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Study reveals a reaction at the heart of many renewable energy technologies

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Study reveals a reaction at the heart of many renewable energy technologies


Study reveals a reaction at the heart of many renewable energy technologies

by Anne Trafton for MIT News

Boston MA (SPX) Jan 17, 2024






A key chemical reaction – in which the movement of protons between the surface of an electrode and an electrolyte drives an electric current – is a critical step in many energy technologies, including fuel cells and the electrolyzers used to produce hydrogen gas.

For the first time, MIT chemists have mapped out in detail how these proton-coupled electron transfers happen at an electrode surface. Their results could help researchers design more efficient fuel cells, batteries, or other energy technologies.



“Our advance in this paper was studying and understanding the nature of how these electrons and protons couple at a surface site, which is relevant for catalytic reactions that are important in the context of energy conversion devices or catalytic reactions,” says Yogesh Surendranath, a professor of chemistry and chemical engineering at MIT and the senior author of the study.



Among their findings, the researchers were able to trace exactly how changes in the pH of the electrolyte solution surrounding an electrode affect the rate of proton motion and electron flow within the electrode.



MIT graduate student Noah Lewis is the lead author of the paper, which appears in Nature Chemistry. Ryan Bisbey, a former MIT postdoc; Karl Westendorff, an MIT graduate student; and Alexander Soudackov, a research scientist at Yale University, are also authors of the paper.



Passing protons

Proton-coupled electron transfer occurs when a molecule, often water or an acid, transfers a proton to another molecule or to an electrode surface, which stimulates the proton acceptor to also take up an electron. This kind of reaction has been harnessed for many energy applications.



“These proton-coupled electron transfer reactions are ubiquitous. They are often key steps in catalytic mechanisms, and are particularly important for energy conversion processes such as hydrogen generation or fuel cell catalysis,” Surendranath says.



In a hydrogen-generating electrolyzer, this approach is used to remove protons from water and add electrons to the protons to form hydrogen gas. In a fuel cell, electricity is generated when protons and electrons are removed from hydrogen gas and added to oxygen to form water.



Proton-coupled electron transfer is common in many other types of chemical reactions, for example, carbon dioxide reduction (the conversion of carbon dioxide into chemical fuels by adding electrons and protons). Scientists have learned a great deal about how these reactions occur when the proton acceptors are molecules, because they can precisely control the structure of each molecule and observe how electrons and protons pass between them. However, when proton-coupled electron transfer occurs at the surface of an electrode, the process is much more difficult to study because electrode surfaces are usually very heterogenous, with many different sites that a proton could potentially bind to.



To overcome that obstacle, the MIT team developed a way to design electrode surfaces that gives them much more precise control over the composition of the electrode surface. Their electrodes consist of sheets of graphene with organic, ring-containing compounds attached to the surface. At the end of each of these organic molecules is a negatively charged oxygen ion that can accept protons from the surrounding solution, which causes an electron to flow from the circuit into the graphitic surface.



“We can create an electrode that doesn’t consist of a wide diversity of sites but is a uniform array of a single type of very well-defined sites that can each bind a proton with the same affinity,” Surendranath says. “Since we have these very well-defined sites, what this allowed us to do was really unravel the kinetics of these processes.”



Using this system, the researchers were able to measure the flow of electrical current to the electrodes, which allowed them to calculate the rate of proton transfer to the oxygen ion at the surface at equilibrium – the state when the rates of proton donation to the surface and proton transfer back to solution from the surface are equal. They found that the pH of the surrounding solution has a significant effect on this rate: The highest rates occurred at the extreme ends of the pH scale – pH 0, the most acidic, and pH 14, the most basic.



To explain these results, researchers developed a model based on two possible reactions that can occur at the electrode. In the first, hydronium ions (H3O+), which are in high concentration in strongly acidic solutions, deliver protons to the surface oxygen ions, generating water. In the second, water delivers protons to the surface oxygen ions, generating hydroxide ions (OH-), which are in high concentration in strongly basic solutions.



However, the rate at pH 0 is about four times faster than the rate at pH 14, in part because hydronium gives up protons at a faster rate than water.



A reaction to reconsider

The researchers also discovered, to their surprise, that the two reactions have equal rates not at neutral pH 7, where hydronium and hydroxide concentrations are equal, but at pH 10, where the concentration of hydroxide ions is 1 million times that of hydronium. The model suggests this is because the forward reaction involving proton donation from hydronium or water contributes more to the overall rate than the backward reaction involving proton removal by water or hydroxide.



Existing models of how these reactions occur at electrode surfaces assume that the forward and backward reactions contribute equally to the overall rate, so the new findings suggest that those models may need to be reconsidered, the researchers say.



“That’s the default assumption, that the forward and reverse reactions contribute equally to the reaction rate,” Surendranath says. “Our finding is really eye-opening because it means that the assumption that people are using to analyze everything from fuel cell catalysis to hydrogen evolution may be something we need to revisit.”



The researchers are now using their experimental setup to study how adding different types of ions to the electrolyte solution surrounding the electrode may speed up or slow down the rate of proton-coupled electron flow.



“With our system, we know that our sites are constant and not affecting each other, so we can read out what the change in the solution is doing to the reaction at the surface,” Lewis says.



The research was funded by the U.S. Department of Energy Office of Basic Energy Sciences.



Research Report:“A molecular-level mechanistic framework for interfacial proton-coupled electron transfer kinetics”


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3D-printed microstructure forest enhances solar steam desalination

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3D-printed microstructure forest enhances solar steam desalination


3D-printed microstructure forest enhances solar steam desalination

by Clarence Oxford

Los Angeles CA (SPX) Jul 24, 2024







To address the global freshwater scarcity issue, researchers in Singapore have developed advanced solar steam generators (SSGs) for seawater desalination. This method, powered by renewable energy, mimics the natural water cycle by using solar energy to evaporate and purify water, offering a potentially cost-effective solution compared to traditional, energy-intensive desalination techniques. However, current SSG technologies face limitations due to the complexity of fabricating designs that maximize surface area for optimal water evaporation.

Drawing inspiration from nature, the team utilized 3D printing to create innovative SSGs. Their findings, published in Applied Physics Reviews, highlight a novel technique for manufacturing efficient SSGs and introduce a groundbreaking method for printing functional nanocomposites using multi-jet fusion (MJF).



“We created SSGs with exceptional photothermal performance and self-cleaning properties,” said Kun Zhou, a professor of mechanical engineering at Nanyang Technological University. “Using a treelike porous structure significantly enhances water evaporation rates and ensures continuous operation by preventing salt accumulation – its performance remains relatively stable even after prolonged testing.”



The technology works by converting light to thermal energy, where SSGs absorb solar energy and convert it to heat to evaporate water. The porous structure of the SSGs aids in self-cleaning by removing accumulated salt, ensuring sustained desalination performance.



“By using an effective photothermal fusing agent, MJF printing technology can rapidly create parts with intricate designs,” Zhou added. “To improve the photothermal conversion efficiency of fusing agents and printed parts, we developed a novel type of fusing agent derived from metal-organic frameworks.”



The SSGs feature miniature tree-shaped microstructures that mimic plant transpiration, forming an efficient, heat-distributing forest.



“Our bioinspired design increases the surface area of the SSG,” Zhou explained. “Using a treelike design increases the surface area of the SSG, which enhances the water transport and boosts evaporation efficiency.”



In both simulated environments and field trials, the SSGs exhibited a high rate of water evaporation. The desalinated water consistently met drinking water standards, even after extended testing.



“This demonstrates the practicality and efficiency of our approach,” Zhou said. “And it can be quickly and easily mass-produced via MJF commercial printers.”



The team’s work shows significant potential for tackling freshwater scarcity.



“Our SSGs can be used in regions with limited access to freshwater to provide a sustainable and efficient desalination solution,” said Zhou. “Beyond desalination, it can be adapted for other applications that require efficient solar energy conversion and water purification.”



Research Report:3D printing of bio-inspired porous polymeric solar steam generators for efficient and sustainable desalination


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Renewables overproduction turns electricity prices negative

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Renewables overproduction turns electricity prices negative


Renewables overproduction turns electricity prices negative

By Nathalie Alonso and Catherine Hours

Paris (AFP) July 24, 2024






With the proliferation of solar panels and wind turbines an unusual phenomenon is becoming more and more frequent: wholesale electricity prices turn negative.

While that may brighten the mood of consumers whose power bills have surged in recent years, it could undermine the further development of renewables, a key element in the fight against global warming.

The increasingly frequent phenomenon is “extremely problematic” for the wind and solar sector, said Mattias Vandenbulcke, strategy director of the renewables industry group France Renouvelables.

“It allows some to have harmful, even dangerous rhetoric which says ‘renewables are useless’,” Vandenbulcke said.

In southern Australia, wholesale electricity prices have been negative some 20 percent of the time since last year, according to the International Energy Agency.

The share of negatively priced hours in southern California was above 20 percent in the first half of the year, more than triple from the same period in 2023, the IEA said.

In the first six months of the year in France, there were negative prices around five percent of the time, beating the record set last year, according to the electricity grid operator RTE.

In Switzerland the price tumbled as far as -400 euros (-$436) per megawatt hour on July 14. The lowest prices are usually recorded around midday during the summer when solar production is at its peak.

– ‘A warning signal’ –

The trend has been accelerating for the past three years as demand in Europe has unexpectedly dropped since the Covid pandemic and the war in Ukraine.

Prices turn negative on the spot wholesale electricity market when production is strong while demand is weak.

Around a fifth of the total is traded on this market, where electricity is bought for the following day.

Negative prices help reduce the bills of consumers, said Rebecca Aron, head of electricity markets at French renewables firm Valorem, but the impact is delayed and difficult to discern among the other factors that send prices higher and lower.

Large, industrial consumers that can shift production to times when prices are negative and buy on wholesale markets can reap the biggest rewards.

Negative prices are “a warning signal that there is way too much production on the electrical grid”, said energy analyst Nicolas Goldberg at Colombus Consulting.

Electricity grids need to be kept constantly in balance. Too much can lead to the electricity to increase in frequency beyond norms for some equipment. Too little can lead to some or all customers losing power.

There are currently few options to stock surplus electricity production so producers have to reduce output.

Many renewable producers stop their output when prices are set to turn negative. It takes one minute to stop output at a solar park, two to three minutes for a wind turbine.

But not all stop their production.

– Tripling renewables –

“Renewable energy can be controlled, but depending on production contracts, there might not necessarily be an incentive to stop,” said Mathieu Pierzo at French grid operator RTE, which has the responsibility for balancing the electricity load.

Some producers are paid a fixed price under their contract or are compensated by the state if prices fall below a certain level.

Fossil fuel and nuclear power plants can adjust their production to some extent, but halting and restarting output is costly.

In the future, solar and wind will also have to “participate more in balancing the electricity system”, Pierzo said.

Solar and wind production is set to rise further as nations agreed at the COP28 climate conference last year to triple renewable energy capacity by 2030 as part of efforts to limit warming to 1.5 degrees Celsius compared with pre-industrial levels.

“Rising frequency of negative prices sends an urgent signal that greater flexibility of supply and demand is needed,” the Paris-based IEA warned last week.

“The appropriate regulatory frameworks and market designs will be important to allow for an uptake in flexibility solutions such as demand response and storage,” it said.

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NREL explores long-term strategies for sustainable perovskite solar panels

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NREL explores long-term strategies for sustainable perovskite solar panels


NREL explores long-term strategies for sustainable perovskite solar panels

by Clarence Oxford

Los Angeles CA (SPX) Jul 24, 2024






Researchers at the National Renewable Energy Laboratory (NREL) are examining the future of perovskite solar panels, focusing on scaling, deploying, and designing panels to be recyclable.

Perovskite solar panels could play a key role in global efforts to reduce greenhouse gas emissions. With the technology still in its developmental stages, researchers are emphasizing the importance of designing these panels to minimize environmental impact.



“When you have a technology in its very early stages, you have the ability to design it better. It’s a cleaner slate,” said Joey Luther, a senior research fellow at the U.S. Department of Energy’s (DOE’s) National Renewable Energy Laboratory (NREL) and coauthor of the newly published article in the journal Nature Materials. “Pushing perovskite PV toward enhanced sustainability makes more sense at this stage. We’re thinking about how we can make sure we have a sustainable product now rather than dealing with sustainability issues toward the end of its practical life.”



The article highlights the PV research community’s influential position to prioritize remanufacturing, recycling, and reliability efforts, aiming to make perovskite PV one of the most sustainable energy sources available.



“Perovskites could unlock the next evolution of high-efficiency PV, and it is our responsibility to assure they are manufactured, used, and recycled sustainably,” said the lead author of the study, Kevin Prince, a former graduate researcher at NREL who now researches perovskites at Helmholtz Zentrum Berlin in Germany.



While silicon solar panels dominate the industry and cadmium telluride (CdTe) panels have established recycling programs, perovskites are at a critical point where sustainability issues can be addressed from the start.



The most effective circular economy begins at the design stage, considering materials sourcing, product lifetime, and end-of-life management. Researchers suggest assessing environmental impacts by looking at carbon emissions during production, embodied energy, sustainable material sourcing, and module circularity.



The journal article identifies critical sustainability concerns for each component of a perovskite solar panel. For instance, lead can be diluted with metals like tin to reduce lead content, though this may affect PV efficiency and durability. Expensive precious metals such as silver and gold could be replaced with cheaper alternatives like aluminum, copper, or nickel. Fluorine-tin oxide is recommended over the scarcer indium-tin oxide for front electrodes.



“We want to have the lowest amount of embodied energy in the fabrication,” Luther said. “We want to have the lowest amount of emissions in the fabrication. At this stage, now is the chance to look at those components. I don’t think we have to change anything. It’s more a matter of what decisions should be made, and these arguments should certainly be discussed.”



The authors discuss various ways to improve the circularity of perovskite panels. Remanufacturing involves reusing parts from old modules to make new ones, while recycling converts waste materials into raw materials for reuse. Attention is needed for the specialized glass used in perovskite modules, which is crucial for structural support and protection while allowing maximum sunlight penetration. Establishing a recycling pathway for this glass will be essential as PV deployment increases.



Silvana Ovaitt, a PV researcher and coauthor of the paper, noted that cleaner electricity grids will lead to cleaner manufacturing processes, further reducing emissions.



“Another concern is the transportation of the final modules and the raw glass because those are the heaviest items,” Ovaitt said. “Local manufacturing will be a great way to reduce those carbon impacts.”



The researchers explain that increasing the durability of PV modules, thereby extending their useful life, is a more effective approach to reducing net energy, energy payback, and carbon emissions than designing for circularity alone. A longer lifespan means panels won’t need to be recycled as often.



“Ultimately, we want to make them as durable as possible,” Luther said. “But we also want to consider the aspects of whenever that time does come. We want to be deliberate about how to take them apart and to reuse the critical components.”



Research Report:Sustainability pathways for perovskite photovoltaics


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