Ultra‐High Surface Area Activated Porous Asphalt for CO2 Capture through Competitive Adsorption at High Pressures

This study reports an improved method for activating asphalt to produce ultra‐high surface area porous carbons. Pretreatment of asphalt (untreated Gilsonite, uGil ) at 400 °C for 3 h removes the more volatile organic compounds to form pretreated asphalt ( uGil‐P ) material with a larger fraction of higher molecular weight π‐conjugated asphaltenes. Subsequent activation of uGil‐P at 900 °C gives an ultra‐high surface area (4200 m² g^?1) porous carbon material ( uGil‐900 ) with a mixed micro and mesoporous structure. uGil‐900 shows enhanced room temperature CO₂ uptake capacity at 54 bar of 154 wt% (35 mmol g^?1). The CH₄ uptake capacity is 37.5 wt% (24 mmol g^?1) at 300 bar. These are relevant pressures in natural gas production. The room temperature working CO₂ uptake capacity for uGil‐900 is 19.1 mmol g^?1 (84 wt%) at 20 bar and 32.6 mmol g^?1 (143 wt%) at 50 bar. In order to further assess the reliability of uGil‐900 for CO₂ capture at elevated pressures, the authors study competitive sorption of CO₂ and CH₄ on uGil‐900 at pressures from 1 to 20 bar at 25 °C. CO₂/CH₄ displacement constants are measured at 2 to 40 bar, and found to increase significantly with pressure and surface area.     

Superior CO2 Adsorption Capacity on N‐doped,High‐Surface‐Area,Microporous Carbons Templated from Zeolite

Zeolite‐templated, high‐surface‐area, microporous, N‐doped carbons exhibit the highest CO₂ uptake capacity recorded to date for any carbon material and one of the highest for any inorganic or organic porous material of up to 6.9 mmol g^?1 at 273 K and ambient pressure and 4.4 mmol g^?1 at ambient temperature and pressure, along with an initial CO₂ adsorption energy of 36 kJ mol^?1 at lower coverage and 20 kJ mol^?1 at higher CO₂ coverage. Combined with their ease of preparation, excellent recyclability and regeneration stability, and high selectivity for CO₂, the N‐doped zeolite‐templated carbons are amongst the most promising solid‐state absorbents reported so far for CO₂ capture and storage.     

Generalized Mechanochemical Synthesis of Biomass‐Derived Sustainable Carbons for High Performance CO2 Storage

Novel mechanochemical activation generates biomass‐derived carbons with unprecedented CO₂ storage capacity due to higher porosity than analogous conventionally activated carbons but similar pore size. The mechanochemical activation, or so‐called compactivation, process involves compression, at 740 MPa, of mixtures of activating agent (KOH) and biomass hydrochar into pellets/disks prior to thermal activation. Despite the increase in surface area and pore volume of between 25% and 75% compared to conventionally activated carbons, virtually all of the porosity of the biomass (sawdust and lignin) derived mechanochemically activated carbons is from small micropores (5.8–6.5 Å), which results in a dramatic increase in CO₂ storage capacity at 25 °C and low pressure (≤1 bar). The ambient temperature CO₂ uptake for a carbon derived from sawdust at 600 °C and a KOH/carbon ratio of 2, rises from 1.3 to 2.0 mmol g^?1 at 0.15 bar, and from 4.3 to 5.8 mmol g^?1 at 1 bar, which is the highest ever reported for carbonaceous materials. The mechanochemically activated carbons have a superior CO₂ working capacity for pressure swing adsorption and vacuum swing adsorption processes and, due to a high packing density, they exhibit excellent volumetric CO₂ uptake that is higher than for any material reported to date.     

Superior Multifunctional Activity of Nanoporous Carbons with Widely Tunable Porosity: Enhanced Storage Capacities for Carbon‐Dioxide,Hydrogen, Water,and Electric Charge

Nanoporous carbons (NPCs) with engineered specific pore sizes and sufficiently high porosities (both specific surface area and pore volume) are necessary for storing energy in the form of electric charges and molecules. Herein, NPCs, derived from biomass pine‐cones, coffee‐grounds, graphene‐oxide and metal‐organic frameworks, with systematically increased pore width (<1.0 nm to a few nm), micropore volume (0.2–0.9 cm³ g^?1) and specific surface area (800–2800 m² g^?1) are presented. Superior CO₂, H_2, and H₂O uptakes of 35.0 wt% (≈7.9 mmol g^?1 at 273 K), 3.0 wt% (at 77 K) and 85.0 wt% (at 298 K), respectively at 1 bar, are achieved. At controlled microporosity, supercapacitors deliver impressive performance with a capacity of 320 and 230 F g^?1 at 500 mA g^?1, in aqueous and organic electrolytes, respectively. Excellent areal capacitance and energy density (>50 Wh kg^?1 at high power density, 1000 W kg^?1) are achieved to form the highest reported values among the range of carbons in the literature. The noteworthy energy storage performance of the NPCs for all five cases (CO₂, H₂, H₂O, and capacitance in aqueous and organic electrolytes) is highlighted by direct comparison to numerous existing porous solids. A further analysis on the specific pore type governed physisorption capacities is presented.     

Metal‐Organic Frameworks for Carbon Dioxide Capture and Methane Storage

In the global transition to a sustainable low‐carbon economy, CO₂ capture and storage technology still plays a critical role for deep emission reduction, particularly for the stationary sources in power generation and industry. However, for small and mobile emission sources in transportation, CO₂ capture is not suitable and it is more practical to use relatively clean energy, such as natural gas. In these two low‐carbon energy technologies, designing highly selective sorbents is one of the key and most challenging steps. Toward this end, metal‐organic frameworks (MOFs) have received continuously intensive attention in the past decades for their highly porous and diversified structures. In this review, the recent progress in developing MOFs for selective CO₂ capture from post‐combustion flue gas and CH₄ storage for vehicle applications are summarized. For CO₂ capture, several promising strategies being used to improve CO₂ adsorption uptake at low pressures are highlighted and compared. In addition, the conventional and novel regeneration techniques for MOFs are also discussed. In the case of CH₄ storage, the flexible and rigid MOFs, whose CH₄ storage capacity is close to the target set by U.S. Department of Energy are particularly emphasized. Finally, the challenge of using MOFs for CH₄ storage is discussed.     

3D Vertically Aligned and Interconnected Porous Carbon Nanosheets as Sulfur Immobilizers for High Performance Lithium‐Sulfur Batteries

A unique nanostructure of 3D and vertically aligned and interconnected porous carbon nanosheets (3D‐VCNs) is demonstrated by a simple carbonization of agar. The key feature of 3D‐VCNs is that they possess numerous 3D channels with macrovoids and mesopores, leading to high surface area of 1750 m² g^?1, which play an important role in loading large amount of sulfur, while vertically aligned microporous carbon nanosheets act as the multilayered physical barrier against polysulfides anions and prevent their dissolution in the electrolyte due to strong adsorption during cycling process. As a result, the 3D hybrid (3D‐S‐VCNs) infiltered with 68.3 wt% sulfur exhibits a high and stable reversible capacity of 844 mAh g^?1 at the current density of 837 mA g^?1 with excellent Coulombic efficiency ≈100%, capacity retention of ≈80.3% over 300 cycles, and good rate ability (the reversible capacity of 738 mAh g^?1 at the high current density of 3340 mA g^?1). The present work highlights the vital role of the introduction of 3D carbon nanosheets with macrovoids and mesopores in enhancing the performance of LSBs.     

Canopy radiation‐ and water‐use efficiencies as affected by elevated [CO2]

This study used an environmentally controlled plant growth facility, EcoCELLs, to measure canopy gas exchanges directly and to examine the effects of elevated [CO₂] on canopy radiation‐ and water‐use efficiencies. Sunflowers (Helianthus annus var. Mammoth) were grown at ambient (399 μmol mol^?1) and elevated [CO₂] (746 μmol mol^?1) for 53 days in EcoCELLs. Whole canopy carbon‐ and water‐fluxes were measured continuously during the period of the experiment. The results indicated that elevated [CO₂] enhanced daily total canopy carbon‐ and water‐fluxes by 53% and 11%, respectively, on a ground‐area basis, resulting in a 54% increase in radiation‐use efficiency (RUE) based on intercepted photosynthetic active radiation and a 26% increase in water‐use efficiency (WUE) by the end of the experiment. Canopy carbon‐ and water‐fluxes at both CO₂ treatments varied with canopy development. They were small at 22 days after planting (DAP) and gradually increased to the maxima at 46 DAP. When canopy carbon‐ and water‐fluxes were expressed on a leaf‐area basis, no effect of CO₂ was found for canopy water‐flux while elevated [CO₂] still enhanced canopy carbon‐flux by 29%, on average. Night‐time canopy carbon‐flux was 32% higher at elevated than at ambient [CO₂]. In addition, RUE and WUE displayed strong diurnal variations, high at noon and low in the morning or afternoon for WUE but opposite for RUE. This study provided direct evidence that plant canopy may consume more, instead of less, water but utilize both water and radiation more efficiently at elevated than at ambient [CO₂], at least during the exponential growth period as illustrated in this experiment.     

Chemically Exfoliating Biomass into a Graphene‐like Porous Active Carbon with Rational Pore Structure,Good Conductivity,and Large Surface Area for High‐Performance Supercapacitors

Active carbons have unique physicochemical properties, but their conductivities and surface to weight ratios are much poorer than graphene. A unique and facile method is innovated to chemically process biomass by “drilling” holes with H₂O₂ and exfoliating into graphene‐like nanosheets with HAc, followed by carbonization at a high temperature for highly graphitized activated carbon with greatly enhanced porosity, unique pore structure, high conductivity, and large surface area. This graphene‐like carbon exhibits extremely high specific capacitance (340 F g^?1 at 0.5 A g^?1) and high specific energy density (23.33 to 16.67 W h kg^?1) with excellent rate capability and long cycling stability (remains 98% after 10 000 cycles), which is much superior to all reported carbons including graphene. Synthesis mechanism for deriving biomass into porous graphene‐like carbons is discussed in detail. The enhancement mechanism for the porous graphene‐like carbon electrode reveals that rationally designed meso‐ and macropores are very critical in porous electrode performance, which can network micropores for diffusion freeways, high conductivity, and high utilization. This work has universal significance in producing highly porous and conductive carbons from biomass including biowastes for various energy storage/conversion applications.     

Investigating the biochar effects on C‐mineralization and sequestration of carbon in soil compared with conventional amendments using the stable isotope (δ13C) approach

Biomass‐derived black carbon (biochar) is considered to be an effective tool to mitigate global warming by long‐term C‐sequestration in soil and to influence C‐mineralization via priming effects. However, the underlying mechanism of biochar (BC) priming relative to conventional biowaste (BW) amendments remains uncertain. Here, we used a stable carbon isotope (δ¹³C) approach to estimate the possible biochar effects on native soil C‐mineralization compared with various BW additions and potential carbon sequestration. The results show that immediately after application, BC suppresses and then increases C‐mineralization, causing a loss of 0.14–7.17 mg‐CO₂–C g^?1‐C compared to the control (0.24–1.86 mg‐CO₂–C g^?1‐C) over 1–120 days. Negative priming was observed for BC compared to various BW amendments (?10.22 to ?23.56 mg‐CO₂–C g^?1‐soil‐C); however, it was trivially positive relative to that of the control (8.64 mg‐CO₂–C g^?1‐soil‐C). Furthermore, according to the residual carbon and δ¹³C signature of postexperimental soil carbon, BC‐C significantly increased (P < 0.05) the soil carbon stock by carbon sequestration in soil compared with various biowaste amendments. The results of cumulative CO₂–C emissions, relative priming effects, and carbon storage indicate that BC reduces C‐mineralization, resulting in greater C‐sequestration compared with other BW amendments, and the magnitude of this effect initially increases and then decreases and stabilizes over time, possibly due to the presence of recalcitrant‐C (4.92 mg‐C g^?1‐soil) in BC, the reduced microbial activity, and the sorption of labile organic carbon (OC) onto BC particles.     

Ecosystem carbon response of an Arctic peatland to simulated permafrost thaw

Permafrost peatlands are biogeochemical hot spots in the Arctic as they store vast amounts of carbon. Permafrost thaw could release part of these long‐term immobile carbon stocks as the greenhouse gases (GHGs) carbon dioxide (CO₂) and methane (CH₄) to the atmosphere, but how much, at which time‐span and as which gaseous carbon species is still highly uncertain. Here we assess the effect of permafrost thaw on GHG dynamics under different moisture and vegetation scenarios in a permafrost peatland. A novel experimental approach using intact plant–soil systems (mesocosms) allowed us to simulate permafrost thaw under near‐natural conditions. We monitored GHG flux dynamics via high‐resolution flow‐through gas measurements, combined with detailed monitoring of soil GHG concentration dynamics, yielding insights into GHG production and consumption potential of individual soil layers. Thawing the upper 10–15 cm of permafrost under dry conditions increased CO₂ emissions to the atmosphere (without vegetation: 0.74 ± 0.49 vs. 0.84 ± 0.60 g CO₂–C m^?2 day^?1; with vegetation: 1.20 ± 0.50 vs. 1.32 ± 0.60 g CO₂–C m^?2 day^?1, mean ± SD, pre‐ and post‐thaw, respectively). Radiocarbon dating (¹⁴C) of respired CO₂, supported by an independent curve‐fitting approach, showed a clear contribution (9%–27%) of old carbon to this enhanced post‐thaw CO₂ flux. Elevated concentrations of CO₂, CH₄, and dissolved organic carbon at depth indicated not just pulse emissions during the thawing process, but sustained decomposition and GHG production from thawed permafrost. Oxidation of CH₄ in the peat column, however, prevented CH₄ release to the atmosphere. Importantly, we show here that, under dry conditions, peatlands strengthen the permafrost–carbon feedback by adding to the atmospheric CO₂ burden post‐thaw. However, as long as the water table remains low, our results reveal a strong CH₄ sink capacity in these types of Arctic ecosystems pre‐ and post‐thaw, with the potential to compensate part of the permafrost CO₂ losses over longer timescales.     

Opening of Bottleneck Pores for the Improvement of Nitrogen Doped Carbon Electrocatalysts

A facile synthesis strategy to control the porosity of ionothermal nitrogen doped carbons is demonstrated. Adenine is used as cheap and biomass based precursor and a mixture of NaCl/ZnCl₂ as combined solvent‐porogen. Variation of the ratio between the two salt influences the pore structure over a wide range. The eutectic mixture leads to micro‐ and mesoporous material with high total pore volume (TPV) of 3.0 cm³ g^?1 and very high surface area of 2900 m² g^?1 essentially rendering the product an “all‐surface‐area” nitrogen doped carbon. Increasing NaCl contents cause a continuous increase of the mesopore size and the formation of additional macropores resulting in a very high maximal TPV of 5.2 cm³ g^?1, showing 2540 m² g^?1 specific surface area using 60 mol% NaCl. Interestingly, the electrocatalytic activity of the samples toward oxygen reduction is strongly affected by the detailed pore structure. The different—however, chemically equivalent—catalysts vary up to 70 mV in their half wave potentials (E _1/2).The sample with optimized pore system shows a high selectivity toward the favored four electron process and an outstanding E _1/2 of ≈880 mV versus reversible hydrogen electrode (RHE), which is one of the best values reported for nitrogen doped carbons so far.     

A High‐Volumetric‐Capacity Cathode Based on Interconnected Close‐Packed N‐Doped Porous Carbon Nanospheres for Long‐Life Lithium–Sulfur Batteries

This study reports a Li–S battery cathode of high volumetric capacity enabled by novel micro‐ and mesostructuring. The cathode is based on monodisperse highly porous carbon nanospheres derived from a facile template‐ and surfactant‐free method. At the mesoscale, the nanospheres structure into interconnected close‐packed clusters of a few microns in extent, thus facilitating the fabrication of dense crack‐free high areal sulfur loading (5 mg cm^?2) cathodes with high electrical conductivity and low cathode impedance. A combination of the nitrogen doping (5 wt%), high porosity (2.3 cm³ g^?1), and surface area (2900 m² g^?1) at the microscale enables high sulfur immobilization and utilization. The cathode delivers among the best reported volumetric capacity to date, above typical Li‐ion areal capacity at 0.2 C over 200 cycles and low capacity fading of 0.1% per cycle at 0.5 C over 500 cycles. The compact cathode structure also ensures a low electrolyte requirement (6 µL mg^?1), which aids a low overall cell weight, and further, among the best gravimetric capacities published to date as well.     

Stomatal acclimation to increased CO2 concentration in a Florida scrub oak species Quercus myrtifolia Willd

Native scrub‐oak communities in Florida were exposed for three seasons in open top chambers to present atmospheric [CO₂] (approx. 350 μmol mol^?1) and to high [CO₂] (increased by 350 μmol mol^?1). Stomatal and photosynthetic acclimation to high [CO₂] of the dominant species Quercus myrtifolia was examined by leaf gas exchange of excised shoots. Stomatal conductance (g_s) was approximately 40% lower in the high‐ compared to low‐[CO₂]‐grown plants when measured at their respective growth concentrations. Reciprocal measurements of g_s in both high‐ and low‐[CO₂]‐grown plants showed that there was negative acclimation in the high‐[CO₂]‐grown plants (9–16% reduction in g_s when measured at 700 μmol mol^?1), but these were small compared to those for net CO₂ assimilation rate (A, 21–36%). Stomatal acclimation was more clearly evident in the curve of stomatal response to intercellular [CO₂] (c_i) which showed a reduction in stomatal sensitivity at low c_i in the high‐[CO₂]‐grown plants. Stomatal density showed no change in response to growth in high growth [CO₂]. Long‐term stomatal and photosynthetic acclimation to growth in high [CO₂] did not markedly change the 2·5‐ to 3‐fold increase in gas‐exchange‐derived water use efficiency caused by high [CO₂].     

A Flexible Porous Carbon Nanofibers‐Selenium Cathode with Superior Electrochemical Performance for Both Li‐Se and Na‐Se Batteries

A flexible and free‐standing porous carbon nanofibers/selenium composite electrode (Se@PCNFs) is prepared by infiltrating Se into mesoporous carbon nanofibers (PCNFs). The porous carbon with optimized mesopores for accommodating Se can synergistically suppress the active material dissolution and provide mechanical stability needed for the film. The Se@PCNFs electrode exhibits exceptional electrochemical performance for both Li‐ion and Na‐ion storage. In the case of Li‐ion storage, it delivers a reversible capacity of 516 mAh g^?1 after 900 cycles without any capacity loss at 0.5 A g^?1. Se@PCNFs still delivers a reversible capacity of 306 mAh g^?1 at 4 A g^?1. While being used in Na‐Se batteries, the composite electrode maintains a reversible capacity of 520 mAh g^?1 after 80 cycles at 0.05 A g^?1 and a rate capability of 230 mAh g^?1 at 1 A g^?1. The high capacity, good cyclability, and rate capability are attributed to synergistic effects of the uniform distribution of Se in PCNFs and the 3D interconnected PCNFs framework, which could alleviate the shuttle reaction of polyselenides intermediates during cycling and maintain the perfect electrical conductivity throughout the electrode. By rational and delicate design, this type of self‐supported electrodes may hold great promise for the development of Li‐Se and Na‐Se batteries with high power and energy densities.     

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries (SIBs). However, its performance has been plagued by the limited initial Coulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium‐pretreated HC (LPHC) as high‐performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)‐based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g^?1 specific capacity, twice of the capacity (≈100 mAh g^?1) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g^?1 current density (4 C rate, 1 C = 250 mA g^?1) with a specific capacity of ≈150 mAh g^?1, ≈15 times of the capacity (10 mAh g^?1) in carbonate. The full cell of Na₃V₂(PO₄)₃‐LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g^?1 based on Na₃V₂(PO₄)₃ cathode, ≈2.5 times of the value (≈40 mAh g^?1) with nontreated HC. This work provides new perception on the anode development for SIBs.     

Full carbon and greenhouse gas balances of fertilized and nonfertilized reed canary grass cultivations on an abandoned peat extraction area in a dry year

Bioenergy crop cultivation on former peat extraction areas is a potential after‐use option that provides a source of renewable energy while mitigating climate change through enhanced carbon (C) sequestration. This study investigated the full C and greenhouse gas (GHG) balances of fertilized (RCG‐F) and nonfertilized (RCG‐C) reed canary grass (RCG; Phalaris arundinacea) cultivation compared to bare peat (BP) soil within an abandoned peat extraction area in western Estonia during a dry year. Vegetation sampling, static chamber and lysimeter measurements were carried out to estimate above‐ and belowground biomass production and allocation, fluxes of carbon dioxide (CO₂), methane (CH₄) and nitrous oxide (N₂O) in cultivated strips and drainage ditches as well as the dissolved organic carbon (DOC) export, respectively. Heterotrophic respiration was determined from vegetation‐free trenched plots. Fertilization increased the above‐ to belowground biomass production ratio and the autotrophic to heterotrophic respiration ratio. The full C balance (incl. CO₂, CH₄ and DOC fluxes from strips and ditches) was 96, 215 and 180 g C m^?2 yr^?1 in RCG‐F, RCG‐C and BP, respectively, suggesting that all treatments acted as C sources during the dry year. The C balance was driven by variations in the net CO₂ exchange, whereas the combined contribution of CH₄ and DOC fluxes was <5%. The GHG balances were 3.6, 7.9 and 6.6 t CO₂ eq ha^?1 yr^?1 in RCG‐F, RCG‐C and BP, respectively. The CO₂ exchange was also the dominant component of the GHG balance, while the contributions of CH₄ and N₂O were <1% and 1–6%, respectively. Overall, this study suggests that maximizing plant growth and the associated CO₂ uptake through adequate water and nutrient supply is a key prerequisite for ensuring sustainable high yields and climate benefits in RCG cultivations established on organic soils following drainage and peat extraction.     

Soil-surface carbon dioxide efflux and microbial biomass in relation to tree density 13 years after a stand replacing fire in a lodgepole pine ecosystem

The effects of fire on soil‐surface carbon dioxide (CO₂) efflux, F_S, and microbial biomass carbon, C_mic, were studied in a wildland setting by examining 13‐year‐old postfire stands of lodgepole pine differing in tree density (< 500 to > 500 000 trees ha^?1) in Yellowstone National Park (YNP). In addition, young stands were compared to mature lodgepole pine stands (～110‐year‐old) in order to estimate ecosystem recovery 13 years after a stand replacing fire. Growing season F_S increased with tree density in young stands (1.0 µmol CO₂ m^?2 s^?1 in low‐density stands, 1.8 µmol CO₂ m^?2 s^?1 in moderate‐density stands and 2.1 µmol CO₂ m^?2 s^?1 in high‐density stands) and with stand age (2.7 µmol CO₂ m^?2 s^?1 in mature stands). Microbial biomass carbon in young stands did not differ with tree density and ranged from 0.2 to 0.5 mg C g^?1 dry soil over the growing season; C_mic was significantly greater in mature stands (0.5–0.8 mg C g^?1 dry soil). Soil‐surface CO₂ efflux in young stands was correlated with biotic variables (above‐ground, below‐ground and microbial biomass), but not with abiotic variables (litter and mineral soil C and N content, bulk density and soil texture). Microbial biomass carbon was correlated with below‐ground plant biomass and not with soil carbon and nitrogen, indicating that plant activity controls not only root respiration, but C_mic pools and overall F_S rates as well. These findings support recent studies that have demonstrated the prevailing importance of plants in controlling rates of F_S and suggest that decomposition of older, recalcitrant soil C pools in this ecosystem is relatively unimportant 13 years after a stand replacing fire. Our results also indicate that realistic predictions and modeling of terrestrial C cycling must account for the variability in tree density and stand age that exists across the landscape as a result of natural disturbances.     

CARBON‐USE STRATEGIES IN MACROALGAE: DIFFERENTIAL RESPONSES TO LOWERED PH AND IMPLICATIONS FOR OCEAN ACIDIFICATION1

Ocean acidification (OA) is a reduction in oceanic pH due to increased absorption of anthropogenically produced CO₂. This change alters the seawater concentrations of inorganic carbon species that are utilized by macroalgae for photosynthesis and calcification: CO₂ and HCO₃^? increase; CO₃^2? decreases. Two common methods of experimentally reducing seawater pH differentially alter other aspects of carbonate chemistry: the addition of CO₂ gas mimics changes predicted due to OA, while the addition of HCl results in a comparatively lower [HCO₃^?]. We measured the short‐term photosynthetic responses of five macroalgal species with various carbon‐use strategies in one of three seawater pH treatments: pH 7.5 lowered by bubbling CO₂ gas, pH 7.5 lowered by HCl, and ambient pH 7.9. There was no difference in photosynthetic rates between the CO₂, HCl, or pH 7.9 treatments for any of the species examined. However, the ability of macroalgae to raise the pH of the surrounding seawater through carbon uptake was greatest in the pH 7.5 treatments. Modeling of pH change due to carbon assimilation indicated that macroalgal species that could utilize HCO₃^? increased their use of CO₂ in the pH 7.5 treatments compared to pH 7.9 treatments. Species only capable of using CO₂ did so exclusively in all treatments. Although CO₂ is not likely to be limiting for photosynthesis for the macroalgal species examined, the diffusive uptake of CO₂ is less energetically expensive than active HCO₃^? uptake, and so HCO₃^?‐using macroalgae may benefit in future seawater with elevated CO₂.     

Phenyl Disulfide Additive for Solution‐Mediated Carbon Dioxide Utilization in Li–CO2 Batteries

Phenyl disulfide (PDS) is employed as an electrolyte additive in lithium–carbon dioxide (Li–CO₂) batteries to allow for a solution‐mediated carbon dioxide reduction pathway. Thiophenolate anions, generated via electrochemical reduction of PDS, act as CO₂ capture agents by forming the adduct S‐phenyl carbonothioate (SPC^?) in solution. A mechanism of SPC^?‐mediated CO₂ capture and utilization is proposed and supported via carbon‐13 nuclear magnetic resonance spectroscopy and Fourier‐transform infrared spectroscopy. Reversible formation and decomposition of lithium carbonate and amorphous carbon during cycling, facilitated by the solution‐mediated pathway, are demonstrated with an array of characterization techniques. Li–CO₂ batteries employing the PDS additive show vastly improved capacity, energy efficiency, and cycle life. The enhanced Li–CO₂ battery performance offered by the proposed solution‐mediated reaction pathway offers a compelling step forward in the pursuit of reversible CO₂ utilization.     

Controllable Chain‐Length for Covalent Sulfur–Carbon Materials Enabling Stable and High‐Capacity Sodium Storage

Room temperature sodium–sulfur batteries have emerged as promising candidate for application in energy storage. However, the electrodes are usually obtained through infusing elemental sulfur into various carbon sources, and the precipitation of insoluble and irreversible sulfide species on the surface of carbon and sodium readily leads to continuous capacity degradation. Here, a novel strategy is demonstrated to prepare a covalent sulfur–carbon complex (SC‐BDSA) with high covalent‐sulfur concentration (40.1%) that relies on ? SO₃H (Benzenedisulfonic acid, BDSA) and SO₄^2? as the sulfur source rather than elemental sulfur. Most of the sulfur is exists in the form of O? S/C? S bridge‐bonds (short/long‐chain) whose features ensure sufficient interfacial contact and maintain high ionic/electronic conductivities of the sulfur–carbon cathode. Meanwhile, the carbon mesopores resulting from the thermal‐treated salt bath can confine a certain amount of sulfur and localize the diffluent polysulfides. Furthermore, the C? S_x? C bridges can be electrochemically broken at lower potential (<0.6 V vs Na/Na⁺) and then function as a capacity sponsor. And the R‐SO units can anchor the initially generated S_x^2? to form insoluble surface‐bound intermediates. Thus SC‐BDSA exhibits a specific capacity of 696 mAh g^?1 at 2500 mA g^?1 and excellent cycling stability for 1000 cycles with 0.035% capacity decay per cycle.