Tuning of Catalytic Activity by Thermoelectric Materials for Carbon Dioxide Hydrogenation

An innovative use of a thermoelectric material (BiCuSeO) as a support and promoter of catalysis for CO₂ hydrogenation is reported here. It is proposed that the capability of thermoelectric materials to shift the Fermi level and work function of a catalyst lead to an exponential increase of catalytic activity for catalyst particles deposited on its surface. Experimental results show that the CO₂ conversion and CO selectivity are increased significantly by a thermoelectric Seebeck voltage. This suggests that the thermoelectric effect can not only increase the reaction rate but also change chemical equilibrium, which leads to the change of thermodynamic equilibrium for the conversion of CO₂ in its hydrogenation reactions. It is also shown that this thermoelectric promotion of catalysis enables BiCuSeO oxide itself to have a high catalytic activity for CO₂ hydrogenation. The generic nature of the mechanism suggests the possibility that many catalytic chemical reactions can be tuned in situ to achieve much higher reaction rates, or at lower temperatures, or have better desired selectivity through changing the backside temperature of the thermoelectric support.     

Effect of Solute Adsorption Properties on Its Separation from Supercritical Carbon Dioxide with a Thin Porous Silica Membrane

A thin porous silica membrane (average pore size of 3.3 mm) was prepared by the sol–gel method and used to separate the solute from supercritical carbon dioxide. The characteristics of solute permeation were investigated in respect of the adsorption properties of the solute, the desorption rate of the solute from the membrane being measured and the potential energy of solute near the silica surface being calculated by the molecular modeling technique. It was found that caffeine was strongly adsorbed to the surface and then slowly desorbed to form an adsorption layer, making the pores narrower and causing a molecular-sieving effect. Therefore, the rejection value was positive. On the other hand, the rejection value of n-octanoic acid, which was well adsorbed and rapidly desorbed, was negative. It is presumed that the molecules filled the pores due to their potential energy and were then forced to flow through the pores by the transmembrane pressure.     

The Potential for Carbon Sequestration Through Reforestation of Abandoned Tropical Agricultural and Pasture Lands

Approximately half of the tropical biome is in some stage of recovery from past human disturbance, most of which is in secondary forests growing on abandoned agricultural lands and pastures. Reforestation of these abandoned lands, both natural and managed, has been proposed as a means to help offset increasing carbon emissions to the atmosphere. In this paper we discuss the potential of these forests to serve as sinks for atmospheric carbon dioxide in aboveground biomass and soils. A review of literature data shows that aboveground biomass increases at a rate of 6.2 Mg ha^{? 1} yr^{? 1} during the first 20 years of succession, and at a rate of 2.9 Mg ha^{? 1} yr^{? 1} over the first 80 years of regrowth. During the first 20 years of regrowth, forests in wet life zones have the fastest rate of aboveground carbon accumulation with reforestation, followed by dry and moist forests. Soil carbon accumulated at a rate of 0.41 Mg ha^{? 1} yr^{? 1} over a 100‐year period, and at faster rates during the first 20 years (1.30 Mg carbon ha^{? 1} yr^{? 1} ). Past land use affects the rate of both above‐ and belowground carbon sequestration. Forests growing on abandoned agricultural land accumulate biomass faster than other past land uses, while soil carbon accumulates faster on sites that were cleared but not developed, and on pasture sites. Our results indicate that tropical reforestation has the potential to serve as a carbon offset mechanism both above‐ and belowground for at least 40 to 80 years, and possibly much longer. More research is needed to determine the potential for longer‐term carbon sequestration for mitigation of atmospheric CO₂ emissions.     

ZnCl2-Modified Activated Carbon from Biomass Coir Pith for the Removal of 2-Chlorophenol by Adsorption Process

Coir pith, a waste biomass, from coconut coir industry was used to prepare activated carbon with ZnCl₂ and employed for the removal of 2-chlorophenol (2-CP) from aqueous solution and wastewater. Zinc chloride–activated coir pith carbon (ZnCPC) was prepared by mixing coir pith with ZnCl₂ in the ratio 2:1 and carbonized at 700°C for 1 h. ZnCPC was characterized using standard physicochemical methods, Brunaver, Emmett, and Teller (BET) surface area, and scanning electron microscopy (SEM) studies. Batch mode adsorption studies were carried out to evaluate the effect of contact time, initial concentration, adsorbent dose, pH, and temperature. The Langmuir adsorption capacity Q ₀ was found to be 149.3 mg g^?1. Kinetic studies showed that the adsorption obeyed second-order and Bangham's model. Equilibrium adsorption data fit better into Langmuir, Freundlich, and D-R isotherms. pH effect and desorption studies showed that ion-exchange mechanism was involved in the adsorption process. Effect of temperature was not significant. Quantitative removal of 2-CP from synthetic wastewater was also achieved. ZnCPC is economically effective compared to commercial activated carbon, because the raw material is abundantly and freely available and it can be used effectively in the treatment of water contaminated with 2-CP.     

Elimination and restoration of voltage dependence in the mitochondrial channel,VDAC, by graded modification with succinic anhydride

Summary The major permeability pathways of the outer mitochondrial membrane are the voltage-gated channels called VDAC. It is known that the conductance of these channels decreases as the transmembrane voltage is increased in the positive or negative direction. These channels are known to display a preference for anions over cations of similar size and valence. It was proposed (Doring & Colombini, 1985b) that a set of positive charges lining the channel may be responsible for both voltage dependence and selectivity. A prediction of this proposal is that progressive replacement of the positive charges with negative charges should at first diminish, and then restore, voltage dependence. At the same time, the channel's preference for anions over cations should diminish then reverse. Succinic anhydride was used to perform these experiments as it replaces positively charged amino groups with negatively charged carboxyl groups. When channels, which had been inserted into phospholipid membranes, were treated with moderate amounts of the anhydride, they lost their voltage dependence and preference for anions. With further succinylation, voltage dependence was regenerated while the channels became cation selective. The voltage needed to close one-half of the channels increased in those treatments in which voltage dependence was diminished. As voltage dependence was restored, the voltage needed to close half of the channels decreased. The energy difference between the open and closed state in the absence of an applied field changed little with succinylation, indicating that the procedure did not cause large changes in VDAC's structure but specifically altered those charges responsible for voltage gating and selectivity.     

中国热带天然林变迁对大气CO2的影响及经济损益评估

我国目前保存较好的热带天然林（包括热带原始林、结构良好的天然更新林,而不包括疏林、残次林、灌木林等）面积约１１８７万ｈｍ２,其中云南南部约有６０万ｈｍ２,海南中南部山区约有５８７万ｈｍ２。在过去的４５年中,我国的热带原始林面积减少了５０％（约１１０ｈｍ２）。在海南岛尖峰岭的实例结果表明,热带原始林的生态系统的Ｃ素库为３４２ｔ／ｈｍ２（其中,森林群落Ｃ素库为２３４ｔ／ｈｍ２,土壤为１０５ｔ／ｈｍ２,凋落物层为３ｔ／ｈｍ２）,系统每年净固定ＣＯ２量为１３３６ｔ／ｈｍ２,折合Ｃ量为０３７３ｔ／ｈｍ２;热带天然更新林生态系统每年净固定ＣＯ２量为７２１３ｔ／ｈｍ２,折合成Ｃ量为１９７ｔ／ｈｍ２。在我国现有的热带天然林生态系统中,森林植被层的Ｃ素库为１４４８亿ｔ,土壤中的Ｃ素库为１４２２亿ｔ,与植被层Ｃ库相当。在减少的热带森林中,Ｃ素库减少了约２２３１亿ｔ、ＣＯ２净同化量减少了０１８３亿ｔ,其经济损益高达２２００亿元。最后从森林与ＣＯ２的关系方面探讨了热带林可持续经营的问题。     

Global Warming Potential of Carbon Dioxide Emissions from Biomass Stored in the Anthroposphere and Used for Bioenergy at End of Life

There is growing interest in understanding how storage or delayed emission of carbon in products based on bioresources might mitigate climate change, and how such activities could be credited. In this research we extend the recently introduced approach that integrates biogenic carbon dioxide (CO₂) fluxes with the global carbon cycle (using biogenic global warming potential [GWP_bio]) to consider the storage period of harvested biomass in the anthroposphere, with subsequent oxidation. We then examine how this affects the climate impact from a bioenergy resource. This approach is compared to several recent methods designed to address the same problem. Using both a 100‐ and a 500‐year fixed time horizon we calculate the GWP_bio factor for every combination of rotational and anthropogenic storage periods between 0 and 100 years. The resulting GWP_bio factors range from ?0.99 (1‐year rotation and 100‐year storage) to +0.44 (100‐year rotation and 0‐year storage). The approach proposed in this study includes the interface between biomass growth and emissions and the global carbon cycle, whereas other methods do not model this. These results and the characterization factors produced can determine the climate change benefits or impacts associated with the storage of biomass in the anthroposphere, and the subsequent release of biogenic CO₂ with the radiative forcing integrated in a fixed time window.     

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.     

Tunable and Efficient Tin Modified Nitrogen‐Doped Carbon Nanofibers for Electrochemical Reduction of Aqueous Carbon Dioxide

Efficient and selective earth‐abundant catalysts are highly desirable to drive the electrochemical conversion of CO₂ into value‐added chemicals. In this work, a low‐cost Sn modified N‐doped carbon nanofiber hybrid catalyst is developed for switchable CO₂ electroreduction in aqueous medium via a straightforward electrospinning technique coupled with a pyrolysis process. The electrocatalytic performance can be tuned by the structure of Sn species on the N‐doped carbon nanofibers. Sn nanoparticles drive efficient formate formation with a high current density of 11 mA cm^?2 and a faradaic efficiency of 62% at a moderate overpotential of 690 mV. Atomically dispersed Sn species promote conversion of CO₂ to CO with a high faradaic efficiency of 91% at a low overpotential of 490 mV. The interaction between Sn species and pyridinic‐N may play an important role in tuning the catalytic activity and selectivity of these two materials.     

Comparison and Analysis of Zinc and Cobalt-Based Systems as Catalytic Entities for the Hydration of Carbon Dioxide

In nature, the zinc metalloenzyme carbonic anhydrase II (CAII) efficiently catalyzes the conversion of carbon dioxide (CO₂) to bicarbonate under physiological conditions. Many research efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolyl)phosphine, and tris(2-benzimidazolylmethyl)amine, in their complexed form either with the Zn²⁺ or the Co²⁺ ion and studied their reaction coordinate for CO₂ hydration. These calculations demonstrated that the ability of the complex to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Furthermore, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts.     

The functional properties of Ompβ, the regularly arrayed porin of the hyperthermophilic bacterium Thermotoga maritima

Abstract The regularly arrayed outer membrane protein, Ompβ, of Thermotoga maritima was purified to homogeneity and was characterized functionally by incorporation into artificial lipid bilayers. The polypeptide has an apparent molecular mass ( M _r) of approx. 40 000 and forms stable trimers in the presence of 1% octyl-polyoxyethylene or 2% SDS which dissociate when boiling the sample. The protein has a secondary structure (predominantly β-sheet) and an amino acid composition characteristic for porins. Pore-forming activity was demonstrated by porin incorporation into artificial bilayers proving that Ompβ is a true porin: selectivity measurements showed a 4.4-fold selectivity for cations over anions. Conductivity of the porin is influenced by surface charges and also depends on the applied voltage.     

Determination of Mass Transfer Coefficients for A Mixture of Compost,Sugarcane Bagasse,and Granulated Activated Carbon as Packing Medium in Biofilter

ABSTRACT

A laboratory-scale biofilter unit packed with a mixture of compost, sugarcane bagasse, and granulated activated carbon (GAC) in the ratio of 55:30:15 by weight was used for a biofiltration study of air stream containing benzene, toluene, ethylbenzene, and o-xylene (BTEX). The effect of superficial velocity on mass transfer coefficient for the packing was studied by maintaining gas flow rates of 3, 4, 5, 6, and 8 L min^?1 for inlet concentrations of 0.1, 0.4, and 0.8 g m^?3 for each of benzene, toluene, ethylbenzene, and o-xylene. The maximum elimination capacity was found to be 20.92, 22.72, 20.73, and 18.94 g m^?3 h^?1 for BTEX, respectively, for stated flow rates. Removal efficiency of BTEX decreased from 99% to 71% for increasing inlet concentration from 0.1 to 0.8 g m^?3. Gas film mass transfer coefficient predicted by modified Onda's equation was within ±10% of the experimental values.     

Multifunctional Effect of p‐Doping,Antireflection, and Encapsulation by Polymeric Acid for High Efficiency and Stable Carbon Nanotube‐Based Silicon Solar Cells

Silicon solar cells among different types of solar energy harvesters have entered the commercial market owing to their high power conversion efficiency and stability. By replacing the electrode and the p‐type layer by a single layer of carbon nanotubes, the device can be further simplified. This greatly augments the attractiveness of silicon solar cells in the light of raw material shortages and the solar payback period, as well as lowering the fabrication costs. However, carbon nanotube‐based silicon solar cells still lack device efficiency and stability. These can be improved by chemical doping, antireflection coating, and encapsulation. In this work, the multifunctional effects of p‐doping, antireflection, and encapsulation are observed simultaneously, by applying a polymeric acid. This method increases the power conversion efficiency of single‐walled carbon nanotube‐based silicon solar cells from 9.5% to 14.4% and leads to unprecedented device stability of more than 120 d under severe conditions. In addition, the polymeric acid‐applied carbon nanotube‐based silicon solar cells show excellent chemical and mechanical robustness. The obtained stable efficiency stands the highest among the reported carbon nanotube‐based silicon solar cells.     

The Role of Convictions and Trust for Public Protest Potential in the Case of Carbon Dioxide Capture and Storage (CCS)

For the public to accept new technologies, trust and convictions play an important role. In the present research, we used structural equation modeling to examine an extensive causal model of the role of convictions and trust for the public's protest potential against carbon dioxide capture and storage (CCS) among a large sample of the general population (N = 769). Trust, convictions, perceived benefits, and risks were included in the model. Our model fitted the data well. Convictions regarding emission reduction, decentralization of energy production, and tampering with natural structures in the deep subsurface influenced the perception of benefits and risks. Trust, in contrast, was barely influential. Perceived benefits were more prominent for public protest potential than perceived risks. However, perceived benefits did not dominate perceived risks as much as earlier studies found for acceptance. We argue that trust can become fully effective as a determinant of perceived risks and benefits only when the public perceives the distinct positioning of the stakeholders involved. Until then, laypeople are likely to draw on their own convictions and intuitive mental concepts for making decisions about accepting a new technology or protesting it.     

Multicomponent Synthesis Strategies,Catalytic Activities,and Potential Therapeutic Applications of Pyranocoumarins: A Comprehensive Review

Fused coumarins, because of their remarkable biological and therapeutic properties, particularly pyranocoumarins, have caught the interest of synthetic organic chemists, leading to the development of more efficient and environmentally friendly protocols for synthesizing pyranocoumarin derivatives. These compounds are the most promising heterocycles discovered in both natural and synthetic sources, with anti-inflammatory, anti-HIV, antitubercular, antihyperglycemic, and antibacterial properties. This review employed the leading scientific databases Scopus, Web of Science, Google Scholar, and PubMed up to the end of 2022, as well as the combining terms pyranocoumarins, synthesis, isolation, structural elucidation, and biological activity. Among the catalysts employed, acidic magnetic nanocatalysts, transition metal catalysts, and carbon-based catalysts have all demonstrated improved reaction yields and facilitated reactions under milder conditions. Herein, the present review discusses the various multicomponent synthetic strategies for pyranocoumarins catalyzed by transition metal-based catalysts, transition metal-based nanocatalysts, transition metal-free catalysts, carbon-based nanocatalysts, and their potential pharmacological activities.     

超临界CO2萃取技术应用于花椒油树脂分离工艺的研究

本文研究了超临界迷萃取花椒油树脂的工艺,探讨了萃取压力、温度和时间等因素对花椒萃取率的影响,通过正交实验法确定了花椒超临界迷流体萃取的最佳工艺：花椒原料粒度为60日,萃取条件为压力32Mpa、温度55℃、时间1h。     

Revising the Concept of Pore Hierarchy for Ionic Transport in Carbon Materials for Supercapacitors

Rapid motion of electrolyte ions is a crucial requirement to ensure the fast charging/discharging and the high power densities of supercapacitor devices. This motion is primarily determined by the pore size and connectivity of the used porous carbon electrodes. Here, the diffusion characteristics of each individual electrolyte component, that is, anion, cation, and solvent confined to model carbons with uniform and well‐defined pore sizes are quantified. As a result, the contributions of micropores, mesopores, and hierarchical pore architectures to the overall transport of adsorbed mobile species are rationalized. Unexpectedly, it is observed that the presence of a network of mesopores, in addition to smaller micropores—the concept widely used in heterogeneous catalysis to promote diffusion of sorbates—does not necessarily enhance ionic transport in carbon materials. The observed phenomenon is explained by the stripping off the surrounding solvent shell from the electrolyte ions entering the micropores of the hierarchical material, and the resulting enrichment of solvent molecules preferably in the mesopores. It is believed that the presented findings serve to provide fundamental understanding of the mechanisms of electrolyte diffusion in carbon materials and depict a quantitative platform for the future designing of supercapacitor electrodes on a rational basis.