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At least 145 records · Page 8

Enhancing Four-Carbon Olefin Production from Acetylene over Copper Nanoparticles in Metal–Organic Frameworks

Four-carbon olefins, such as 1-butene and 1,3-butadiene, are important chemical feedstocks for the production of adhesives and synthetic rubber. These compounds are found in the C 4 fraction of “green oil” products that can arise during the hydrogenation of acetylene. Here, we demonstrate that control of the catalyst structure increases the yield and productivity of these important olefins with a family of catalyst materials comprising Cu nanoparticles (CuNPs) bound within the pores of Zr-based metal–organic frameworks. Using carbon monoxide as a probe molecule, we characterize the surfaces of these catalytic CuNPs with diffuse reflectance infrared Fourier transform spectroscopy, revealing that the electronic structure of the CuNP surfaces is size-dependent. Furthermore, we find that as the CuNP diameter decreases, the selectivity for C 4 products increases and that lowering the stoichiometric ratio of H 2 /acetylene improves the selectivity and productivity of the catalyst.

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Geochemical reactions and alteration of pore architecture in saturated shale after injection of stimulation fluid

Pore architecture regulates fluid flow between unconventional shale reservoir and hydraulically-induced fractures. Imbibition of stimulation fluid may change this architecture and alter hydrocarbon flow. Hydrothermal experiments were conducted at reservoir conditions (125 °C, 45 MPa) to test two hypotheses: 1) Shale, not stimulation fluid, dominates the geochemistry of an unconventional reservoir containing formation water; and 2) Mineral dissolution and precipitation induced by stimulation fluid is transient and manifests across micro-, meso-, and macro-scales of pore architecture. Experiments replicated a shut-in well in the Cretaceous Baxter Shale, Green River Basin, Wyoming USA. Stimulation fluid was injected into one experiment after formation water (I = 0.35 mol/kg, pH = 6.4) and core reacted for 48 days. This novel approach equilibrated rock and formation water and saturated pores with formation water before introducing stimulation fluid. The second experiment served as a control. Trends of aqueous calcium, silica and aluminum in the injection experiment suggest transient dissolution of calcite and feldspar and/or quartz as well as clay and barite precipitation; mineralogic evidence was limited to calcite dissolution and barite precipitation. The rock maintained reducing conditions (Eh = +0.08 to -0.16 V) despite injection of oxidizing stimulation fluid (Eh = 1.1 V). pH of the stimulation fluid-formation water mixture evolved from 2.3 to pre-injection values (~6) within 24 h. The results indicate that mineral dissolution and precipitation manifest in macropores with barely detectable alteration to micro- and mesopores. Formation water or organic matter in pores may have inhibited access of stimulation fluid to micro- and mesopores

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Class-based separations of mixed solid–liquid systems with condensable solvent washing and extraction: The dilemma of pizza box recycling

As primary feedstocks deplete across the world, raw material extraction becomes increasingly expensive. Awareness of the environmental impact of primary extraction has motivated the development of energy- and reagent-efficient methods for material reuse. This work confronts an emblematic challenge of modern recycling: the soiled pizza box. While the fibers constituting corrugated cardboard are generally recyclable, pizza contaminants such as sauces and oils complicate their reuse, resulting in municipal prohibitions on the recycling of used pizza boxes in cardboard recycling streams and a representative of 275 kg/year per US household of food waste that is directed to landfill. This challenge is common to many materials, and engineering strategies must be developed to tackle complex/mixed feedstocks. To address the mixed composition of the pizza box (and similar materials), an environmentally benign, non-toxic organic solvent is applied to remove and fractionate components from mixed materials. The solvent employed in this process, dimethyl ether (DME), is a condensable hygroscopic gas, which facilitates its removal and recovery for reuse. Further, the results of this study indicate that 1) DME is capable of solubilizing and extracting components from soiled cardboard and other materials, (resulting in cardboard drier than new/unused cardboard) facilitating its recycling, and 2) the DME-soluble components of the system phase separate into aqueous and fatty acid/oil fractions (potentially ~27.5 kg/year per US household). Condensable solvent-driven washing and extraction enable the efficient separation of multiple intermediate product streams, suggesting a pathway to enable technology development necessary for achieving clean production in a circular economy.

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Elucidating the Role of Hydrogen Bond Donor and Acceptor on Solvation in Deep Eutectic Solvents Formed by Ammonium/Phosphonium Salts and Carboxylic Acids

Deep eutectic solvents (DESs) constitute a rapidly emerging class of sustainable liquids that have been widely studied and employed in chemical separations, catalysis, and electrochemistry. The unique physicochemical and solvation properties of DESs can be highly tailored by choosing the appropriate hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD). Understanding the role of the HBA and HBD on the multiple solvation interactions in DESs is important to enable their judicious selection for particular applications. As such, this work constitutes the first study to exploit chromatography to measure solute–solvent interactions of DESs using a wide array of known probe molecules. The constituent components of 20 DESs, formed by ammonium and phosphonium-based salts and carboxylic acids, are systematically modulated to delineate the contribution of the HBA and HBD toward individual solvation properties. Solute–solvent interactions measured in this study are used to interpret and explain the performance of DESs in desulfurization of fuels and extraction of natural products. The results from this study can be used to predict and understand the performance of DESs in various chemical processes where solvation interactions heavily influence outcomes.

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Fast inversion, preconditioned quantum linear system solvers, fast Green's-function computation, and fast evaluation of matrix functions

Preconditioning is the most widely used and effective way for treating ill-conditioned linear systems in the context of classical iterative linear system solvers. We introduce a quantum primitive called fast inversion, which can be used as a preconditioner for solving quantum linear systems. The key idea of fast inversion is to directly block encode a matrix inverse through a quantum circuit implementing the inversion of eigenvalues via classical arithmetics. We demonstrate the application of preconditioned linear system solvers for computing single-particle Green's functions of quantum many-body systems, which are widely used in quantum physics, chemistry, and materials science. We analyze the complexities in three scenarios: the Hubbard model, the quantum many-body Hamiltonian in the plane-wave-dual basis, and the Schwinger model. We also provide a method for performing Green's function calculation in second quantization within a fixed-particle manifold and note that this approach may be valuable for simulation more broadly. Aside from solving linear systems, fast inversion also allows us to develop fast algorithms for computing matrix functions, such as the efficient preparation of Gibbs states. Furthermore, we introduce two efficient approaches for such a task, based on the contour-integral formulation and the inverse transform, respectively.

97 MATHEMATICS AND COMPUTING↗

Investigating the Variation in Solvation Interactions of Choline Chloride-Based Deep Eutectic Solvents Formed Using Different Hydrogen Bond Donors

Choline chloride-based deep eutectic solvents (DESs) have gained widespread recognition as green solvents in catalysis and separation science as their designer properties permit solvation properties to be modulated by the choice of the hydrogen bond donor (HBD) as well as its molar ratio. Despite being one of the most popular classes of DESs, very little is currently understood regarding how their solvation characteristics differ among themselves as well as from other classes of DESs. Previous studies have shown that the catalytic activity, extraction efficiency, and solubilities of natural compounds can be influenced by the type of choline salt and HBD, but no study has systematically related these parameters with its solvation properties. In this study, inverse gas chromatography was employed for the first time to study the individual solvation characteristics of a diverse range of choline chloride and acetate-based DESs composed of amides, diols, organic acids, and carbohydrates. Furthermore, hydrogen bond acidity was found to be a dominant interaction for all DESs, especially those composed of organic acid HBDs. DESs composed of isomers of butane diol and hexane diol as HBDs exhibited higher hydrogen bond basicity and dispersive-type interactions compared to those composed of urea, acetamide, and organic acids with the position of the hydroxyl functional group influencing their solvation interactions. Choline acetate-based DESs exhibited lower dipolarity and stronger hydrogen bond basicity and dispersive-type interactions compared to choline chloride DESs. The solvation models developed in this study were used to interpret and explain DES behavior in previously reported studies involving catalysis, organic synthesis, and extractions demonstrating that the measured solute–solvent interactions can serve to predict the performance of choline chloride-based DESs when used in various applications.

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CAG12 - A CSCM based procedure for flow of an equilibrium chemically reacting gas

The Conservative Supra Characteristic Method (CSCM), an implicit upwind Navier-Stokes algorithm, is extended to the numerical simulation of flows in chemical equilibrium. The resulting computer code known as Chemistry and Gasdynamics Implicit - Version 2 (CAG12) is described. First-order accurate results are presented for inviscid and viscous Mach 20 flows of air past a hemisphere-cylinder. The solution procedure captures the bow shock in a chemically reacting gas, a technique that is needed for simulating high altitude, rarefied flows. In an initial effort to validate the code, the inviscid results are compared with published gasdynamic and chemistry solutions and satisfactorily agreement is obtained.

Green, M. J.↗

CHESS 2025: Field-collected vegetation attributes and site photos

This dataset represents field observations of vegetation samples collected as part of the Colorado Headwaters Ecological Spectroscopy Study (CHESS) during June and July of 2025. Samples were collected in the field using tablet computers and digital forms, with target data differing by sample type (individual trees, individual shrubs, or 1-meter square plots of meadow and subshrub vegetation). Field samples were collected within 72 hours of airborne data collection using the National Ecological Observatory Network’s Aerial Observation Platform (NEON AOP). The NEON AOP collected waveform LiDAR (Light Detection and Ranging) and imaging spectrometer data in 426 spectral bands from the visible to shortwave infrared. Remote sensing data for the project is available on ESS-DIVE (DOI and citation to be added upon publication). Field data collected included canopy height and per-species horizontal proportional cover for meadow plots, species identity and height information for shrubs, as well as species identity, height, diameter at breast height, and health assessment information for trees. Photos of the focal site and surrounding landscape were taken for all sampling sites and are included in this archive. Green leaves or needles were collected for plant trait and foliar chemistry analysis. This data is archived separately (DOI and citation to be added upon publication). High-precision geospatial data for each sample (crown perimeter polygons for trees and shrubs, plot boundaries for meadow plots) is available here (Henderson et al., 2026). Field and remote sensing protocols largely followed those of a previous field and airborne imaging campaign performed in 2018 (described in Chadwick et al. 2020). Field data from the 2018 campaign can be found here (Chadwick et al., 2020 doi:10.15485/1618130). Because different field measurements were taken for meadow, shrub, and tree sites, data from these three sample types are archived as separate tables (chess_meadow_site_cleaned.csv, chess_shrub_site_cleaned.csv, chess_tree_site_cleaned.csv). Meadow proportional cover data is stored in a separate table (chess_meadow_cover_cleaned.csv). Taxonomy was treated identically between sample types, and the dataset shares a common set of voucher specimens (chess_voucher_IDs_cleaned.csv), as well as a single species list (chess_species_list_cleaned.csv). All taxonomic determinations were performed to the species level, and adhere to the Global Biodiversity Information Facility (GBIF) backbone taxonomy as of January 10th, 2026 (GBIF Secretariat 2023). CHESS Project Description: The Colorado Headwaters Ecological Spectroscopy Study (CHESS) comprised a multi-week airborne remote sensing and field observation campaign in the Upper Gunnison Basin, Colorado, conducted in June and July of 2025. Airborne remote sensing was conducted by the National Ecological Observatory Network Airborne Observation Platform (NEON AOP), concurrent with a field campaign run by the Rocky Mountain Biological Laboratory (RMBL), the Lawrence Berkeley National Laboratory (LBNL) and SLAC National Accelerator Laboratory Watershed Function Science Focus Area (SFA), and NASA-JPL (Jet Propulsion Laboratory) Earth Surface Mineral Dust Source Investigation (EMIT) program. Between June 10 and July 18, 2025, the NEON AOP flight team collected high-resolution aerial imaging spectroscopy and Light Detection and Ranging (LiDAR) data over three domains: the Upper East River (CRBU), Almont Triangle (ALMO), and the Upper Taylor Basin (UPTA). In coordination with the flights, a field campaign acquired ground-truth observations, including observations of vegetation composition, foliar traits, forest demography, and subsurface properties in 18 core sampling areas within the domains. Additional surface water observations were taken at over 380 point locations. All CHESS campaign datasets can be found within the CHESS ESS-DIVE data portal: https://data.ess-dive.lbl.gov/portals/chess. Funding Acknowledgment: Field and remote-sensing data acquisition was performed under a grant from the National Aeronautics and Space Administration (80NSSC24K1005). This work was also supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231.

2018 NEON and 2025 CHESS Campaigns↗

Ecological Study of Lagoons Surrounding the John F. Kennedy Space Center, Brevard County, Florida : Theses and Project Reports - Volume 2

Many of the detailed studies done in connection with Ecological Study of the Lagoons surrounding the John F. Kennedy Space Port were performed as Master's Thesis investigations by various graduate students enrolled at F. I. T. during and subsequent to the report. The scope and purpose of what we came to call "the KSC Baseline Study" caught the imagination and interest of our student body. Many who were not financially or otherwise connected with the project found their inspiration in studies that were directly connected with project, and thus added materially to the totality of the knowledge gained. An example of one such study is the first article included in this Volume, A Master's Thesis study performed by Shen Phillip Chen, who chose the site for his investigation so that his results would correlate with and extend the results of others. In addition to the Master's Theses contained in this Volume, six other graduate studies must be acknowledged here as contributing to this Report, although they have not reached the stage of final publication. Ms. Sandra Fettes has completed a study of the amounts of five trace metals in mangrove leaves from plants at various locations around the Kennedy Space Center. Mr. Bernard Cohenour has isolated and identified a number of oil consuming bacteria endemic in the waters of the Indian Rivers. Mr. Charles Waterhouse has analyzed historic data of tidal gauges in the lagoonal area and correlated it with wind field records. Mr. Renkert Meyer has measured the vertical and horizontal currents of the lagoons and is attempting an interpretation of them in terms of the wind field as a driving force. Mr. Richard Campbell has measured the rate of nitrogen fixation in both the water columns and the sediments under them in the lagoons. Mr. Craig Weiderhold has measured thl3 annual variations in the populations of benthic invertebrates in the lagoons. An integral part of the F. I. T. curriculum is a requirement that each undergraduate student perform an independent study during his Senior year and submit his results in the form and format of a professional scientific report. While none of these senior Project Reports have been included in this Volume because of space limitations, many of them aided significantly in the overall study. Typical of these were: light and dark bottle studies of the blue-green algae respiration; writing and executing computer studies comparing the water chemistry data from various sites; detection and identification of nitrogen fixation bacteria in the Indian River; measurement of dissolved oils and greases in the river, photographically recording the benthic life-forms found in the river bottom; measuring the vertical structure of drift and slope currents in too lagoons; and measurement of water level variations along the long axis of a lagoon as a function of wind stress. These articles are published as a part of this Final Report in an effort to make available for the record as much of the basic data as possible. The few articles published on the Indian River have in general not contained much detailed data, so that comparisons of current status to conditions of the past are difficult or impossible. A major effort of both the Oceanographic and Ecological communities for the past decade has been the retrieval and storage of basic data in order to permit determinations of trends or changes in baseline conditions. It is believed that the information compiled here will be of great value in any future investigations.

Source record↗

Electrochemical-driven green recovery of lithium, graphite and cathode from lithium-ion batteries using water

The expected exponential increase in consumption of lithium-ion batteries (LIBs) would pose a unique challenge to the availability of near-critical resources like lithium and graphite in the upcoming decade. In this work, we present a lithium recovery process that utilizes a degradation mechanism, i.e., lithium plating, as a tool to concentrate metallic lithium at the anode/separator interface for convenient extraction at room temperature – using only water. Electrochemical characterization of fast charged (1–6 C) LIBs yielded a maximum capacity fade of 50% over ten cycles. The lithium plating was confirmed via voltage plateau analysis, coulombic efficiency, and DC resistance measurements. A maximum lithium plating condition was observed to exist between 4C and 5C, thereby limiting the energy consumption in the extraction process. Post-mortem film thickness measurement showed an incrementing film deposition with a maximum of 35 µm thickness. SEM and XPS analysis confirmed increasing concentration of a dense dendritic metallic lithium deposition on the anode/separator interface with C-rate. A green recovery process was adopted to extract the concentrated metallic lithium using distilled water. The lithium from the plated film, solid/electrolyte interface (SEI), electrolyte, anode, and cathode, was extracted as salts. A 37% improvement in lithium recoverability was achieved with fast charging under ambient conditions. XPS analysis showed ~92% of lithium yield with no residual lithium in the graphite. In addition, the battery-grade graphite was recovered with 97% purity after heat treatment of the washed anode film, and concentrated transition metals oxides in the cathode to 93% purity for convenient extraction.

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Novel alkali intercalated and acid-exfoliated biochars with enhanced surface areas for contaminant adsorption applications

Cost-effective and eco-friendly adsorbents are essential in environmental engineering and biochar is a promising material from the perspective. A novel and efficient surface modification approach involving alkali intercalation and acid exfoliation was designed in this study to enhance the physicochemical properties of biochar. Here, the alkali intercalation process utilizes potassium hydroxide (KOH), while acid exfoliation involves varying HNO 3 , H 2 SO 4 , and H 3 PO 4 concentrations. A simple two-stage pyrolysis process was employed to facilitate the intercalation-exfoliation modification. The modified biochars were characterized using BET, SEM, XRD, etc., to understand physicochemical properties. To quantify the effectiveness of the modifications, adsorption of malachite green dye as a model moiety was investigated. Dye removal sorption rates exceeding 99 % were recorded in the case of the biochars modified through a two-step process using KOH and 0.1MH 3 PO 4 . Specifically, the highest contaminant removal of 99.9 % was recorded when 60 mg of the KOH-0.1MH 3 PO 4 biochar was employed, which is significantly higher than unmodified biochar’s 45.41 % removal at a higher dosage of 100 mg. Moreover, the adsorption kinetics revealed that all the modified biochars attained the maximum removal concentrations (~99 % removal) in a mere 300 min, indicating a tenfold improvement in adsorption rate from unmodified biochar's requirement of over 5000 min. The results achieved through this study provide a cost-effective, fast, and environment-friendly technology for enhancing the adsorption characteristics and performance of biochars toward contaminant removal.

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Helical Organic and Inorganic Polymers

Despite being a staple of synthetic plastics and biomolecules, helical polymers are scarcely studied with Gaussian-basis-set ab initio electron-correlated methods on an equal footing with molecules. This article introduces an ab initio second-order many-body Green’s-function [MBGF(2)] method with nondiagonal, frequency-dependent Dyson self-energy for infinite helical polymers using screw-axis-symmetry-adapted Gaussian-spherical-harmonics basis functions. Together with the Gaussian-basis-set density-functional theory for energies, analytical atomic forces, translational-period force, and helical-angle force, it can compute correlated energy, quasiparticle energy bands, structures, and vibrational frequencies of an infinite helical polymer, which smoothly converge at the corresponding oligomer results. These methods can handle incommensurable structures, which have an infinite translational period and are hard to characterize by any other method, just as efficiently as commensurable structures. We apply them to polyethylene (2/1 helix), polyacetylene (Peierls’ system), and polytetrafluoroethylene (13/6 helix) to establish the quantitative accuracy of MBGF(2)/cc-pVDZ in simulating their (angle-resolved) ultraviolet photoelectron spectra, and of B3LYP/cc-pVDZ or 6-31G** in reproducing their structures, infrared and Raman band positions, phonon dispersions, and (coherent and incoherent) inelastic neutron scattering spectra. We then predict the same properties for infinitely catenated chains of nitrogen or oxygen and discuss their possible metastable existence under ambient conditions. They include planar zigzag polyazene (N2)x (Peierls’ system), 11/3-helical isotactic polyazane (NH)x, 9/4-helical isotactic polyfluoroazane (NF)x, and 7/2-helical polyoxane (O)x as potential high-energy-density materials.

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Bettye Washington Greene: An Industrial Chemist and Inventor Who Lit a Path for Innovation

American civil rights pioneer John Lewis once wrote: “You are a light. You are the light. Never let anyone— any person or any force—dampen, dim or diminish your light.” At a time when the civil rights movement was shedding light on inequalities for African Americans, Dr. Bettye Washington Greene (March 20, 1935 – June 16, 1995) was forging a path that would light the way–figuratively and literally—for generations to come. She was one of the few African American women to earn a Ph.D. in chemistry in the 1960s, an era marked by the passing of the Voting Rights Act of 1965. Washington Greene’s doctoral thesis evaluated light-scattering methods to determine the size of particles, which influences molecular effectiveness, activity, and stability. The fundamental knowledge she provided critically aided the pharmaceutical, catalyst and cosmetics industries [1]. Following her doctoral defense, Bettye went on to become the first African American female employed in a scientific research role at the Dow Chemical Company, where her innovations were awarded three patents.

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Dual Tunability for Uncatalyzed N‐Alkylation of Primary Amines Enabled by Plasma‐Microdroplet Fusion

Abstract The fusion of non‐thermal plasma with charged microdroplets facilitates catalyst‐free N‐alkylation for a variety of primary amines, without halide salt biproduct generation. Significant reaction enhancement (up to >200×) is observed over microdroplet reactions generated from electrospray. This enhancement for the plasma‐microdroplet system is attributed to the combined effects of energetic collisions and the presence of reactive oxygen species (ROS). The ROS (e.g., O 2 ⋅ − ) act as a proton sink to increase abundance of free neutral amines in the charged microdroplet environment. The effect of ROS on N‐alkylation is confirmed through three unique experiments: (i) utilization of radical scavenging reagent, (ii) characterization of internal energy distribution, and (iii) controls performed without plasma, which lacked reaction acceleration. Establishing plasma discharge in the wake of charged microdroplets as a green synthetic methodology overcomes two major challenges within conventional gas‐phase plasma chemistry, including the lack of selectivity and product scale‐up. Both limitations are overcome here, where dual tunability is achieved by controlling reagent concentration and residence time in the microdroplet environment, affording single or double N‐alkylated products. Products are readily collected yielding milligram quantities in eight hours. These results showcase a novel synthetic strategy that represents a straightforward and sustainable C−N bond‐forming process.

Chemistry↗

Modulating solvation interactions of deep eutectic solvents formed by ammonium salts and carboxylic acids through varying the molar ratio of hydrogen bond donor and acceptor

Deep eutectic solvents (DESs) have gained increasing popularity in separation science due to the fact that their physico-chemical properties can be easily fine-tuned by varying the type or ratio of hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD). While it is well-known that the molar ratio of HBA/HBD affects the melting point of a eutectic mixture, much less is understood regarding its effect on the magnitude of individual solvation interactions. This is largely due to the fact that established solvatochromic dye methods lack sensitivity when the HBA/HBD ratio is varied slightly in a eutectic mixture. Herein, this study is the first to measure the variation of DES solvation interactions with small changes in the molar ratio of HBA/HBD using inverse gas chromatography (IGC). Solute-solvent interactions of three different DES systems comprised of ammonium salts and organic acids were examined. The probe molecules were studied for 18 eutectic mixtures of varied HBA and HBD composition. We report DES hydrogen bond basicity, hydrogen bond acidity, and dispersive-type interactions exhibited the greatest change when the molar ratio of HBA/HBD was varied in the eutectic mixture. Results from this study demonstrate that the HBA/HBD ratio can be used to modulate the solvation characteristics for this class of DESs in separations and that the stoichiometric ratio of the HBA/HBD is important in ensuring their reproducible preparation.

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Sub-volt conversion of activated biochar and water for H 2 production near equilibrium via biochar-assisted water electrolysis

Sluggish water oxidation reactions limit water electrolysis for H 2 production, which can be alleviated by the use of carbon-based ma- terials like agricultural wastes as reducing agents. Biochar from such biomass can reduce equilibrium cell potentials at standard condi- tions from 1.23 V to 0.21 V by avoiding direct water splitting at the anode. However, some challenges hinder biochar oxidation, including poor biochar binding, electrode caking, and surface passivation. We find that enhanced C/O ratio, crystallinity, and negative zeta potential improve biochar oxidation kinetics at mod- erate temperatures. Smaller particle sizes and better mixing pre- vent electrode caking, enhancing biochar stability. Here, we report sub-volt biochar-coupled H 2 production, often referred to as a bio- char-assisted water electrolysis (BAWE), yielding 250 mA/g cat H 2 current at 100% Faradaic efficiency. Over 1 mA current was observed at a near-equilibrium cell potential of 0.2 V cell potential. Using a single-junction solar cell-powered BAWE, 15 mA H 2 is generated at 1 Sun, resulting in 4.8% solar-to-hydrogen efficiency, equivalent to 35% when the energy of H 2 relative to H 2 O (without biochar) is assumed.

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