Nav: Home

Penn chemists lay groundwork for countless new, cleaner uses of methane

March 24, 2016

Methane is the world's most abundant hydrocarbon. It's the major component of natural gas and shale gas and, when burned, is an effective fuel. But it's also a major contributor to climate change, with 24 times greater potency as a greenhouse gas than carbon dioxide.

With a new method, a research team led by chemists at the University of Pennsylvania has demonstrated the potential to use methane not as a fossil fuel but as a versatile chemical building block with which to make more complex molecules, such as pharmaceuticals and other value-added substances.

The reaction also offers a way of taking advantage of the properties of methane without releasing greenhouse gases.

"Finding ways to use methane besides burning it as a fuel constitutes a practical approach to using this abundant gas," said Daniel Mindiola, senior author on the paper and a Presidential Professor in Penn's Department of Chemistry in the School of Arts & Sciences. "Our method will hopefully provide inspiration to move away from burning our resources and instead using them more as a carbon building block to prepare more valuable materials."

The study will be published in Science.

Mindiola collaborated on the work with Kyle Smith, a graduate student in Mindiola's lab and the paper's lead author; Simon Berritt, director of Penn's High Throughput Screening Center based in the Department of Chemistry; Mariano González-Moreiras, a visiting scholar; Seihwan Ahn and Mu-Hyun Baik of Korea's Advanced Institute of Science and Technology; and Milton R. Smith III, a professor at Michigan State University who, together with Rob Maleczka, first discovered the chemical reaction known as carbon-hydrogen borylation upon which the current work builds.

Methane is comprised of a carbon atom bonded to four hydrogen atoms. When it is burned, all four of the carbon-hydrogen bonds are broken, resulting in the production of carbon dioxide and water, both of which are greenhouse gases.

"If only one or two hydrogen bonds could be broken efficiently, then it might be possible to connect carbon atoms from two or more methane molecules to make larger hydrocarbons," said Michigan State's Smith. "For example, gasoline is a mixture of hydrocarbons containing between four and 12 carbon atoms. The polyethylene used to make garbage bags and milk jugs is composed of millions of carbon atoms."

Selectively controlling the carbon-hydrogen bonds has been difficult, however. Chemists have therefore considered methane relatively inert unless burned. In addition, because methane is a gas at ambient temperatures and pressures, it is not the easiest chemical to manipulate.

But Mindiola had a brainstorm: what if he tried a borylation reaction using methane while varying pressure conditions? Carbon-hydrogen borylation is a process developed by Smith and colleagues in which a hydrocarbon reacts with a boron-containing compound, catalyzed by a metal. The reaction results in the replacement of a carbon-hydrogen bond on the hydrocarbon with a carbon-boron bond. This bond can then later be easily swapped to bond the carbon to any number of other chemical groups. Though borylation was discovered more than a decade ago, no one had tried it using methane, the simplest of hydrocarbons.

The researchers decided to attempt this. Taking advantage of known conditions reported in the literature for other substrates, they determined the right combination of compounds and catalysts that might work, then used a computational approach to evaluate different conditions and reagents that might improve the reaction's efficiency. Finally, they used Penn's High Throughput Screening Center, one of only a handful of such facilities in the country, which allows for the testing of 96 different reactions at once, to identify the most efficient conditions for the reaction.

The Penn facility is unique in that it allows for reactions to be done under high-pressure conditions, which permitted the team to use methane in a gaseous state as opposed to working under ambient conditions.

The most favorable reaction, conducted under relatively mild conditions of 150 degrees Celsius and 500 pound per square inch of methane, using the metal iridium as a catalyst, resulted in yields as high as 52 percent borylated methane with high selectivity for the carbon-hydrogen borylation of one C-H bond as opposed to multiple bonds.

"It turns out methane is not as inert as one would have expected," Mindiola said. "We were able to borylate it using off-the-shelf reagents, which is very convenient."

The team is currently evaluating other reagents to do a similar reaction. For example, they are trying to find alternative catalysts because iridium, though commercially available, is relatively rare and expensive. Cobalt may offer a promising alternative. They are also testing silicon compounds as an alternative to those containing the rarer boron.

Methane is currently so abundant that the petrochemical industry burns approximately $50 million of methane each year in gas flares, in part due to a lack of storage capacity. And while some methane is used for steam reforming, a process that forms carbon monoxide and hydrogen that can be used in fuel cells or to make ammonia for fertilizers, the researchers believe the borylation reaction can offer a meaningful alternative use for methane.

"I think this work is going to inspire a lot of chemistry and get people thinking about methane in a different way," Mindiola said. "That doesn't mean that the natural gas industry is going to borylate all the methane they're extracting -- there is a lot out there and boron is rare -- but it's another valuable option."

Mindiola noted that this work complements another paper, published in the same issue of Science, led by the University of Michigan's Melanie Sanford. That report identifies a way to perform borylation of methane's carbon-hydrogen bonds selectively, borylating either one or two bonds, and to expand this method to the second most abundant hydrocarbon, ethane. Implementing both reactions could make it more feasible for methane to be used by the pharmaceutical industry as well as many others to craft designer molecules with a plethora of uses.
-end-
The study was supported by the University of Pennsylvania, the Ministry of Education of Spain, Korea's Institute for Basic Science and the National Institutes of Health.

University of Pennsylvania

Related Climate Change Articles:

The black forest and climate change
Silver and Douglas firs could replace Norway spruce in the long run due to their greater resistance to droughts.
For some US counties, climate change will be particularly costly
A highly granular assessment of the impacts of climate change on the US economy suggests that each 1°Celsius increase in temperature will cost 1.2 percent of the country's gross domestic product, on average.
Climate change label leads to climate science acceptance
A new Cornell University study finds that labels matter when it comes to acceptance of climate science.
Was that climate change?
A new four-step 'framework' aims to test the contribution of climate change to record-setting extreme weather events.
It's more than just climate change
Accurately modeling climate change and interactive human factors -- including inequality, consumption, and population -- is essential for the effective science-based policies and measures needed to benefit and sustain current and future generations.
Climate change scientists should think more about sex
Climate change can have a different impact on male and female fish, shellfish and other marine animals, with widespread implications for the future of marine life and the production of seafood.
Climate change prompts Alaska fish to change breeding behavior
A new University of Washington study finds that one of Alaska's most abundant freshwater fish species is altering its breeding patterns in response to climate change, which could impact the ecology of northern lakes that already acutely feel the effects of a changing climate.
Uncertainties related to climate engineering limit its use in curbing climate change
Climate engineering refers to the systematic, large-scale modification of the environment using various climate intervention techniques.
Public holds polarized views about climate change and trust in climate scientists
There are gaping divisions in Americans' views across every dimension of the climate debate, including causes and cures for climate change and trust in climate scientists and their research, according to a new Pew Research Center survey.
The psychology behind climate change denial
In a new thesis in psychology, Kirsti Jylhä at Uppsala University has studied the psychology behind climate change denial.

Related Climate Change Reading:

Climate Change: What Everyone Needs to Know®
by Joseph Romm (Author)

Climate change will have a bigger impact on humanity than the Internet has had. The last decade's spate of superstorms, wildfires, heat waves, and droughts has accelerated the public discourse on this topic and lent credence to climatologist Lonnie Thomson's 2010 statement that climate change "represents a clear and present danger to civilization." In June 2015, the Pope declared that action on climate change is a moral issue.

This book offers the most up-to-date examination of climate change's foundational science, its implications for our future, and the core clean energy solutions.... View Details


This Changes Everything: Capitalism vs. The Climate
by Naomi Klein (Author)

The most important book yet from the author of the international bestseller The Shock Doctrine, a brilliant explanation of why the climate crisis challenges us to abandon the core “free market” ideology of our time, restructure the global economy, and remake our political systems.

In short, either we embrace radical change ourselves or radical changes will be visited upon our physical world. The status quo is no longer an option.

In This Changes Everything Naomi Klein argues that climate change isn’t just another issue to be neatly filed between taxes and... View Details


Climate Change: The Facts
by J.Abbot (Author), J.S. Armstrong (Author), A.Bolt (Author), R.Carter (Author), R.Darwall (Author), J.Delingpole (Author), C.Essex (Author), S.Franks (Author), K.Green (Author), D.Laframboise (Author), N.Lawson (Author), B.Lewin (Author), R.Lindzen (Author), J.Marohasy (Author), R.McKitrick (Author), P.Michaels (Author), A.Moran (Author), J.Nova (Author), G.Paltridge (Author), I.Plimer (Author), W.Soon (Author), M.Steyn (Author), A.Watts (Author), Alan Moran (Editor)

Tirelessly promoted by princes, presidents, actors and activists, "climate change" has become a dominant theme of global politics. But what's really going on as the "pause" in global warming prepares to enter its third decade? In this new anthology, leading scientists and commentators from the United States, the United Kingdom, Canada and Australia consider the climate from every angle - the science, the policy and the politics. View Details


A Global Warming Primer: Answering Your Questions About The Science, The Consequences, and The Solutions
by Jeffrey Bennett (Author)

Winner:
2017 NSTA, Outstanding Science Trade Books
2017 Children's Book Council, Best STEM Books
Nautilus Book Award, Silver, Ecology and Environment

Is human-induced global warming a real threat to our future? Most people will express an opinion on this question, but relatively few can back their opinions with solid evidence. Many times we’ve even heard pundits say “I am not a scientist” to avoid the issue altogether. But the truth is, the basic science is not that difficult. Using a question and answer format, this book will help readers achieve three major... View Details


Climate Change: The Facts 2017
by Jennifer Marohasy (Editor)

Climate Change: The Facts 2017 contains 22 essays by internationally-renowned experts and commentators, including Dr Bjorn Lomborg, Dr Matt Ridley, Professor Peter Ridd, Dr Willie Soon, Dr Ian Plimer, Dr Roy Spencer, and literary giant Clive James. The volume is edited by Dr Jennifer Marohasy, Senior Fellow at the Institute of Public Affairs. Fourteen of the contributors currently hold or have held positions at a university or a scientific research organisation.

Dr Jennifer Marohasy said, "Climate Change: The Facts 2017 presents the case for climate change policies... View Details


Don't Even Think About It: Why Our Brains Are Wired to Ignore Climate Change
by George Marshall (Author)

Most of us recognize that climate change is real yet we do nothing to stop it. What is the psychological mechanism that allows us to know something is true but act as if it is not? George Marshall's search for the answers brings him face to face with Nobel Prize-winning psychologists and Texas Tea Party activists; the world's leading climate scientists and those who denounce them; liberal environmentalists and conservative evangelicals. What he discovers is that our values, assumptions, and prejudices can take on lives of their own, gaining authority as they are shared, dividing people in... View Details


Climate of Hope: How Cities, Businesses, and Citizens Can Save the Planet
by Michael Bloomberg (Author), Carl Pope (Author)

NEW YORK TIMES BESTSELLER

From Mayor Michael Bloomberg and former head of the Sierra Club Carl Pope comes a manifesto on how the benefits of taking action on climate change are concrete, immediate, and immense. They explore climate change solutions that will make the world healthier and more prosperous, aiming to begin a new type of conversation on the issue that will spur bolder action by cities, businesses, and citizens―and even, someday, by Washington.

"Climate of Hope is an inspiring must read." ―Former Vice President Al Gore,... View Details


The Thinking Person's Guide to Climate Change
by Robert Henson (Author)

Everybody can be a thinking person when it comes to climate change, and this book is a perfect roadmap.  Start a web search for “climate change” and the first three suggestions are “facts,” “news,” and “hoax.” The Thinking Person's Guide to Climate Change is rooted in the first, up to date on the second, and anything but the last. Produced by one of the most venerable atmospheric science organizations, it is a must-read for anyone looking for the full story on climate change.

Using global research and written with nonscientists in mind, the Guide breaks... View Details


Enviromedics: The Impact of Climate Change on Human Health
by Jay Lemery (Author), Paul Auerbach (Author)

Many of us have concerns about the effects of climate change on Earth, but we often overlook the essential issue of human health. This book addresses that oversight and enlightens readers about the most important aspect of one of the greatest challenges of our time.

The global environment is under massive stress from centuries of human industrialization. The projections regarding climate change for the next century and beyond are grim. The impact this will have on human health is tremendous, and we are only just now discovering what the long-term outcomes may be.

By... View Details


Dire Predictions, 2nd Edition: Understanding Climate Change
by Michael E. Mann (Author), Lee R. Kump (Author)

Explore global warming with graphics, illustrations, and charts that separate climate change fact from fiction, presenting the truth about global warming in a way that's both accurate and easy to understand. Respected climate scientists Michael E. Mann and Lee R. Kump address important questions about global warming and climate change, diving into the information documented by the IPCC (Intergovernmental Panel on Climate Change) and breaking it down into clear graphics that explain complex climate questions in simple illustrations that present the truth of the global warming problem clearly.... View Details

Best Science Podcasts 2017

We have hand picked the best science podcasts for 2017. Sit back and enjoy new science podcasts updated daily from your favorite science news services and scientists.
Now Playing: TED Radio Hour

Simple Solutions
Sometimes, the best solutions to complex problems are simple. But simple doesn't always mean easy. This hour, TED speakers describe the innovation and hard work that goes into achieving simplicity. Guests include designer Mileha Soneji, chef Sam Kass, sleep researcher Wendy Troxel, public health advocate Myriam Sidibe, and engineer Amos Winter.
Now Playing: Science for the People

#448 Pavlov (Rebroadcast)
This week, we're learning about the life and work of a groundbreaking physiologist whose work on learning and instinct is familiar worldwide, and almost universally misunderstood. We'll spend the hour with Daniel Todes, Ph.D, Professor of History of Medicine at The Johns Hopkins University, discussing his book "Ivan Pavlov: A Russian Life in Science."