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NNadir's Journal
NNadir's Journal
December 4, 2023

New Carbon Allotropes: Graphyne, Graphdiyne and Beyond.

When I was a kid, one was taught there were two carbon allotropes, diamond and graphite.

The world has changed; there are too many allotropes of carbon to count.

I'm way behind on my readings in Chemical Reviews, and the following paper is from the past April: Graphynes and Graphdiynes for Energy Storage and Catalytic Utilization: Theoretical Insights into Recent Advances Hao Li, Jong Hyeon Lim, Yipin Lv, Nannan Li, Baotao Kang, and Jin Yong Lee Chemical Reviews 2023 123 (8), 4795-4854.

It discusses some carbon allotropes of which I was unaware.

The history of the discovery of new carbon allotropes, beginning with "fullerene" (C60), through carbon nanotubes and beyond:

The caption:

Figure 1. Timeline of the development of carbon allotrope materials. Transmission electron microscope (TEM) images of (a) fullerene, (33) (b) carbon nanotube, (35) (c) graphene film, (18) and (d) GDY film. (38) (a) Reprinted with open access article from ref (34). Copyright 2019 MDPI under CC-BY (https://www.mdpi.com/openaccess). (b) Reprinted with open access article from ref (36). Copyright 2018 Springer Nature under CC-BY (https://creativecommons.org/licenses/by/4.0/). (c) Reprinted with open access article from ref (37). Copyright 2017 Springer Nature under CC-BY (https://creativecommons.org/licenses/by/4.0/). (d) Reprinted with permission from ref (5). Copyright 2019 American Chemical Society. (e) Atomic force microscope (AFM) image of a GY flake. Reprinted with permission from ref (39). Copyright 2022 American Chemical Society. (f) Picture of a wafer-scale GDY film. Reprinted with permission from ref (40). Copyright 2021 Elsevier.

The caption:

Figure 3. GYF containing different numbers (n = 1, 2, 3, and 4) of acetylene linkages inserted between C(sp2) atoms.

The caption:

Figure 4. Theoretically predicted structures of ?-GY, ?-GY, ?-GY, GDY, and 6,6,12-GY with lattice vectors (a1 and a2).

It's an odd thing to come to the end of one's life and recognize how little one actually knows.

December 2, 2023

Issues in Water Chlorination Toxicology: ID of High Molecular Weight Halogenated Molecules in Drinking Water

The paper to which I'll refer in this post is this one: Unravelling High-Molecular-Weight DBP Toxicity Drivers in Chlorinated and Chloraminated Drinking Water: Effect-Directed Analysis of Molecular Weight Fractions Huiyu Dong, Amy A. Cuthbertson, Michael J. Plewa, Chad R. Weisbrod, Amy M. McKenna, and Susan D. Richardson Environmental Science & Technology 2023 57 (47), 18788-18800.

In my personal professional work, I am often tasked, although it's hardly my main focus, with the peripheral task of understanding environmental contaminants found environmental matrices as they appear in human blood, skin, and other biological matrices. This was a big concern during the Covid crisis, particularly with the components of hand sanitizers subject to percutaneous absorption.

One thing is very clear these days if one regularly reads the environmental literature, as I do: The breadth and number of environmental contaminants in water, land, and indeed the air, is rising very fast.

The chlorination of water - it's disinfection - has saved many tens of millions of lives, perhaps hundreds of millions of lives and prevented the disease related disability even more widely - but like any technology, it introduces its own set of risks; one must carefully weigh risk benefit analysis with any technology. One also would be well advised to reconsider any widely used technology based on environmental changes which may change that risk/benefit analysis.

This article is a reflection of this type of analysis, and I would add, involves some very sophisticated science with which I am enamored, high resolution mass spectrometry.

From the article's introduction:

Disinfection of drinking water is one of the ten public health achievements in the 20th century. (1) Various disinfectants, e.g., free chlorine, chloramine (NH2Cl), chlorine dioxide (ClO2), and ozone (O3), can reduce the spread of waterborne diseases by inactivating pathogens in water. (2) The disinfectant simultaneously reacts with natural or anthropogenic organic matter and halides to form toxic disinfection byproducts (DBPs), which are associated with the potential for adverse health conditions, including cancer and reproductive or developmental effects. (3) To date, >700 DBPs have been identified, approximately 100 of which have been investigated for their occurrence, formation, and quantitative cytotoxicity and genotoxicity. (3?5) However, >50% of the total organic halogen (TOX) formed during disinfection remains unknown. (6) Due to the adverse health effects associated with DBPs in drinking water, the World Health Organization, United States, European Union, China, and other countries have currently set up guidelines or regulations for several DBPs in drinking water. (7?9) For example, 11 DBPs including four trihalomethanes (THMs) and five haloacetic acids (HAAs) have been regulated in the U.S. However, most DBPs are not yet adequately identified, regulated, or controlled in drinking water. (7)

As chloramination forms lower levels of regulated THMs and HAAs than chlorination, chloramine has been increasingly adopted as a secondary disinfectant to maintain a residual disinfection ability in distribution systems. (10?12) However, TOX formed during chloramination (generally less than that from chlorination) can still reach considerable levels, depending on the chloramine dose, Cl/N ratio, pH, and other conditions. (13) Moreover, in chloraminated drinking water, up to 70% of TOX formed remains unknown, a significantly higher unknown fraction than observed for chlorination (?50% of TOX unknown). (14,15) The unknown TOX formed during chlorination and chloramination may contain a substantial amount of toxic DBPs, which need identification. (16,17)

Continued efforts have been made to identify unknown DBPs in drinking water, especially for the toxicity drivers. (18?28) The identification of unknown DBPs and corresponding toxicity assessments significantly enriched the knowledge of unknown TOX. One of the tricky challenges in the assessment of complex drinking water mixtures is the identification of those DBPs that contribute significantly to observed toxicity. A recent forcing factor study of U.S. drinking waters, which combined the quantification of 72 DBPs with whole-water cytotoxicity measurements, found unregulated dihaloacetonitriles to be the main cytotoxicity drivers in drinking water, along with iodo acids in chloraminated drinking waters containing iodide. (29) When measured whole-water toxicity data are not available, another approach called “TIC-Tox” is often used, where each measured low-molecular-weight DBP is multiplied by the reported cytotoxicity or genotoxicity index of that DBP measured in Chinese hamster ovary (CHO) cells. (30) However, the TIC-Tox method is limited to the ?100 low-molecular-weight known DBPs for which quantitative cellular toxicity data have been evaluated. For unknown/unquantified DBPs, it is difficult to use the TIC-Tox method to identify unknown DBP toxicity drivers. (7)...

The authors explain that while the analytical technology traditionally used for water analysis, GC/MS or GC/MS/MS (Gas Chromatography Mass Spectrometry, single quad and tandem respectively), these are really only suitable for volatile compounds. The authors chose to use a related technology, LC/MSn, where n refers to high resolution mass spectrometry which can pick up heavier molecular weight compounds. In fact they use the highest resolution for of mass spectrometry commercially available, FT-ICR-MS, Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. (In my dreams...) In fact they use the mass spectrometer with the highest resolution in the world, the 21 Tesla FT-ICR-MS at the National Magnetic Laboratory located in neofascist Floridastan. It has a mass resolution of over 1 million ppm. (Ron DeSantis has yet to completely kill science in his Taliban inspired state, inasmuch as the facility is funded by the United States Government, from which Desantis probably wants, along with his fellow racists, to secede, and not his provincial anti-science zealots in his government.) This mass resolution, giving five significant figures after the decimal point, is sufficient to clearly delineate the number of chlorine atoms in a molecule based on the isotopic distribution of chlorine's two isotopes, 35Cl having an exact mass of 34.96885269 amu, and 37Cl having an exact mass of 36.96590259 amu.

A figure in the paper describes this procedure for a sample contaminant:

The caption:

Figure 4. Isotopic pattern matching for high-molecular-weight CHOCl, CHOCl2, and CHOCl3 DBPs in the FT-ICR mass spectra of chloraminated drinking water (sample 1 in SC). Theoretical isotopic structures of CHOCl, CHOCl2, and CHOCl3 are shown for each isotopic peak. ?m values between masses calculated from the assigned isotopic composition with experimentally derived masses (FT-ICR-MS) are in the range of 11–25 ppb.

The distribution of types of halogenated contaminants.

The caption:

Figure 3. Quantified DBPs formed in chloraminated (sample 1 in SC) and chlorinated (sample 2 in SC) drinking waters. All DBP analyses were conducted in duplicate.

The abbreviations in the graphic are described in the text:

65 regulated and priority unregulated DBPs (all low molecular weight) from 8 DBP classes were also quantified for comparison using liquid–liquid extraction, derivatization, and GC-MS. Method details have been published and can be found in Text S5. (29,62) 4 THMs, 6 iodinated trihalomethanes (I-THMs), 8 bromo/chloro haloacetic acids (Br/Cl-HAAs), 4 iodinated haloacetic acids (I-HAAs), 10 haloacetonitriles (HANs), 7 halonitromethanes (HNMs), 9 haloketones (HKs), 13 haloacetamides (HAMs), and 4 trihaloacetaldehydes (tri-HALs) were included in the target DBP analysis. Speciated TOX (TOCl, TOBr, and TOI) was analyzed using combustion ion chromatography; details have been published and are provided in Text S6. (29)

A type of analysis using 2D plots of atomic ratios in molecules (Van Krevelen plots) is utilized to give a general overview of the types of molecules found among the halogenated species:

The caption:

Figure 5. Van Krevelen plots of high-molecular-weight CHOCl, CHOCl2, and CHOCl3 DBPs formed in chloraminated (a–c, sample 1 in SC) and chlorinated (d–f, sample 2 in SC) drinking water samples (less than 1 kD fraction). With the color of circles from gray to red, the relative abundance of DBPs increased in water samples. Regions 1–7 in Figure 5a indicate lipids (1), aliphatic/peptides (2), carbohydrates (3), unsaturated hydrocarbons (4), lignin/CRAM (carboxylic-rich aromatic moieties)-like (5), tannins (6), and aromatic structures (7).

The paper also includes studies of the toxicology of sample compounds.

I trust you're having a pleasant weekend.
December 2, 2023

Nuclearelectrica and Framatome Agree on Production of Lu-177, a medical radioisotope.

The news item is here: Nuclearelectrica and Framatome in lutetium-177 agreement.


Romania's Nuclearelectrica and France's Framatome have signed a cooperation agreement on exploring the production of the medical isotope lutetium-177 at the Cernavoda nuclear power plant.


A technical feasibility study will be conducted, based on Framatome's work on isotope production in Canada. The agreement will look at how to "maximise the existing infrastructure to convert target into medical isotopes".

Lutetium-177 is a beta-emitting radioisotope used in targeted radionuclide therapy to treat prostate cancer by destroying cancer cells while leaving healthy cells unaffected.

François Gauché, Director of Framatome Healthcare, said: "We are excited about this project with Nuclearelectrica. Mass access to nuclear medicine is closely linked to the development of large scale, reliable and diversified supply chains and we want to play our part in the fight against cancer by helping build these supply chains, to better serve the patients in the future, we will need regional nuclear medicine production hubs and this project is a great opportunity to strengthen the supply chain in Europe."

For full disclosure, I have personally worked with Bernard Fontana, pictured in the article, the CEO of Framochem, albeit earlier in his career, when he was not working in the nuclear industry but rather peripherally in the pharmaceutical industry.
December 2, 2023

Status of the Chemical Waste Drums (DDT) Dumped Off the Coast of Los Angeles County Decades Ago.

The paper to which I'll refer in this post is this one: Wide-Area Debris Field and Seabed Characterization of a Deep Ocean Dump Site Surveyed by Autonomous Underwater Vehicles Sophia T. Merrifield, Sean Celona, Ryan A. McCarthy, Andrew Pietruszka, Heidi Batchelor, Robert Hess, Andrew Nager, Raymond Young, Kurt Sadorf, Lisa A. Levin, David L. Valentine, James E. Conrad, and Eric J. Terrill Environmental Science & Technology 2023 57 (46), 18162-18171.

This issue of the scientific journal Environmental Science & Technology is largely devoted to the role of AI/machine learning as a tool in Environmental Science.

This particular paper is open to the public to read; no subscription is required.

These drums contain the now banned insecticide DDT, which is known to interfere with shell formation of birds; banning it was a major milestone in Environmental Law, which in this generation is decaying like the drums. They also contain oil refining residues from the many refineries in the LA area, in Torrance, El Segundo, and Wilmington.

The drums are off the coast of Palos Verdes (a wealthy enclave in LA county) in the San Pedro undersea basin, between Palos Verdes and Catalina Island.

My generation will leave the planet in much worse shape than we found it, as did the previous generation who dumped these drums, although on scale we easily exceeded: We used up the world's best ores but worse, rejected the only technology that might have prevented climate change.

Again, the paper is open sourced, but a few excerpts are in order:

The historical practice of ocean dumping in United States waters has been driven by both the economics of hazard disposal and a desire to place contaminants far from population centers. With the formation of the Environmental Protection Agency (EPA) in 1970 and a growing body of science that revealed the negative impacts of dumping to the environment, the process became federally regulated with strict guidelines and a permit approval process when the 1972 Marine Protection, Research, and Sanctuaries Act was passed by Congress (MPRSA (1)). Twenty-six years later, an outright ban of industrial waste dumping was enacted through the Ocean Dumping Ban Act of 1998 (Public Law 100-688), with remaining permitted dumping activities limited to sewage and dredge spoil disposal. Prior to legal protection, the ocean was a favored disposal site for industrial waste, with 23 known sites used offshore the Atlantic, Gulf, and Pacific Coasts. (2) Disposal took the form of both containerized waste and bulk dumping. (3)

Southern California’s coastal ocean hosts productive fisheries, is home to now protected ecosystems, and has an established tourism industry that is based on coastal recreation. Dump sites offshore California were established as early as the 1930s, became regulated in 1961, and were used for a variety of industrial purposes including disposal of waste from oil and gas production and the chemical manufacturing industry. Concern over these historical practices and their impact on the environment were described to the California Regional Water Quality Board in 1985. (5) The report documented extensive regulated dumping of a variety of bulk and containerized materials and the possibility of short-dumping, disposal prior to reaching the sanctioned dumping location. The San Pedro Basin, located in Southern California waters between Santa Catalina Island and Palos Verdes Peninsula at depths ranging from 600 to 900 m, was a dump site for military munitions (6) and a range of industrial wastes, including waste from refineries and chemical production. This included waste byproduct containing the pesticide dichlorodiphenyltrichloroethane (DDT), generated by the Montrose Chemical Corporation. Between 1947 and 1961, up to 700 t of DDT contained within acid sludge were dumped. (5) While only accounting for a small fraction of the total overall waste recorded as dumped, the DDT waste byproducts are of particular concern due to the long life of the chemical. DDT is now well understood to be both toxic and stable with long-lasting negative environmental impacts (7) including contamination of food webs, altering reproduction cycles, and contributing to cancer within wildlife. (8,9) As an endocrine disrupter and immune suppressor, recent studies have demonstrated human health linkages between DDT exposure from fish consumption and breast cancer in women that can be passed down through generations. (10) Interest is growing to develop a long-term strategy to assess the risk this dump site poses for both the surrounding marine ecosystem (11) and the coastal population of Southern California. To date, no systematic survey of the locations and conditions of the dump site has been conducted, due in part to the historical technical challenges associated with deep water survey. Although the presence of DDT in seafloor sediment samples has been recognized for decades, (12,13) it was only recently that surveys investigated whether barrels found on the seafloor could be a source. (14) Several studies have been published documenting the negative impacts of DDT to the marine food web in Southern California including birds, (15) dolphins, (9) and humans. (16)...

Graphics may be observed by opening the full article using the link.

I note, with some disgust, that the reason for dumping the drums with disregard for future generations was "economics." It was "cheap" to just dump the chemical waste drums in the ocean. The question of course, is "'cheap' for whom?" It's not cheap for us, this generation, it's a liability. Many pseudo-environmentalists - at least I attach the prefix "pseudo" to them - argue for example that solar cells and wind turbines are "cheap." Nevertheless, in less than 30 years, all of the wilderness rendered into industrial parks for this ineffective fantasy - if "effectiveness involved addressing the most serious environmental issue before us, climate change - will be largely chemical waste sites with rotting infrastructure. Of course, the decision by my awful generation to embrace this mass and land intensive garbage was never about climate change. It was about stopping the required growth of nuclear energy, which was our last best hope for a sustainable energy system. In this, the dangerous so called "renewable energy" fantasy was successful at entrenching the use of fossil fuels and preventing the growth of our last best hope for a sustainable world.

I'm given to platitudes and cliches in my writing these days, so I'll appeal to glass houses and throwing stones.

History will not forgive us, nor should it.

Have a nice weekend.

December 2, 2023

As someone who respects and values your participation at DU; I'd like to clarify my note on the graphics here.

For the record, to my knowledge, I am not Jewish.

This said, I grew up surrounded by Jewish culture on Long Island and - this of course is sometimes a trope, even if true - many of my closest friends were Jewish, and in my dating life, I had a number of Jewish lovers, Jewish teachers, and many casual Jewish associates, classmates and the like. I worked in Pharmacies as a kid, at that time on Long Island, that profession was heavily dominated by Jewish Pharmacists. For the first four years of my working life, all of my bosses were Jewish. In fact, my very first job - in a Sandwich shop, not a pharmacy - the owner was a holocaust survivor, tattooed arm and everything. When I moved to California, in a time I was experiencing poverty and depression, a Jewish friend helped me get on my feet, going so far as to take care of me when I was sick, feed me when I was hungry. Nearly five decades later, I'm still grateful.

I am naturally drawn to historical topics, particularly those related to the Second World War, since when I was a boy, it felt like everyone's Dad, everyone's uncles, older male cousins were involved in that war. Because of my close association with Jewish culture, and my youthful (now discarded) view of the Second World War as a "Good War," the Holocaust was a subject that ultimately entered into my independent (non-professional and non-academic) study of history. It follows that to study the Second World War in any serious way, and/or the Holocaust in any serious way, one must be familiar with Nazism. I would note that in the times of the rebirth of fascism - not just in Europe, but also in the United States, South America, and - I concede, not being a fan of Netanyahu - Israel, a study of Nazism has some instructional and warning merit. The uniform feature of fascism is demonization of the "other;" a feature of people like DeSantis, Trump, Abbott and the like. This demonization can take place on many levels, one of which is the basest level, appeals to the most ignorant members of a culture who are open to suggestion because of shallow intellects, suggestion enflamed by crudity, obscenity, and caricature.

In Germany, this level, appeal to the lowest dregs of society, the sort of thing we see or have seen on Fox News with the likes - if what I hear is correct, I have never tuned into Fox News - Carlson, Hannity, and for that matter tabloids like the New York Post, was Das Stuermer, which was founded by Julius Streicher, who was hanged at Nuremberg. This inflammatory rag was published and widely subscribed in the 1920's and remained in print until March of 1945.

It was so crude that it was actually banned by the Nazis for short periods, although apparently Hitler himself was an avid and enthusiastic reader.

I would not expect that most Americans would have exposure to Das Stuermer, since most people don't have a holocaust library, even one of the modest size of mine, and thus would not be likely to be aware of the similarity between the depiction of the war criminal Henry Kissinger as depicted in the cartoon you posted and the graphic cartoons in Das Stuermer, (Das Sturmer, if one does not add the "e" to account for the umlaut). I am however familiar with them, and the depiction of Kissinger in the cartoon is similar to those in Das Stuermer, specifically the fatty thick double chin, the exaggerated nose, the big ears and lips.

My note is decidedly not intended to accuse you of antisemitism, but merely to note the aspect of which I am familiar, but you, and I suspect most Americans, are probably not. Whether the cartoonist is aware of the similarity is not for me to say.

One can, of course, google images of cartoons from Das Sturmer, and easily discern of what I am writing.

For the record, I have no dog to hunt in the Hamas-Israel war. As far as I'm concerned a pox on both their houses. I certainly agree that Netanyahu and Kissinger are war criminals, and I'm sure the leaders of Hamas clearly are as well, although I cannot identify them by name. I'm very sure there are both Israelis and Palestinians who would agree with this statement, surely not all, and perhaps not even a majority, but enough to matter.

What does matter more, to my mind, are the innocents caught in the crossfire. In this, this war breaks my heart as much as any war. I have great sympathy for the views of Kurt Vonnegut who dug bodies out of the smoldering heaps of Dresden's rubble, who wrote that whenever he talked about it, people reminded him of the Holocaust, to which he replied, "I know; I know." To my mind, a Dresden baby burned alive by my country is not qualitatively different than a murdered Israeli baby or a bombed Palestinian baby.

I note that when Picasso painted Guernica, his most famous painting, in 1937, most of the civilized world regarded any bombing of civilians from aircraft as a war crime, notably Americans and Brits, but by 1943, just six years after, they would be creating firestorms in Hamburg, the first of many German and Japanese cities to be fire bombed. In this way, 1937 was preferable to the 1940's and certainly all the decades thereafter.

I sincerely believe that your post was intended to make a point about two men, both of whom happen to be Jewish, whose lives have been marked by contempt for humanity, expressed in both cases by indiscriminate bombing, but from my own reading, given what may be somewhat esoteric knowledge of a particular and often forgotten aspect of Nazism, its supporting publications, I had to note as much about the caricature and note that this aspect disturbed me from the prism of my specific attention to this increasingly obscure point of history.

November 30, 2023

Apocryphal Account of the Cause of the Deepwater Horizon Platform Failure: Batteries.

Last night I attended a lecture by the Princeton University Science Librarian who formerly ran the USGS library.

She described her work during the Deepwater Horizon oil disaster which took place in 2010. Her access to literature proved to be a key aspect of addressing the disaster. She was under intense pressure.

The disaster, which killed more human beings (11 directly) than radiation releases at Fukushima has, although Fukushima if familiar to all antinukes and other people who can carry on endlessly about it, has gone down the Orwellian "Memory Hole."

Anyone and everyone can talk all about Fukushima, albeit from a perspective (usually) of extreme ignorance, but no one gives a rat's ass about Deepwater Horizon anymore. This is similar to the big concern over so called "nuclear waste" which has a spectacular record of not killing anyone in over half a century, while not giving a rat's ass about the 19,000 people (roughly) who die each day from fossil fuel waste, aka "air pollution," not even mentioning climate change.

Like all disasters, there were three issues, addressing the immediate consequences at Deepwater Horizon, monitoring the long term consequences. According to the librarian the cause was a battery failure, because the batteries powering the blowout valves, designed to prevent an explosion, were not designed to function at low temperatures.

I was surprised to hear this, but apparently it's been known for some time, and can actually be found on the Wikipedia page for the Horizon Deepwater event. But again, no one gives a shit anymore about Deepwater Horizon.

Have a nice day.

November 28, 2023

The lithium/carbon dioxide battery.

The paper to which I'll refer in this post is this one: Boosted Reaction Kinetics of Li–CO2 Batteries by Atomic Layer-Deposited Mo2N on Hydrogen Substituted Graphdiyne Junxiang Zhang, Guicai Qi, Jianli Cheng, Paula Ratajczak, Zhuanpei Wang, Francois Beguin, and Bin Wang ACS Sustainable Chemistry & Engineering 2023 11 (45), 16185-16193.

My interest in this system does not at all contradict my frequent statement of the second law of thermodynamics in this form: "Storing energy wastes it."

Nevertheless, I do use batteries; my recently wrecked car was a hybrid car; I am looking to replace it; I own a battery powered lawnmower, and just purchased a battery powered snow blower. These batteries contain lithium, manganese, nickel and cobalt, the latter having a high moral cost, since cobalt is largely mined by modern day slaves.

Disturbed as I am by my moral hypocrisy, I do read a fair number of papers on batteries in my general reading, but this one really caught my eye because it's cobalt free, and because it reduces carbon dioxide to elemental carbon.

From the introduction:

Electric vehicles with longer driving mileage and unmanned aerial vehicles with prolonged cruise duration require urgently higher energy density of batteries. (1?4) Lithium–carbon dioxide (Li–CO2) battery, which demonstrates a high theoretical energy density of 1876 W h·kg–1 and a high discharge plateau (?2.8 V vs Li+/Li), has attracted increasing attention as one of the promising next-generation metal-gas batteries. (5?7) Li–CO2 batteries can simultaneously realize the fixation of greenhouse gas CO2 and high energy density supply, which show enormous application potentiality in CO2-rich situations such as deep-sea work and Mars exploration (96% of its atmosphere on Mars is CO2). The main reaction process involved in aprotic Li–CO2 batteries is as follows: 4Li+ + 3CO2 + 4e- ? Li2CO3 + C. (8?10) However, the sluggish kinetics of the discharged product Li2CO3 with stable chemical stability during recharging have greatly restricted the rate performance and cycling stability of Li–CO2 batteries. Meanwhile, the arduous decomposition of insulating Li2CO3 during recharging also leads to high overpotential and consequent electrolyte degradation. (11?13) The continuous accumulation of undecomposed Li2CO3 on the cathode occupies the reaction sites and severely blocks the CO2 diffusion channels, further resulting in large polarization and poor cycling performance of the batteries. Therefore, efficient cathode catalysts are highly imperative to boost the decomposition of Li2CO3 and facile reaction kinetics.

In recent years, several kinds of cathode catalysts, including carbon materials, (14?20) noble metals, (10,12,21?26) transition metals and their compounds, (27?36) metal–organic frameworks, (37,38) and covalent organic frameworks, (39,40) have been developed and improved the electrochemical performance of Li–CO2 batteries. Among them, integrating an efficient metal catalyst into highly conductive carbon have shown significantly facilitated kinetics in Li–CO2batteries as well as other gas-involved catalytic reactions. (29,32,36) A variety of carbon/metal composite catalysts, such as ultrathin Ir nanosheets on N-doped carbon fibers, (21) RuO2 on carbon nanotubes (CNTs), (22) ultrafine Ru nanoparticles on activated carbon nanofibers, (23) ZnS quantum dots on N-doped reduced graphene oxide(GO), (27) adjacent Co single atom/GO, (35) Ru–Cu nanoparticles on graphene, (41) Mo2C/CNTs, (42) Ru–Co nanoparticles on carbon nanofibers, (43) etc., have been prepared and showed outstanding catalytic activity and remarkably reduced the voltage gap between CO2 reduction and evolution process. However, reported carbon/metal composite catalysts have several drawbacks: weak bonding strength between carbon and metal catalysts, uneven distribution of the nanoparticles, and limited catalyst utilization, leading to the formation of large aggregates and high loading but partly inefficient catalytic behavior. Moreover, the loading amount, crystal structure, and catalytic sites of metal catalysts are difficult to precisely regulate to further improve and optimize their catalytic activity.

The emerged graphdiyne (GDY) material is a novel allotrope of carbon (44) which contains both sp and sp2 hybridized carbon atoms in the carbon framework and possesses a large specific surface area, uniform pore structure, and excellent electrochemical stability. Different from traditional carbon materials like graphene and CNTs, it was suggested that the coexistence of sp and sp2 carbon atoms is favorable for chelating metal atoms and facilitating the charge transfer between metal atoms and GDY. (45) These merits make GDY an ideal substrate for anchoring metal catalysts with suppressed aggregation. So, GDY/metal composite catalysts such as GDY-WS2 (46) and MoS2/N-GDY (47) have shown efficient catalytic activity in hydrogen evolution reaction (HER). In addition, single metal atoms can be stably anchored and evenly dispersed on GDY, such as Ni(Fe)/GDY, (48) Pd/GDY, (49) and Mo/GDY, (50) with highly efficient catalytic activity to the HER and the nitrogen reduction reaction. At the same time, GDY can be synthesized through a copper-catalyzed C–C cross-coupling reaction, which makes it possible to precisely adjust its morphology and chemical properties, including conductivity, pore structure, and affinity for metal atoms, thereby conveniently optimizing the catalytic activity of the GDY/metal catalyst...

The authors show how to address some of the kinetic drawbacks of these batteries by the plasma assisted atomic layer deposition of a molybdenum nitride catalyst.

This hardly ready for prime time, and it will certainly do nothing to make so called "renewable energy" a significant viable and sustainable form of energy, which it has not been, is not now, and never will be, batteries or no batteries.

Nevertheless a system that reduces carbon dioxide to elemental carbon should always be of interest.

In this sense it's a cool paper.

Earlier I wrote about such a system (which I view as a tool to make carbon based materials and electrodes for the FFC and Hall-Heroult reduction of ores to metals) here: Electrolysis of Lithium-Free Molten Carbonates

I see a lot of potential in this molten carbonate system, assuming it isn't lost in the shuffle.

Have a nice day tomorrow.
November 26, 2023

At the Mauna Loa CO2 Observatory, the Week to Week 10 Year Comparator Is the 3rd Highest Ever.

As I've indicated repeatedly in my DU writings, somewhat obsessively I keep a spreadsheet of the weekly data at the Mauna Loa Carbon Dioxide Observatory, which I use to do calculations to record the dying of our atmosphere, a triumph of fear, dogma and ignorance that did not have to be, but nonetheless is, a fact.

Facts matter.

When writing these depressing repeating posts about new records being set, reminiscent, over the years, to the ticking of a clock at a deathwatch, I often repeat some of the language from a previous post on this awful series, as I have been doing here with some modifications. It saves time.

As I note in this series of posts, the concentrations of the dangerous fossil fuel waste carbon dioxide which are killing the planet fluctuate sinusoidally over the year, with the rough sine wave superimposed on a quadratic axis:

Monthly Average Mauna Loa CO2

About two months ago we hit the autumnal local minimum for 2023, 418.29 ppm; the concentrations will rise until May or June. We may reasonable expect readings well in excess of 426 ppm, since we are doing nothing at all to address climate change.

There is considerable noise in these readings, and a way of leveling them is to look at the data over a 10 year period, which the observatory reports along with week to week comparators in the previous year.

Here is the current report of weekly data at the observatory:

Week beginning on November 19, 2023: 421.21 ppm
Weekly value from 1 year ago: 418.38 ppm
Weekly value from 10 years ago: 395.26 ppm
Last updated: November 26, 2023

Weekly average CO2 at Mauna Loa (Accessed 11/26/2023)

The comparator with week 46 of 2022 is a relatively modest 2.83 ppm higher; the average for 2023 for week to week comparators to 2022 is 2.55 ppm, with four readings being in the top 50 out of 2495 weekly readings in my spreadsheet, the highest being 4.40 ppm recorded in the week beginning 7/23/2023 (the ninth highest of all).

For this week it is the comparator with week 46 of 2013 that is remarkable. It is 25.95 ppm higher in 2023, the third highest of all such comparators going back to 1984. All of the top 50 ten year week to comparators have taken place since 2019 (when there were two), with 11 of these in 2023, and 16 in 2022.

Things are getting worse faster than ever.

People can lie, to each other and to themselves, but numbers don't lie.

Have a pleasant Sunday.
November 25, 2023

Hey! My Atrevida tee shirt finally came!

Perhaps you remember, among all the mass shootings, that guy Rich Fierro who was there with his wife, his daughter and her boyfriend enjoying the drags show at the QClub when a shooter walked in.

Mr. Fierro was unarmed but ran toward the shooter in the QClub Drag Show. tackled him and beat the shit out of him with the help of other patrons, including a drag performer who stomped him with his high heels.

His daughter's boyfriend was killed in the shooting.

Mr. Fierro and his wife own a small brewery and bar in Colorado Springs, Atrevida Brewery

Supporters rushed in to the small business after Mr. Fierro's brave selfless and courageous act:

The kegs were emptied but the hearts are full at Atrevida Beer Co. in Colorado Springs


Drinkers rushed to support owners Jess and Rich Fierro after finding out about their involvement in the Club Q shooting

I don't live in Colorado, but I went on line to order a tee shirt from them. I guess they must have been overwhelmed with orders, because the shirt never came, until a few days ago. I forgot about it. If they hadn't sent the shirt, and if I remembered it, I wouldn't have cared, but finally it came.



Diversity, it's on tap!

I can't wait to summer to wear it.

November 25, 2023

Well, I have singlehandedly assured New Jersey there will be no snowfall in our state this year.

After 28 years in my home, I bought a snowblower.

I'm too old to handle the sidewalk with my back. It's one of the Ego battery powered jobs, roughly 700 bucks.

This, I'm sure, will prevent it from snowing in NJ until after my death.

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