming climate will affect soils. The question being whether a warming climate will result in carbon transferring from soils to the atmosphere as greenhouse gases, creating additional global warming.”

Soils are an important part of the carbon cycle. In the natural carbon cycle, carbon dioxide is taken up by plants and photosynthesized. If the plants aren’t harvested for food or fuel, they decay and their organic matter makes its way to the soil where it is processed by tiny microbes – bacteria and fungi – that release the carbon dioxide back into the atmosphere.

Soils are critical because they store about 2.3 trillion tons of carbon – more than twice as much as the atmosphere or vegetation. In comparison, burning fossil fuels releases about 9 billion tons of carbon dioxide per year.

Soils are also a long-term reservoir of carbon. Carbon cycles very slowly deep in the soil, where it can remain for 50,000 years. So a critical question is how long will soils contain these rich deposits of carbon? Will the carbon stay put? Or will it enter the atmosphere in the near future, greatly amplifying climate change?

The Arctic tundra is an area that is particularly worrisome. Cold temperatures suppress microbial growth, which helps trap the vast stores of carbon in the soil. But global warming is causing the Arctic permafrost to thaw, triggering the microbes to become active and respire carbon dioxide into the atmosphere.

Equipment Ron and her team use to sample greenhouse gases flowing from the land to the atmosphere. They later determine how old the carbon is in these gas samples using carbon-14 dating. Photo: Margaret Torn.
Equipment Torn and her team use to sample greenhouse gases flowing from the land into the atmosphere. They later determine how old the carbon is in these gas samples using carbon-14 dating. Photo: Margaret Torn.

Torn’s group drills wells in the Alaskan ground to directly measure the flow of carbon dioxide and methane from the land to the atmosphere. They measure these gas flows in areas where the permafrost is intact and where it is thawing, trying to understand the environmental variables that are controlling the release of greenhouse gases.

They see very high methane concentrations in areas where the permafrost is thawing. However, this summer they found that in some areas specialized microbes consume this methane before it is released, so carbon dioxide is released into the atmosphere instead. This is good news for the environment, because carbon dioxide is a less potent greenhouse gas than methane.

They also take soil core samples from different regions in Barrow, and then incubate them at different temperatures back home at Berkeley Lab. They find that one handful of soil has thousands of different kinds of microbes and billions of cells, which respond to the environment differently. They also determine how old the carbon is in the samples using carbon-14 dating.

“One thing we’ve seen this summer is that the carbon that is being decomposed just above the permafrost is more than 2500 years old,” described Torn. “So this place that we’re studying has been storing carbon for a long, long time. But that carbon can be decomposed and released as carbon dioxide very quickly when the conditions are right.”

These results have been validated by other recent experiments, but they contradict the old belief that carbon hidden deep in soil will remain there forever due to the soil’s material properties. “The field is evolving rapidly. We’re trying to unravel the mystery of why we see older carbon in the soil, trying to create a more realistic view,” explained Torn. “It is more complex. It’s the interaction between the entire ecosystem and the material properties that’s important.”

Of course the more complicated, realistic view makes climate modeling more challenging. Climate models are computer programs that simulate how the climate has changed in the past and how it will change in the future. They are critical to understanding our planet and how to limit the impact of human activity upon it. But scientists know that their climate models are wrong when it comes to soil carbon. This is why scientists need new data, like they are acquiring in Alaska, to test and improve their models.

“We can do so much better than we’re doing,” exclaimed Torn. “So we feel pretty confident that we can make improvements. It may not be perfect, but our work is going to make predictions more robust and believable.”

This is a repost of my KQED QUEST blog titled, “The Great Escape: How Soil Protects Us from Carbon Emissions.”

How Hot Will It Get?

Muir Glacer melt, Alaska. 1882 photo taken by G.D. Hazard; 2005 photo taken by Bruce F. Molnia. Courtesy of the Glacier Photograph Collection, National Snow and Ice Data Center/World Data Center for Glaciology.
Muir Glacer melt, Alaska. 1882 photo taken by G.D. Hazard; 2005 photo taken by Bruce F. Molnia. Courtesy of the Glacier Photograph Collection, National Snow and Ice Data Center/World Data Center for Glaciology.

Stay tuned for the next Science at the Theater, a free public lecture hosted by Lawrence Berkeley National Laboratory. It will be held on Monday April 22 at 7 pm at the Berkeley Repertory Theater.

Scientists will talk about their latest research findings on how the earth’s climate is changing, from the arctic to the rainforest. Participating speakers will address critical questions: What happens when the permafrost thaws? What do computer models predict about our future climate – floods, droughts, hurricanes and heat waves? What role do our forests play in carbon absorption? What kind of carbon tax might actually work?

Come find out what to expect and if there is anything you can do about it!