CO2‐Speicherung. Chancen und Risiken

Anthropogenic emissions of carbon dioxide (CO₂) into the atmosphere have had a significant impact on the Earth's carbon cycle. As part of the global effort to reduce climate change, the geological storage of CO₂ has been accepted as a method that may provide up to 25 % of the total reduction of emissions, although this figure is still subject to change. In Germany and worldwide, geological storage capacities are expected to be sufficient for several decades. Carbon dioxide can be captured from sources such as large‐scale industrial (energy, steel, cement or chemical) facilities and transported to long‐term storage sites in deep saltwater‐bearing aquifers. Above the porous sandstone reservoirs in which the CO₂ is to be stored, an impermeable cap rock is required to provide a barrier for the upward‐migrating gas. In time, a significant quantity of the CO₂ can be retained within the reservoir pore space by capillary forces, dissolved in water to form carbonic acid, or deposited as carbonate minerals. The storage site must be free of potential leakage pathways. To this end, extensive monitoring programs need to be carried out. The Ketzin pilot site, an example of such a program, has shown CO₂ storage on a research scale to be safe and reliable.     

Modelling effects of geoengineering options in response to climate change and global warming: Implications for coral reefs

Climate change will have serious effects on the planet and on its ecosystems. Currently, mitigation efforts are proving ineffectual in reducing anthropogenic CO₂ emissions. Coral reefs are the most sensitive ecosystems on the planet to climate change, and here we review modelling a number of geoengineering options, and their potential influence on coral reefs. There are two categories of geoengineering, shortwave solar radiation management and longwave carbon dioxide removal. The first set of techniques only reduce some, but not all, effects of climate change, while possibly creating other problems. They also do not affect CO₂ levels and therefore fail to address the wider effects of rising CO₂, including ocean acidification, important for coral reefs. Solar radiation is important to coral growth and survival, and solar radiation management is not in general appropriate for this ecosystem. Longwave carbon dioxide removal techniques address the root cause of climate change, rising CO₂ concentrations, they have relatively low uncertainties and risks. They are worthy of further research and potential implementation, particularly carbon capture and storage, biochar, and afforestation methods, alongside increased mitigation of atmospheric CO₂ concentrations.     

Catholyte‐Free Electrocatalytic CO2 Reduction to Formate

Electrochemical reduction of carbon dioxide (CO₂) into value‐added chemicals is a promising strategy to reduce CO₂ emission and mitigate climate change. One of the most serious problems in electrocatalytic CO₂ reduction (CO₂R) is the low solubility of CO₂ in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte‐free electrocatalytic CO₂ reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm^?2, despite the decrease in CO₂ solubility. Furthermore, a significantly high formate concentration of 41.5 g L^?1 is obtained as a one‐path product at 343 K with high PCD (51.7 mA cm^?2) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V.     

CO2 – Baustein des Lebens und Treiber der globalen Erwärmung

For hundreds of millions of years, nature uses carbon dioxide in photosynthesis as a vital building block of life. The compound is also an essential part of the carbon cycle and is co‐responsible for the transport of carbon between Earth's spheres. However, over the last years CO₂ has been closely associated with global warming since the immense emissions from mainly the burning of fossil resources has led to a vast increase in atmospheric CO₂‐levels. Therefore, not only a reduction of emissions on a global scale is crucial but also a trend towards renewable resources is clearly visible and necessary due to depleting fossil resources. In this context, the use of CO₂ as an abundant resource in the chemical industry can contribute its share.     

An Iron Complex with a Bent,O‐Coordinated CO2 Ligand Discovered by Femtosecond Mid‐Infrared Spectroscopy

The activation of carbon dioxide by transition metals is widely recognized as a key step for utilizing this greenhouse gas as a renewable feedstock for the sustainable production of fine chemicals. However, the dynamics of CO₂ binding and unbinding to and from the ligand sphere of a metal have never been observed in the time domain. The ferrioxalate anion is used in aqueous solution as a unique model system for these dynamics and femtosecond UV‐pump mid‐infrared‐probe spectroscopy is applied to explore its photoinduced primary processes in a time‐resolved fashion. Following optical excitation, a neutral CO₂ molecule is expelled from the complex within about 500 fs to generate a highly intriguing pentacoordinate ferrous dioxalate that carries a bent carbon dioxide radical anion ligand, that is, a reductively activated form of CO₂, which is end‐on‐coordinated to the metal center by one of its two oxygen atoms.     

An Iron Complex with a Bent,O‐Coordinated CO2 Ligand Discovered by Femtosecond Mid‐Infrared Spectroscopy

The activation of carbon dioxide by transition metals is widely recognized as a key step for utilizing this greenhouse gas as a renewable feedstock for the sustainable production of fine chemicals. However, the dynamics of CO₂ binding and unbinding to and from the ligand sphere of a metal have never been observed in the time domain. The ferrioxalate anion is used in aqueous solution as a unique model system for these dynamics and femtosecond UV‐pump mid‐infrared‐probe spectroscopy is applied to explore its photoinduced primary processes in a time‐resolved fashion. Following optical excitation, a neutral CO₂ molecule is expelled from the complex within about 500 fs to generate a highly intriguing pentacoordinate ferrous dioxalate that carries a bent carbon dioxide radical anion ligand, that is, a reductively activated form of CO₂, which is end‐on‐coordinated to the metal center by one of its two oxygen atoms.     

Mechanistic Aspects of a Highly Active Dinuclear Zinc Catalyst for the Co‐polymerization of Epoxides and CO2

The dinuclear zinc complex reported by us is to date the most active zinc catalyst for the co‐polymerization of cyclohexene oxide (CHO) and carbon dioxide. However, co‐polymerization experiments with propylene oxide (PO) and CO₂ revealed surprisingly low conversions. Within this work, we focused on clarification of this behavior through experimental results and quantum chemical studies. The combination of both results indicated the formation of an energetically highly stable intermediate in the presence of propylene oxide and carbon dioxide. A similar species in the case of cyclohexene oxide/CO₂ co‐polymerization was not stable enough to deactivate the catalyst due to steric repulsion.     

Graphene Oxide Membranes with Heterogeneous Nanodomains for Efficient CO2 Separations

Achieving high membrane performance in terms of gas permeance and carbon dioxide selectivity is an important target in carbon capture. Aiming to manipulate the channel affinity towards CO₂ to implement efficient separations, gas separation membranes containing CO₂‐philic and non‐CO₂‐philic nanodomains in the interlayer channels of graphene oxide (GO) were formed by intercalating poly(ethylene glycol) diamines (PEGDA). PEGDA reacts with epoxy groups on the GO surface, constructing CO₂‐philic nanodomains and rendering a high sorption capacity, whereas unreacted GO surfaces give non‐CO₂‐philic nanodomains, rendering low‐friction diffusion. Owing to the orderly stacking of nanochannels through cross‐linking and the heterogeneous nanodomains with moderate CO₂ affinity, a GO‐PEGDA500 membrane exhibits a high CO₂ permeance of 175.5 GPU and a CO₂/CH₄ selectivity of 69.5, which is the highest performance reported for dry‐state GO‐stacking membranes.     

Electrochemical Reduction of Carbon Dioxide to Value‐Added Products: The Electrocatalyst and Microbial Electrosynthesis

The electrochemical reduction of carbon dioxide (CO₂) to value‐added products obtains great attention and investigation worldwide in recent years. The commercialization of this green process relies on the progress of relating high‐performance electrocatalysts and their feasibility with proper reactor design. The microbial electrosynthesis (MES) is an alternative route to reduce CO₂ with electroactive bio‐film electrode as catalyst. This review presents the research status and development of cathode catalysts, particularly focusing on the active sites and development tendency, for highly efficient electrochemical reduction CO₂ from personal viewpoint. Some of our results are also presented to exhibit contributions. MES shows a similar process to the typical electrochemical reduction of CO₂. Their combination is an important trend, and the future research in this field is full of challenges and opportunities.     

Elucidating the Electrocatalytic CO2 Reduction Reaction over a Model Single‐Atom Nickel Catalyst

Designing effective electrocatalysts for the carbon dioxide reduction reaction (CO₂RR) is an appealing approach to tackling the challenges posed by rising CO₂ levels and realizing a closed carbon cycle. However, fundamental understanding of the complicated CO₂RR mechanism in CO₂ electrocatalysis is still lacking because model systems are limited. We have designed a model nickel single‐atom catalyst (Ni SAC) with a uniform structure and well‐defined Ni‐N₄ moiety on a conductive carbon support with which to explore the electrochemical CO₂RR. Operando X‐ray absorption near‐edge structure spectroscopy, Raman spectroscopy, and near‐ambient X‐ray photoelectron spectroscopy, revealed that Ni⁺ in the Ni SAC was highly active for CO₂ activation, and functioned as an authentic catalytically active site for the CO₂RR. Furthermore, through combination with a kinetics study, the rate‐determining step of the CO₂RR was determined to be *CO₂^?+H⁺→*COOH. This study tackles the four challenges faced by the CO₂RR; namely, activity, selectivity, stability, and dynamics.     

Effect of Elevated Carbon Dioxide Exposure on Nutrition-Health Properties of Micro-Tom Tomatoes

(1) Background: The anthropogenically induced rise in atmospheric carbon dioxide (CO₂) and associated climate change are considered a potential threat to human nutrition. Indeed, an elevated CO₂ concentration was associated with significant alterations in macronutrient and micronutrient content in various dietary crops. (2) Method: In order to explore the impact of elevated CO₂ on the nutritional-health properties of tomato, we used the dwarf tomato variety Micro-Tom plant model. Micro-Toms were grown in culture chambers under 400 ppm (ambient) or 900 ppm (elevated) carbon dioxide. Macronutrients, carotenoids, and mineral contents were analyzed. Biological anti-oxidant and anti-inflammatory bioactivities were assessed in vitro on activated macrophages. (3) Results: Micro-Tom exposure to 900 ppm carbon dioxide was associated with an increased carbohydrate content whereas protein, minerals, and total carotenoids content were decreased. These modifications of composition were associated with an altered bioactivity profile. Indeed, antioxidant anti-inflammatory potential were altered by 900 ppm CO₂ exposure. (4) Conclusions: Taken together, our results suggest that (i) the Micro-Tom is a laboratory model of interest to study elevated CO₂ effects on crops and (ii) exposure to 900 ppm CO₂ led to the decrease of nutritional potential and an increase of health beneficial properties of tomatoes for human health.     

Direct Electrochemical Capture and Release of Carbon Dioxide Using an Industrial Organic Pigment: Quinacridone

Limiting anthropogenic carbon dioxide emissions constitutes a major issue faced by scientists today. Herein we report an efficient way of controlled capture and release of carbon dioxide using nature inspired, cheap, abundant and non‐toxic, industrial pigment namely, quinacridone. An electrochemically reduced electrode consisting of a quinacridone thin film (ca. 100 nm thick)on an ITO support forms a quinacridone carbonate salt. The captured CO₂ can be released by electrochemical oxidation. The amount of captured CO₂ was quantified by FT‐IR. The uptake value for electrochemical release process was 4.61 mmol g^?1. This value is among the highest reported uptake efficiencies for electrochemical CO₂ capture. For comparison, the state‐of‐the‐art aqueous amine industrial capture process has an uptake efficiency of ca. 8 mmol g^?1.     

Toward efficient catalysts for electrochemical CO2 conversion to C2 products

With impressive progress in carbon capture and renewable energy, carbon dioxide (CO₂) conversion into useful chemicals has become a potential tool against climate change. Electrochemical CO₂ conversion into C₂ products (ethylene and ethanol) is an especially economically promising approach and an active research area. Nonetheless, catalyst layer design for CO₂ conversion is challenging because of the complex CO₂-to-C₂ reaction pathways. In this review, we highlight key ideas in catalyst layer design for CO₂ conversion to C₂ in the past few years. We identify three fundamental principles to control catalyst selectivity—local CO₂ and CO concentration, local pH, and intermediate–catalyst interaction. To achieve these goals, we introduce design strategies for both catalytic materials and overall catalyst layer morphology.     

On the Possible Roles of the Zn Cation in the Carbon Dioxide Hydration Reaction: An Ab Initio RHF-SCF MO Study of Transition Structures on the [OH2 + CO2] [ZnOH2CO2]2+ and [Zn(NH3)3OH2CO2]2+ Reactive Hypersurfaces

Transition structures and related minima on the reactive energy hypersurfaces for the hydration of carbon dioxide in the presence of a bare zinc ion and with the cation liganded with three ammonia molecules are determined in the RHF MO SCF framework at a relatively high level of basis-set representation. For the sake of comparison, the standard intramolecular proton transfer model in absence of zinc is revisited and the corresponding transition structure (TS) located. In the coordination sphere of zinc, the standard mechanism of hydration in vacuo is modified: a nucleophilic attack of water onto zinc-activated carbon dioxide. The reactive path goes via TS signaling synchronous movements in the coordination sphere of zinc: Water goes away from and carbon dioxide toward the metal. For the model systems [ZnOH₂CO₂]²⁺, this TS connects with a valley having a geminal carbonic acid (gCA) as product; the carbon–oxygen interaction of the in vacuo complex H₂O···CO₂ is transformed into a covalent bond by its binding to zinc: H₂O—CO₂-Zn is a minimum on this energy hypersurface. The standard path for intramolecular proton transfer, namely, H₂O—CO₂—Zn changing into (HO)₂—CO—Zn, is not catalyzed by the metal. For the ammonia-ligand model system, the carbon dioxide hydration follows the same pathway as in the bare-zinc case. A possible irreversible mechanism of carbon dioxide hydration catalyzed by carbonic anhydrases at pH lower than 6 can be suggested based on the present study; here, a central role is played by an intermolecular deprotonation of gCA by water found at the active-site cleft around the metal center. This zinc–water mechanism is extrapolated to include a general acid catalysis of bicarbonate/carbon dioxide interconversion in water. Results obtained with a hydronium ion replacing zinc and an ancillary water acting as a proton acceptor for the gCA strongly suggest that, in water at pHs lower than 7, direct deprotonation of gCA offers a low-activation channel to produce carbonic acid; in the reverse direction, protonation of the hydroxyl oxygen in bicarbonate leading to gCA offers a reasonable answer to the instability of this anion in solution at low pH. This picture agrees with the one reported by Paneth and O'Leary. [J. Am. Chem. Soc. 107, 7381 (1985)] based on experimental kinetic information.     

Salting-in/Salting-out Mechanism of Carbon Dioxide in Aqueous Electrolyte Solutions

The solvation of carbon dioxide in sea water plays an important role in the carbon circle and the world climate. The salting-out/salting-in mechanism of CO₂ in electrolyte solutions still remains elusive at molecule level. The ability of ion salting-out/salting-in CO₂ in electrolyte solution follows Hofmeister Series and the change of water mobility induced by salts can be predicted by the viscosity B-coefficients. In this work, the chemical potential of carbon dioxide and the dynamic properties of water in aqueous NaCl, KF and NaClO₄ solutions are calculated and analyzed. According to the viscosity B-coefficients, NaClO₄ (0.012) should salt out the carbon dioxide relative to in pure water, but the opposite effect is observed for it. Our simulation results suggest that the salting-in effect of NaClO₄ is due to the strongly direct anion-CO₂ interaction. The inconsistency between Hofmeister Series and the viscosity B-coefficient suggests that it is not always right to indicate whether a salt belongs to salting-in or salting-out just from these properties of the salt solution in the absence of solute.     

Electrocatalytic Production of C3‐C4 Compounds by Conversion of CO2 on a Chloride‐Induced Bi‐Phasic Cu2O‐Cu Catalyst

Electrocatalytic conversion of carbon dioxide (CO₂) has recently received considerable attention as one of the most feasible CO₂ utilization techniques. In particular, copper and copper‐derived catalysts have exhibited the ability to produce a number of organic molecules from CO₂. Herein, we report a chloride (Cl)‐induced bi‐phasic cuprous oxide (Cu₂O) and metallic copper (Cu) electrode (Cu₂O_Cl) as an efficient catalyst for the formation of high‐carbon organic molecules by CO₂ conversion, and identify the origin of electroselectivity toward the formation of high‐carbon organic compounds. The Cu₂O_Cl electrocatalyst results in the preferential formation of multi‐carbon fuels, including n‐propanol and n‐butane C3–C4 compounds. We propose that the remarkable electrocatalytic conversion behavior is due to the favorable affinity between the reaction intermediates and the catalytic surface.     

Homogeneous Light‐Driven Catalytic Direct Carboxylation with CO2

Carbon dioxide is a ubiquitous and inexpensive one‐carbon source for chemical synthesis, and the efficient incorporation of CO₂ into organic molecules is of widespread research interest both for economic and ecological reasons. The methodologies to employ carbon dioxide as a single‐carbon unit to construct molecules relevant for agrochemical and pharmaceutical research include many elegant approaches, including asymmetric transformations. Even though remarkable achievements have been made in the field of light‐driven catalysis, especially photoredox catalysis, homogeneous light‐driven catalytic carboxylation by employing CO₂ as the key reagent has only become a subject of increasing attention in recent years. Therefore, this concise review will discuss the latest advances in this research area.     

Palladium‐catalyzed carbonylation of primary amines in supercritical carbon dioxide

The chemoselectivity of the palladium‐catalyzed carbonylation of amines was affected by the addition of MeOH in supercritical carbon dioxide. The results show different selectivity in supercritical carbon dioxide CO₂(sc) from that in alcohol. Methyl carbamate and its derivatives were obtained in high yields in CO₂(sc).     

Oxygenates from the Electrochemical Reduction of Carbon Dioxide

Electrochemical reduction of carbon dioxide (CO₂) driven by renewable electricity to give chemicals and fuels is considered an ideal approach that can alleviate both carbon emission and energy tension stress. High‐value chemicals such as oxygenates can be effectively produced from the electroreduction of CO₂, and this is highly attractive to promote the economy and applicability of CO₂ utilization. This review focuses on recent advancements in the electrochemical reduction of CO₂ to formic acid, methanol, ethanol, acetic acid, and other oxygenates. The principles of the process, influencing factors, and typical catalysts are summarized. On the basis of the aforementioned discussions, we present future prospects for further development of the electroreduction of CO₂ to oxygenates.     

Efficient Photoelectrochemical Reduction of Carbon Dioxide to Formic Acid: A Functionalized Ionic Liquid as an Absorbent and Electrolyte

Photoelectrochemical (PEC) reduction of carbon dioxide (CO₂) is a potential method for production of fuels and chemicals from a C1 feedstock accumulated in the atmosphere. However, the low solubility of CO₂ in water, and complicated processes associated with capture and conversion, render CO₂ conversion inefficient. A new concept is proposed in which a PEC system is used to capture and convert CO₂ into formic acid. The process is assisted by an ionic liquid (1‐aminopropyl‐3‐methylimidazolium bromide) aqueous solution, which functions as an absorbent and electrolyte at ambient temperature and pressure. Within this PEC reduction strategy, the ionic liquid plays a critical role in promoting the conversion of CO₂ to formic acid and suppressing the reduction of H₂O to H₂. At an applied voltage of 1.7 V, the Faradaic efficiency for formic acid production is as high as 94.1 % and the electro‐to‐chemical efficiency is 86.2 %.