Textile grade polyacrylonitrile (PAN) was used as a precursor material for carbon fiber preparation. E-beam irradiated polyacrylonitrile grafted carbon nanofibers were dispersed in polyacrylonitrile solution (dissolved in dimethyl formamide). Carbon nanofibers (CNF) infused polyacrylonitrile solution was wet spun on a lab-scale wet-spinning setup to form 50 to 70 µm diameter fibers with 3.2 wt.% CNF-PAN, 6.4 wt.% CNF-PAN, and neat PAN. Precursor fibers were characterized for thermal, mechanical and morphological properties using various techniques. Drawing the precursor fibers further enhanced polymer chain orientation and coalesced the voids, enhancing tensile strength and modulus by more than 150% compared to those of the undrawn fibers. Precursor composite fibers on carbonization showed enhanced strength, compared to that of pristine PAN fibers, by four times and stiffness by 14 times. The carbon-carbon composite fibers were further characterized with SEM/FIB, XRD and tensile strength. The property improvements were dependent on the uniform distribution of carbon nanofibers, and surface modification of carbon nanofibers further enabled their dispersion in the composite fibers. Furthermore, 3.2 wt.% CNFs in PAN fibers showed maximum improvement in properties compared to 6.4 wt.% CNF in PAN fibers, indicating that the property enhancements go through a maximum and then drop off due to challenge in getting uniform distribution of nanofibers.

Multi walled carbon nanotubes (MWCNTs) were decorated by activated carbon nanoparticles of resorcinol-formaldehyde aerogels. Carbon nanospheres and MWCNTs were mixed by equal mass ratios for different durations. The products were characterized by Raman spectroscopy, thermal gravimetric analysis, nanoscanning electron microscopy, transmission electron microscopy and x-ray diffraction. The results indicated that a significant decoration with carbon nanoparticles occurred onto the MWCNTs.

An Au/K bicatalyst-assisted chemical vapor deposition process using C2H2(g) to grow high-density carbon nanocoils (CNCs) uniformly on the fibers in carbon fiber cloth substrates three-dimensionally was developed. An as-deposited substrate (2.5 × 1.0 cm2) showed a high electrochemical active surface area (16.53 cm2), suggesting its potential usefulness as the electrode in electrochemical devices. The unique one-dimensional (1D) helical structure of the CNCs shortened the diffusion pathways of the ions in the electrolyte and generated efficient electron conduction routes so that the observed serial resistance R s was low (3.7 Ω). By employing two-electrode systems, a liquid-state supercapacitor (SC) in H2SO4(aq) (1.0 M) and a solid-state SC with a polypropylene (PP) separator immersed in H2SO4(aq) (1.0 M)/polyvinylalcohol were assembled and investigated by using CNC-based electrodes. Both devices exhibited approximate rectangular shape profiles in the cyclic voltammetry measurements at various scan rates. The observations indicated their electric double-layer capacitive behaviors. From their galvanostatic charge/discharge curves, the specific capacitances of the liquid SC and the solid SC were measured to be approximately 137 and 163 F/g, respectively. In addition, the solid-state CNC-based SC possessed excellent energy density (15.3 W h/kg) and power density (510 W/kg). The light weight solid SC (0.1965 g, 2.5 × 1.0 cm2) was bendable up to 150° with most of the properties retained.

In the presented work, the properties of carbon materials obtained in the reaction of sodium bicarbonate (C-SB) and ammonium oxalate (C-AO) with magnesium by combustion synthesis were investigated. For the materials obtained in this way, the influence of the type of precursor on their properties was analyzed, including: Degree of crystallinity, porous structure, surface topography, and electrochemical properties. It has been shown that the products obtained in magnesiothermic process were found to contain largely the turbostratic carbon forming a petal-like graphene material. Both materials were used as modifiers of carbon paste electrodes, which were then used to determine the concentration of chlorophenol solutions by voltammetric method. It was shown that the peak current determined from the registered differential pulse voltammograms was mainly influenced by the volume of mesopores and the adsorption capacity of 4-chlorophenol for both obtained carbons.

Microbial transformations of organic carbon (OC) generate a large flux of CO2 into the atmosphere and influence the C balance of terrestrial and aquatic ecosystems. Yet, inherent heterogeneity in natural environments precludes direct quantification of multiple microbial C fluxes that underlie CO2 production. Here we used a continuous flow bioreactor coupled with a stable C isotope analyzer to determine the effects of temperature and C availability (cellobiose concentration) on C fluxes and 13C discrimination of a microbial population growing at steady-state in a homogeneous, well-mixed environment. We estimated C uptake affinity and C use efficiency (CUE) to characterize the physiological responses of microbes to changing environmental conditions. Temperature increased biomass-C specific respiration rate and C uptake affinity at lower C availability, but did not influence those parameters at higher C availability. CUE decreased non-linearly with increasing temperature. The non-linear, negative relationship between CUE and temperature was more pronounced under lower C availability than under relatively high C availability. We observed stable isotope fractionation between C substrate and microbial biomass C (7~12‰ depletion), and between microbial biomass and respired CO2 (4~10‰ depletion). Microbial discrimination against 13C-containing cellobiose during C uptake was influenced by temperature and C availability, while discrimination during respiration was only influenced by C availability. Shifts in C uptake affinity with temperature and C availability may have modified uptake-induced 13C fractionation. By stressing the importance of C availability on temperature responses of microbial C fluxes, C uptake affinity, CUE, and isotopic fractionation, this study contributes to a fundamental understanding of C flow through microbes. This will help guide parameterization of microbial responses to varying temperature and C availability within Earth-system models.

The alloying of noble metals with Cu is one of the most effective strategies for improving catalytic performance and reducing cost in electrocatalytic carbon dioxide reduction reactions (CO2RR). Previous works usually focused on the influence of morphology and composition on the catalytic activity, but lacked the study of the valence state ratio of metals and the electron transfer behavior on alloys. In this work, PdCu-2 alloy (Pd/Cu molar ratio is 1:2) was obtained by a simple one-step solvothermal method, which can effectively convert CO2 to CO with a maximum Faradaic efficiency (FE) of 85% at -0.9 V (vs. RHE). Then, the effect of the chemical state of Pd and Cu on the catalytic performance was investigated. The X-ray photoelectron spectroscopy (XPS) shows that the binding energy of Pd in PdCu alloy has a negative shift, which has affected the adsorption of key intermediates. When the proportion of oxidized state and zero-valent metal in the alloy is about 1:2, the PdCu alloy shows the best catalytic activity. In addition, the transient photovoltage (TPV) measurements further demonstrate that due to the introduction of Cu, the electron transfer rate of PdCu-2 becomes the slowest, which helps the accumulation of electrons on PdCu-2 and leads to the improvement of catalytic performance for electrocatalytic CO2RR. This work can provide more insights into the alloy catalysts of electrocatalytic CO2RR.

Membrane electrode assembly (MEA) electrolyzers offer a means to scale up CO2-to-ethylene electroconversion using renewable electricity and close the anthropogenic carbon cycle. To date, excessive CO2 coverage at the catalyst surface with limited active sites in MEA systems interferes with the carbon-carbon coupling reaction, diminishing ethylene production. With the aid of density functional theory calculations and spectroscopic analysis, here we report an oxide modulation strategy in which we introduce silica on Cu to create active Cu-SiOx interface sites, decreasing the formation energies of OCOH* and OCCOH*-key intermediates along the pathway to ethylene formation. We then synthesize the Cu-SiOx catalysts using one-pot coprecipitation and integrate the catalyst in a MEA electrolyzer. By tuning the CO2 concentration, the Cu-SiOx catalyst based MEA electrolyzer shows high ethylene Faradaic efficiencies of up to 65% at high ethylene current densities of up to 215 mA cm-2; and features sustained operation over 50 h.

The global warming conjugated with our reliance to petrol derived processes and products have raised strong concern about the future of our planet, asking urgently to find sustainable substitute solutions to decrease this reliance and annihilate this climate change mainly due to excess of CO2 emission. In this regard, the exploitation of microorganisms as microbial cell factories able to convert non-edible but renewable carbon sources into biofuels and commodity chemicals appears as an attractive solution. However, there is still a long way to go to make this solution economically viable and to introduce the use of microorganisms as one of the motor of the forthcoming bio-based economy. In this review, we address a scientific issue that must be challenged in order to improve the value of microbial organisms as cell factories. This issue is related to the capability of microbial systems to optimize carbon conservation during their metabolic processes. This initiative, which can be addressed nowadays using the advances in Synthetic Biology, should lead to an increase in products yield per carbon assimilated which is a key performance indice in biotechnological processes, as well as to indirectly contribute to a reduction of CO2 emission.

Staphylococcus aureus forms biofilms that cause considerable morbidity and mortality in patients who receive implanted devices such as prosthetics or fixator pins. An ideal surface for such medical devices would inhibit biofilm growth. Recently, it was reported that surface modification of stainless steel materials with carbon-infiltrated carbon nanotubes (CICNT) inhibits the growth of S. aureus biofilms. The purpose of this study was to investigate this antimicrobial effect on titanium materials with CICNT coated surfaces in a variety of surface morphologies and across a broader spectrum of S. aureus isolates. Study samples of CICNT-coated titanium, and control samples of bare titanium, a common implant material, were exposed to S. aureus. Viable bacteria were removed from adhered biofilms and quantified as colony forming units. Scanning electron microscopy was used to qualitatively analyze biofilms both before and after removal of cells. The CICNT surface was found to have significantly fewer adherent bacteria than bare titanium control surfaces, both via colony forming unit and microscopic analyses. This effect was most pronounced on CICNT surfaces with an average nanotube diameter of 150 nm, showing a 2.5-fold reduction in adherent bacteria. Since S. aureus forms different biofilm structures by isolate and by growth conditions, we tested 7 total isolates and found a significant reduction in the biofilm load in six out of seven S. aureus isolates tested. To examine whether the anti-biofilm effect was due to the structure of the nanotubes, we generated an unstructured carbon surface. Significantly more bacteria adhered to a nonstructured carbon surface than to the 150 nm CICNT surface, suggesting that the topography of the nanotube structure itself has anti-biofilm properties. The CICNT surface possesses anti-biofilm properties that result in fewer adherent S. aureus bacteria. These anti-biofilm properties are consistent across multiple isolates of S. aureus and are affected by nanotube diameter. The experiments performed in this study suggest that this effect is due to the nanostructure of the CICNT surface.

The manipulation of carbon nitride (CN) structures is one main avenue to enhance the activity of CN-based photocatalysts. Increasing the efficiency of photocatalytic heterogeneous materials is a critical step toward the realistic implementation of sustainable schemes for organic synthesis. However, limited knowledge of the structure/activity relationship in relation to subtle structural variations prevents a fully rational design of new photocatalytic materials, limiting practical applications. Here, the CN structure is engineered by means of a microwave treatment, and the structure of the material is shaped around its suitable functionality for Ni dual photocatalysis, with a resulting boosting of the reaction efficiency toward many CX (X = N, S, O) couplings. The combination of advanced characterization techniques and first-principle simulations reveals that this enhanced reactivity is due to the formation of carbon vacancies that evolve into triazole and imine N species able to suitably bind Ni complexes and harness highly efficient dual catalysis. The cost-effective microwave treatment proposed here appears as a versatile and sustainable approach to the design of CN-based photocatalysts for a wide range of industrially relevant organic synthetic reactions.

In this paper, a brief overview is presented of natural gas as a fuel resource with subsequent carbon capture and re-use as a means to facilitate reduction and eventual elimination of man-made carbon emissions. A particular focus is shale gas and, to a lesser extent, methane hydrates, with the former believed to provide the most reasonable alternative as a transitional fuel toward a low-carbon future. An emphasis is placed on the gradual elimination of fossil resource usage as a fuel over the coming 35 to 85 years and its eventual replacement with renewable resources and nuclear power. Furthermore, it is proposed that synthesis of chemical feedstocks from recycled carbon dioxide and hydrogen-rich materials should be undertaken for specific applications in the transport sector which require access to high energy density fuels. To achieve the latter, carbon dioxide capture is imperative and possible synthetic routes for chemical feedstock production are briefly reviewed.

Molecular dynamics (MD) simulations have been performed on the interaction between carbon nanoring (CNR) and single-wall carbon nanotube (SWCNT). The results show that, the CNR can spontaneously insert into the hollow interior of the SWCNTs to form a DNA-like double-helix, or collapse to a linked double graphitic nanoribbon and wrap in a helical manner around a tube. Further analyses of energy components show that this unique phenomenon is the result of the Van der Waals interaction. The spiral configuration of the CNR takes the least amount of energy and achieves the maximum occupancy. The sizes of CNR and SWCNT should meet the required conditions to guarantee the spiral form in the insertion and wrapping processes. Two CNRs can also be encapsulated in the SWCNT to form a helix at the same time. Furthermore, we also studied the encapsulation process of CNRs modified with -OH and -H functional groups.

Mexico has more than 750,000 ha of mangroves and more than 400,000 ha of seagrasses. However, approximately 200,000 ha of mangroves and an unknown area of seagrass have been lost due to coastal development associated with urban, industrial and tourist purposes. In 2018, the approved reforms to the General Law on Climate Change (LGCC) aligned the Mexican law with the international objectives established in the 2nd Article of the Paris Agreement. This action proves Mexico's commitment to contributing to the global target of stabilizing the greenhouse gas emissions concentration in the planet. Thus, restoring and conserving mangrove and seagrass habitats could contribute to fulfilling this commitment. Therefore, as a first step in establishing a mitigation and adaptation plan against climate change with respect to conservation and restoration actions of these ecosystems, we evaluated Mexican blue carbon ecosystems through a systematic review of the carbon stock using the standardized method of Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA). We used the data from 126 eligible studies for both ecosystems (n = 1220). The results indicated that information is missing at the regional level. However, the average above and below ground organic carbon stocks from mangroves in Mexico is 113.6 ± 5.5 (95% CI [99.3-118.4]) Mg Corg ha-1 and 385.1 ± 22 (95% CI [344.5-431.9]) Mg Corg ha-1, respectively. The variability in the Corg stocks for both blue carbon ecosystems in Mexico is related to variations in climate, hydrology and geomorphology observed along the country's coasts in addition to the size and number of plots evaluated with respect to the spatial cover. The highest values for mangroves were related to humid climate conditions, although in the case of seagrasses, they were related to low levels of hydrodynamic stress. Based on the official extent of mangrove and seagrass area in Mexico, we estimate a total carbon stock of 237.7 Tg Corg from mangroves and 48.1 Tg Corg from seagrasses. However, mangroves and seagrasses are still being lost due to land use change despite Mexican laws meant to incorporate environmental compensation. Such losses are largely due to loopholes in the legal framework that dilute the laws' effectiveness and thus ability to protect the ecosystem. The estimated emissions from land use change under a conservative approach in mangroves of Mexico were approximately 24 Tg CO2e in the last 20 years. Therefore, the incorporation of blue carbon into the carbon market as a viable source of supplemental finance for mangrove and seagrass protection is an attractive win-win opportunity.

To meet sustainability objectives in the transport sector, natural fiber (NF) and recycled carbon fiber (RCF) have been developed, although they have been typically limited to low to medium performance components. This work has considered the effect of interlayer hybridization of woven NF and non-woven RCF with woven virgin carbon fibers (VCF) on the mechanical and damping performance of hybrid laminates, produced using double bag vacuum infusion (DBVI). The mean damping ratio of the pure laminates showed a trend of NF>RCF>VCF, which was inversely proportional to their modulus. The tensile, flexural and damping properties of hybrid laminates were dominated by the outermost ply. The VCF-RCF and VCF-NF hybrid laminates showed a comparatively greater mean damping ratio. The results of this work demonstrate a method for the uptake of alternative materials with a minimal impact on the mechanical properties and improved damping performance.

Countries have pledged to different national and international environmental agreements, most prominently the climate change mitigation targets of the Paris Agreement. Accounting for carbon stocks and flows (fluxes) is essential for countries that have recently adopted the United Nations System of Environmental-Economic Accounting - ecosystem accounting framework (UNSEEA) as a global statistical standard. In this paper, we analyze how spatial carbon fluxes can be used in support of the UNSEEA carbon accounts in five case countries with available in-situ data. Using global multi-date biomass map products and other remotely sensed data, we mapped the 2010-2018 carbon fluxes in Brazil, the Netherlands, the Philippines, Sweden and the USA using National Forest Inventory (NFI) and local biomass maps from airborne LiDAR as reference data. We identified areas that are unsupported by the reference data within environmental feature space (6-47% of vegetated country area); cross-validated an ensemble machine learning (RMSE=9-39 Mg C [Formula: see text] and [Formula: see text]=0.16-0.71) used to map carbon fluxes with prediction intervals; and assessed spatially correlated residuals (<5 km) before aggregating carbon fluxes from 1-ha pixels to UNSEEA forest classes. The resulting carbon accounting tables revealed the net carbon sequestration in natural broadleaved forests. Both in plantations and in other woody vegetation ecosystems, emissions exceeded sequestration. Overall, our estimates align with FAO-Forest Resource Assessment and national studies with the largest deviations in Brazil and USA. These two countries used highly clustered reference data, where clustering caused uncertainty given the need to extrapolate to under-sampled areas. We finally provide recommendations to mitigate the effect of under-sampling and to better account for the uncertainties once carbon stocks and flows need to be aggregated in relatively smaller countries. These actions are timely given the global initiatives that aim to upscale UNSEEA carbon accounting.

It is largely unknown how South America's Andean forests affect the global carbon cycle, and thus regulate climate change. Here, we measure aboveground carbon dynamics over the past two decades in 119 monitoring plots spanning a range of >3000 m elevation across the subtropical and tropical Andes. Our results show that Andean forests act as strong sinks for aboveground carbon (0.67 ± 0.08 Mg C ha-1 y-1) and have a high potential to serve as future carbon refuges. Aboveground carbon dynamics of Andean forests are driven by abiotic and biotic factors, such as climate and size-dependent mortality of trees. The increasing aboveground carbon stocks offset the estimated C emissions due to deforestation between 2003 and 2014, resulting in a net total uptake of 0.027 Pg C y-1. Reducing deforestation will increase Andean aboveground carbon stocks, facilitate upward species migrations, and allow for recovery of biomass losses due to climate change.

Enzymes that catalyze carbon-carbon bond formation can be exploited as biocatalyst for synthetic organic chemistry. However, natural enzymes frequently do not possess the required properties or specificities to catalyze industrially useful transformations. This mini-review describes recent work using knowledge-guided site-specific mutagenesis of key active site residues to alter substrate specificity, stereospecificity and reaction specificity of these enzymes. In addition, examples of de novo designed enzymes that catalyze C-C bond reactions not found in nature will be discussed.

This study is the first report on the preparation of mesoporous carbon/silica (MCS) nanocomposites with tunable mesoporosity and hydrophobicity using natural rubber (NR) as a renewable and cheap carbon source. A series of mesoporous nanocomposites based on NR and hexagonal mesoporous silica (HMS) were prepared via an in situ sol-gel process and used as precursors; then, they were converted into MCS materials by controlled carbonization. The NR/HMS precursors exhibited a high dispersion of rubber phase incorporated into the mesostructured silica framework as confirmed by small-angle X-ray scattering and high-resolution transmission electron microscopy. An increase in the carbonization temperature up to 700 °C resulted in MCS nanocomposites with a well-ordered mesostructure and uniform framework-confined wormhole-like channels. The NR/HMS nanocomposites possessed high specific surface area (500-675 m2 g-1) and large pore volume (1.14-1.44 cm3 g-1). The carbon content of MCS (3.0-16.1 wt%) was increased with an increase in the H2SO4 concentration. Raman spectroscopy and X-ray photoelectron spectroscopy revealed the high dispersion of graphene oxide-like carbonaceous moieties in MCS materials; the type and amount of oxygen-containing groups in obtained MCS materials were determined by H2SO4 concentration. The enhanced hydrophobicity of MCS nanocomposites was related to the carbon content and the depletion of surface silanol groups, as confirmed by the water sorption measurement. The study on the controlled release of diclofenac in simulated gastrointestinal environment suggests a potential application of MCS materials as drug carriers.

In this study, we reported sustainable and economical upcycling methods for utilizing plastics such as polyethylene terephthalate (PET) and polypropylene (PP) compiled from the garbage of a residential area as cheap precursors for the production of high-value carbon materials such as graphene (G), carbon spheres (CS), and carbon nanotubes (CNTs) using different thermal treatment techniques. Graphene, carbon spheres, and carbon nanotubes were successfully synthesized from PET, PP, and PET, respectively via catalytic pyrolysis. XRD and FTIR analyses were conducted on the three materials, confirming the formation of carbon and their graphitic structure. TEM images displayed uniform and consistent morphological structures of the fabricated materials. EDX data confirmed that the prepared carbon-based materials only contained carbon and oxygen without any significant contaminations. XPS results revealed significant peaks in the C 1s spectra associated with sp2 and sp3 hybridized carbon for the three materials. BET spectra showed that the prepared CNTs (54.872 m2 g-1) have the highest surface area followed by carbon spheres (54.807 m2 g-1). The thermal stability of graphene surpassed both carbon spheres and carbon nanotubes which is mainly attributed to the stronger inter-molecular bonds of graphene. Based on the characterization of the prepared materials, these materials are promising to be utilized in environmental remediation applications due to their high carbon content, low cost, and high surface area.

Levodopa is a precursor of dopamine, having important beneficial effects in the treatment of Parkinson's disease. In this study, levodopa was accurately detected by means of cyclic voltammetry using carbon-based (C-SPCE), mesoporous carbon (MC-SPCE) and ordered mesoporous carbon (OMC-SPCE)-modified screen-printed sensors. Screen-printed carbon sensors were initially used for the electrochemical detection of levodopa in a 10-3 M solution at pH 7.0. The mesoporous carbon with an organized structure led to better electroanalysis results and to lower detection and quantification limits of the OMC-SPCE sensor as compared to the other two studied sensors. The range of linearity obtained and the low values of the detection (0.290 µM) and quantification (0.966 µM) limit demonstrate the high sensitivity and accuracy of the method for the determination of levodopa in real samples. Therefore, levodopa was detected by means of OMC-SPCE in three dietary supplements produced by different manufacturers and having various concentrations of the active compound, levodopa. The results obtained by cyclic voltammetry were compared with those obtained by using the FTIR method and no significant differences were observed. OMC-SPCE proved to be stable, and the electrochemical responses did not vary by more than 3% in repeated immersions in a solution with the same concentration of levodopa. In addition, the interfering compounds did not significantly influence the peaks related to the presence of levodopa in the solution to be analyzed.