Thursday, April 04, 2024

Fuel Cells: Oxidation processes of phosphoric acid revealed by tender X-rays



HELMHOLTZ-ZENTRUM BERLIN FÜR MATERIALIEN UND ENERGIE
HT PEM FC 

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THE ILLUSTRATION SHOWS FOUR DIFFERENT OXIDATION PATHWAYS (1-4) OF AQUEOUS PHOSPHORIC ACID (H3PO3), WHICH COULD BE ELUCIDATED BY XANES AT BESSY II. ALL THESE REACTIONS DEPEND ON THE HUMIDITY PRESENT.

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CREDIT: HZB/JACS




The interactions between phosphoric acid and the platinum catalyst in high-temperature PEM fuel cells are more complex than previously assumed. Experiments at BESSY II with tender X-rays have decoded the multiple oxidation processes at the platinum-electrolyte interface. The results indicate that variations in humidity can influence some of these processes in order to increase the lifetime and efficiency of fuel cells. 

 

Hydrogen fuel cells convert chemical energy from hydrogen into electrical energy through separate reactions of hydrogen fuels and oxidizing agents (oxygen). Among hydrogen fuel cells, high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) are attractive for micro-stationary electricity sources. One disadvantage of these HT-PEMFCs is that the phosphoric acid (H3PO4) proton conductor leaches out of the H3PO4-doped polybenzimidazole membrane and poisons the platinum catalyst. Recent studies show further complications during the operation of the HT-PEMFC, where some of H3PO4 might be reduced to H3PO3, which may further poison the platinum catalysts, leading to a significant loss of performance.

Complex processes and interactions

An earlier study by Prof. Dr Marcus Bär's team showed that opposite processes also take place at the interface between Pt and aqueous H3PO3 and that the interactions between the platinum catalyst and the H3PO3/H3PO4 are very complex: while H3PO3 can lead to poisoning of the platinum catalyst, at the same time platinum might catalyzes the oxidation of H3PO3 back to H3PO4.

Experiments under realistic conditions

In order to investigate the oxidation behaviour of aqueous H3PO3 under conditions close to HT-PEMFCs working conditions, Bär's team has now analysed the chemical processes using an in-housed designed heatable electrochemical cell compatible for in situ tender X-ray studies at the OÆSE end-station recently set up in the Energy Materials In-situ Laboratory Berlin (EMIL). They used intense X-ray light in the tender X-ray energy range (2 keV – 5 keV), which is provided by the EMIL beamline at the X-ray source BESSY II. In this energy range, X-ray absorption near-edge structure spectroscopy (XANES) at the P K-edge is used to monitor oxidation processes from H3PO3 to H3PO4.

Different oxidation reactions examined

"We have thus uncovered different processes for this oxidation reaction, including platinum-catalysed chemical oxidation, electrochemical oxidation under positive potential bias at the platinum electrode, and heat-promoted oxidation. These in situ spectroscopic results are also confirmed by ion-exchange chromatography and in situ electrochemical characterisations," explains Enggar Wibowo, first author of the study and a PhD candidate in Bär’s team. "Remarkably, all of these oxidation pathways involve reactions with water, which shows that the humidity inside the fuel cell has a significant influence on these processes."

Humidity as a factor for improvements

In addition, the results also point to possible improvements of the operating conditions of HT-PEM fuel cells, e.g. by controlling the humidification to oxidise the H3PO3 back to H3PO4. “Corresponding adjustments to the operation conditions of HT-PEMFCs could be implemented to prevent catalyst poisoning by H3PO3 and enhance efficiency of those fuel cells,” Wibowo points out.

Outlook to BESSY III

"The work clarifies a key degradation pathway of fuel cells and is a contribution on the way to an H2-based energy supply," says Prof. Dr.-Ing. Marcus Bär. "It also shows the great benefit of tender X-rays, and we are looking forward to BESSY III, which aims to close the "tender X-ray" gap," he adds.

WOMENS HEALTH

Extending Medicaid coverage after birth may increase postpartum treatment for depression, anxiety


A new study found that extending Medicaid eligibility for birthing people increase treatment for perinatal mood and anxiety disorder by more than 20 percentage points, compared to birthing people with commercial insurance


Peer-Reviewed Publication

BOSTON UNIVERSITY SCHOOL OF PUBLIC HEALTH




Extending postpartum Medicaid eligibility extensions may increase treatment for perinatal mood and anxiety disorders (PMADs), a leading cause of perinatal illness and mortality, according to a new study led by Boston University School of Public Health (BUSPH) and Brown University researchers.

Published in the journal Health Affairs, the study found that retaining Medicaid coverage after birth increased outpatient mental health and medication treatment for PMADs by 20.5 percentage points, compared to birthing people who received commercial coverage. Retaining postpartum Medicaid also appeared to significantly lower patients’ out-of-pocket spending for mental healthcare.

The majority of US states have now extended postpartum Medicaid coverage to 12 months through the American Rescue Plan Act, but the new findings provide critical data and insight into the role of Medicaid coverage on perinatal mental health, and why Medicaid extensions are so important for the health of low-income birthing people postpartum. Without this coverage, many people would otherwise become uninsured or struggle to pay for high-cost commercial insurance and medical care. Untreated PMADs can increase birthing people’s risk of substance use, depression, anxiety, and suicide, as well as developmental delays among their newborns. Estimates show that one in three pregnancy-related deaths occur between six weeks and one year after childbirth.

“We know that maternal mental health conditions are a leading cause of maternal morbidity and mortality, and postpartum mood and anxiety disorders are the most commonly occurring maternal mental health condition,” says study lead and corresponding author Dr. Sarah Gordon, assistant professor of health law, policy & management at BUSPH, and who served as a senior advisor on health policy for the US Department of Health and Human Services from 2021-2024. “Evidence-based treatments are available and effective, but underutilized. Insufficient health insurance coverage is one reason for low treatment rates among the postpartum population that extending postpartum Medicaid coverage can address.”

For the study, Dr. Gordon and colleagues utilized data on insurance claims and income, as well as birth records in Colorado between 2014-2019, before Colorado extended Medicaid eligibility. The researchers compared postpartum PMAD treatment among patients with incomes at or below 138 percent of the federal poverty level (FPL) and who were eligible to remain in Medicaid after 60 days postpartum, to patients with incomes above 138 percent of the FPL, who were ineligible to receive Medicaid beyond 60 days postpartum and enrolled in commercial insurance.

Compared to birthing people with commercial health insurance, remaining on Medicaid for 12 months postpartum was also linked to a 16 percentage point increase in patients filling a prescription medication for depression or anxiety, and a 7.3 percentage point increase in patients receiving at least one outpatient mental health visit. Retaining Medicaid beyond 60 days postpartum was associated with almost a 20 percentage point increase in “continuous” postpartum treatment, which is considered three or more outpatient mental health visits or prescription refills.

This extended Medicaid coverage also alleviated healthcare costs for birthing people, lowering out-of-pocket costs by $40.84 for outpatient mental health visits, and by $3.24 for each prescription refill, compared to costs for commercially insured birthing people.

Medicaid-insured birthing people may have higher PMAD treatment rates because of more affordable care, and fewer gaps in coverage that likely occur among birthing people who became ineligible for Medicaid. The researchers say these findings underscore the fact that commercial insurance is not an equal alternative for low-income postpartum people, and losing Medicaid eligibility can be detrimental to both health and finances.

“Our findings suggest that postpartum Medicaid extensions are likely an important policy lever to promote postpartum maternal mental health by lowering barriers to accessing treatment,” Dr. Gordon says. “However, mental health screening and referrals, availability of providers, and quality of mental healthcare are also critical to supporting the mental health of postpartum people.”

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About Boston University School of Public Health

Founded in 1976, Boston University School of Public Health is one of the top ten ranked schools of public health in the world. It offers master's- and doctoral-level education in public health. The faculty in six departments conduct policy-changing public health research around the world, with the mission of improving the health of populations—especially the disadvantaged, underserved, and vulnerable—locally and globally.