Novel Technological Paradigm of the Application of Carbon Dioxide as a C1 Synthon in Organic Chemistry: I. Synthesis of Hydroxybenzoic Acids, Methanol, and Formic Acid

Bazhenov S., Chuboksarov V., Maximov A., Zhdaneev O.

Carbon dioxide is one of the main contributors to global climate change. The Russian Federation plays an essential role as one of the primary fossil fuel producers and CO 2 emitters globally. Therefore, introducing novel carbon capture, utilization, and storage (CCUS) technologies will inevitably contribute to further Russia's economic and industrial development. Moreover, CCUS should be intensified due to the cross-border tax under Carbon Border Adjustment Mechanism (CBAM) introduced by European Union. This paper presents a brief review of the CO 2 capture strategies and their comparison. A short overview of different CCUS technologies with a partial focus on the studies by the Russian researchers is presented. CO 2 transportation, utilization, and storage aspects are highlighted, considering Russia's potential. The model scheme of the CCUS plant based on existing technologies is given, and the economic estimations and consequences relative to Russian policy under the CBAM tax are discussed. The markable financial losses are shown; thus, the commercial success of CCUS can only bring a radical reduction in cost, which is only expected by 2040.

Singh T., Jalwal S., Chakraborty S.

Depletion of fossil fuel for global energy need emits large amount of greenhouse gas carbon dioxide into the biosphere. Carbon dioxide constitutes a sustainable C1 feedstock and costeffective raw material for the synthesis of bulk and fine chemicals. The catalytic hydrogenation of CO 2 to formic acid, and methanol is an attractive protocol owing to their application in chemical industry and as potential renewable hydrogen storage materials. Catalytic hydrogenation reactions are atom-economical, green and sustainable synthetic routes towards various new environmentally benign transformations. Homogeneous catalytic hydrogenation reactions based on earth-abundant, eco-friendly, first-row base metals for the preparation of an assortment of organic scaffolds is currently of paramount importance in academia and industry. The surge in base metal catalysis is evident from the increase in reports available in the literature in recent years.

Do Not Cite, Quote or Distribute 4-1 Total pages: 139 1 Chapter 4: Sea Level Rise and Implications for Low Lying Islands, Coasts and Communities 2 3 Coordinating Lead Authors: Michael Oppenheimer (USA), Bruce Glavovic (New Zealand), Tuhin Ghosh 4 (India) 5 6 Lead Authors: Amro Abd-Elgawad (Egypt), Rongshuo Cai (China), Miguel Cifuentes-Jara (Costa Rica), 7 Rob Deconto (USA), John Hay (Cook Islands), Jochen Hinkel (Germany), Federico Isla (Argentina), 8 Alexandre K. Magnan (France), Ben Marzeion (Germany), Benoit Meyssignac (France), Zita Sebesvari 9 (Hungary), AJ Smit (South Africa), Roderik van de Wal (Netherlands) 10 11 Contributing Authors: Maya Buchanan (USA), Gonéri Le Cozannet (France), Catia Domingues 12 (Australia), Virginie Duvat (France), Tamsin Edwards (UK), Miguel D. Fortes (Philippines), Thomas 13 Frederikse (Netherlands), Jean-Pierre Gattuso (France), Robert Kopp (USA), Erwin Lambert (Netherlands), 14 Elizabeth McLeod (USA), Mark Merrifield (USA), Siddharth Narayan (US), Robert J. Nicholls (UK), 15 Fabrice Renaud (UK), Jonathan Simm (UK), Jon Woodruff (USA), Poh Poh Wong (Singapore), Siyuan Xian 16 (USA) 17 18 Review Editors: Ayako Abe-Ouchi (Japan), Kapil Gupta (India), Joy Pereira (Malaysia) 19 20 Chapter Scientist Maya Buchanan (USA) 21 22 Date of Draft: 20 April 2018 23 24 Notes: TSU Compiled Version 25 26

Wei D., Sang R., Sponholz P., Junge H., Beller M.

Efficient hydrogen storage and release are essential for effective use of hydrogen as an energy carrier. In principle, formic acid could be used as a convenient hydrogen storage medium via reversible CO2 hydrogenation. However, noble metal-based catalysts are currently needed to facilitate the (de)hydrogenation, and the CO2 produced during hydrogen release is generally released, resulting in undesirable emissions. Here we report an α-amino acid-promoted system for reversible CO2 hydrogenation to formic acid using a Mn-pincer complex as a homogeneous catalyst. We observe good stability and reusability of the catalyst and lysine as the amino acid at high productivities (CO2 hydrogenation: total turnover number of 2,000,000; formic acid dehydrogenation: total turnover number of 600,000). Employing potassium lysinate, we achieve >80% H2 evolution efficiency and >99.9% CO2 retention in ten charge–discharge cycles, avoiding CO2 re-loading steps between each cycle. This process was scaled up by a factor of 18 without obvious drop of the productivity. Formic acid is a convenient hydrogen storage medium with storage release occurring via reversible hydrogenation of CO2 and facilitated by noble metal-based catalysts. Now, reversible storage release is demonstrated using a non-noble, Mn-based catalyst in the presence of an amino acid.

Shao Y., Kosari M., Xi S., Zeng H.C.

Bowker M., Lawes N., Gow I., Hayward J., Esquius J.R., Richards N., Smith L.R., Slater T.J., Davies T.E., Dummer N.F., Kabalan L., Logsdail A., Catlow R.C., Taylor S., Hutchings G.J.

The rise in atmospheric CO2 concentration and the concomitant rise in global surface temperature have prompted massive research effort in designing catalytic routes to utilize CO2 as a feedstock. Prime among these is the hydrogenation of CO2 to make methanol, which is a key commodity chemical intermediate, a hydrogen storage molecule, and a possible future fuel for transport sectors that cannot be electrified. Pd/ZnO has been identified as an effective candidate as a catalyst for this reaction, yet there has been no attempt to gain a fundamental understanding of how this catalyst works and more importantly to establish specific design criteria for CO2 hydrogenation catalysts. Here, we show that Pd/ZnO catalysts have the same metal particle composition, irrespective of the different synthesis procedures and types of ZnO used here. We demonstrate that all of these Pd/ZnO catalysts exhibit the same activity trend. In all cases, the β-PdZn 1:1 alloy is produced and dictates the catalysis. This conclusion is further supported by the relationship between conversion and selectivity and their small variation with ZnO surface area in the range 6-80 m2g-1. Without alloying with Zn, Pd is a reverse water-gas shift catalyst and when supported on alumina and silica is much less active for CO2 conversion to methanol than on ZnO. Our approach is applicable to the discovery and design of improved catalysts for CO2 hydrogenation and will aid future catalyst discovery.

Ren M., Zhang Y., Wang X., Qiu H.

High-efficiency utilization of CO2 facilitates the reduction of CO2 concentration in the global atmosphere and hence the alleviation of the greenhouse effect. The catalytic hydrogenation of CO2 to produce value-added chemicals exhibits attractive prospects by potentially building energy recycling loops. Particularly, methanol is one of the practically important objective products, and the catalytic hydrogenation of CO2 to synthesize methanol has been extensively studied. In this review, we focus on some basic concepts on CO2 activation, the recent research advances in the catalytic hydrogenation of CO2 to methanol, the development of high-performance catalysts, and microscopic insight into the reaction mechanisms. Finally, some thinking on the present research and possible future trend is presented.

Zhang X., Kirilin A.V., Rozeveld S., Kang J.H., Pollefeyt G., Yancey D.F., Chojecki A., Vanchura B., Blum M.

Irrgang A.M., Bendixen M., Farquharson L.M., Baranskaya A.V., Erikson L.H., Gibbs A.E., Ogorodov S.A., Overduin P.P., Lantuit H., Grigoriev M.N., Jones B.M.

Arctic coasts are vulnerable to the effects of climate change, including rising sea levels and the loss of permafrost, sea ice and glaciers. Assessing the influence of anthropogenic warming on Arctic coastal dynamics, however, is challenged by the limited availability of observational, oceanographic and environmental data. Yet, with the majority of permafrost coasts being erosive, coupled with projected intensification of erosion and flooding, understanding these changes is critical. In this Review, we describe the morphological diversity of Arctic coasts, discuss important drivers of coastal change, explain the specific sensitivity of Arctic coasts to climate change and provide an overview of pan-Arctic shoreline change and its multifaceted impacts. Arctic coastal changes impact the human environment by threatening coastal settlements, infrastructure, cultural sites and archaeological remains. Changing sediment fluxes also impact the natural environment through carbon, nutrient and pollutant release on a magnitude that remains difficult to predict. Increasing transdisciplinary and interdisciplinary collaboration efforts will build the foundation for identifying sustainable solutions and adaptation strategies to reduce future risks for those living on, working at and visiting the rapidly changing Arctic coast. Arctic coasts are increasingly affected by erosion and flooding, owing to decreasing sea ice, thawing permafrost and rising sea levels. This Review examines the changes in Arctic coastal morphodynamics and discusses the broader impacts on Arctic systems.

Hjort J., Streletskiy D., Doré G., Wu Q., Bjella K., Luoto M.

The warming and thawing of ice-rich permafrost pose considerable threat to the integrity of polar and high-altitude infrastructure, in turn jeopardizing sustainable development. In this Review, we explore the extent and costs of observed and predicted infrastructure damage associated with permafrost degradation, and the methods available to mitigate such adverse consequences. Permafrost change imposes various threats to infrastructure, namely through warming, active layer thickening and thaw-related hazards such as thermokarst and mass wasting. These impacts, often linked to anthropogenic warming, are exacerbated through increased human activity. Observed infrastructure damage is substantial, with up to 80% of buildings in some Russian cities and ~30% of some road surfaces in the Qinghai–Tibet Plateau reporting damage. Under anthropogenic warming, infrastructure damage is projected to continue, with 30–50% of critical circumpolar infrastructure thought to be at high risk by 2050. Accordingly, permafrost degradation-related infrastructure costs could rise to tens of billions of US dollars by the second half of the century. Several mitigation techniques exist to alleviate these impacts, including convection embankments, thermosyphons and piling foundations, with proven success at preserving and cooling permafrost and stabilizing infrastructure. To be effective, however, better understanding is needed on the regions at high risk. Permafrost thaw and degradation threaten circumpolar infrastructure. This Review documents observed and projected infrastructure impacts, as well as the mitigation strategies available to minimize them.

Ghosh A., Reddy G.N., Siddhique P. K. M., Chatterjee S., Bhattacharjee S., Maitra R., Lyubimov S.E., Arzumanyan A.V., Naumkin A., Bhaumik A., Chowdhury B.

Compositional doping by nitrogen and sulfur into a carbon matrix with a distinct hollow sphere architecture was achieved via a simple approach and the co-doped carbon material was used as a bifunctional catalyst for an efficient CO2–epichlorohydrin cycloaddition reaction.

Smith S.L., O’Neill H.B., Isaksen K., Noetzli J., Romanovsky V.E.

Permafrost temperatures have increased in polar and high-elevation regions, affecting the climate system and the integrity of natural and built environments. In this Review, we outline changes in the thermal state of permafrost, focusing on permafrost temperatures and active-layer thickness. Increases in permafrost temperature vary spatially owing to interactions between climate, vegetation, snow cover, organic-layer thickness and ground ice content. In warmer permafrost (temperatures close to 0 °C), rates of warming are typically less than 0.3 °C per decade, as observed in sub-Arctic regions. In colder permafrost (temperatures less than −2 °C), by contrast, warming of up to about 1 °C per decade is apparent, as in the high-latitude Arctic. Increased active-layer thicknesses have also been observed since the 1990s in some regions, including a change of 0.4 m in the Russian Arctic. Simulations unanimously indicate that warming and thawing of permafrost will continue in response to climate change and potentially accelerate, but there is substantial variation in the magnitude and timing of predicted changes between different models and scenarios. A greater understanding of longer-term interactions between permafrost, climate, vegetation and snow cover, as well as improved model representation of subsurface conditions including ground ice, will further reduce uncertainty regarding the thermal state of permafrost and its future response. Permafrost thaw is directly governed by the thermal characteristics of the frozen ground. This Review outlines the status of and mechanisms influencing the thermal state of permafrost, revealing widespread increases in permafrost temperatures and active-layer thicknesses.

Gorbunov D.N., Nenasheva M.V., Terenina M.V., Kardasheva Y.S., Kardashev S.V., Naranov E.R., Bugaev A.L., Soldatov A.V., Maximov A.L., Karakhanov E.A.

In view of the growing environmental concerns and the need to involve alternative sources of raw materials in the chemical industry, intensive research efforts in the last decades have focused on carbon dioxide reactions. In this context, the present review discusses prior studies that were aimed at producing commercially important compounds, such as acids, alcohols, organic carbonates, and polycarbonates, in homogeneous catalytic systems that contain transition-metal complexes. Such systems have been traditionally valued for their high activity and selectivity under relatively mild conditions. The review provides systematized information both on CO2 reactions with hydrogen to produce C1 chemicals such as formic acid and methanol, and on CO2 interactions with organics (e.g., olefins, alcohols, and epoxides) to produce valuable chemical compounds.

Sen R., Koch C.J., Galvan V., Entesari N., Goeppert A., Prakash G.K.

• First example of integrated CO 2 capture and conversion to methanol using a commercial Cu/ZnO/Al 2 O 3 catalyst is demonstrated. • An efficient and recyclable alcohol assisted system was developed for CO 2 hydrogenation with methanol yields up to 90%. • A 120% increase in methanol yield was achieved using ethylene glycol as the solvent. • A renewable methanol synthesis is reported using the combination of heterogeneous catalysis and air as the carbon source. A highly effective liquid phase system for hydrogenation of CO 2 to methanol using a heterogeneous Cu/ZnO/Al 2 O 3 catalyst under batch conditions was developed. Among the screened solvents, glycols were found to have a marked promoting effect on methanol formation at a relatively low temperature range of 170–200 °C using molecular H 2 . Relative to the solventless system, ethylene glycol enhanced the CO 2 conversion values by up to 120% which is close to the calculated equilibrium limit. CH 3 OH yields of up to 90% were achieved. The catalyst was remarkably stable and recyclable over multiple hydrogenation cycles. Furthermore, CO 2 captured by alkali hydroxides as well as amines were successfully hydrogenated to CH 3 OH with the Cu/ZnO/Al 2 O 3 catalyst for the first time with >90% yields. The catalytic process and the plausible reaction pathways were evaluated by control experiments, which suggest that the hydrogenation in the presence of an alcohol proceeds through the formation of formate ester as an intermediate. Finally, the integration of direct air capture (DAC) and hydrogenation of CO 2 was demonstrated efficiently as a novel methanol synthesis process using the combination of heterogeneous catalysis and air as a renewable carbon source. Such scalable processes have considerable potential for synthesis of renewable methanol in an efficient and relatively cost-effective approach.

Bondarenko G.N., Ganina O.G., Lysova A.A., Fedin V.P., Beletskaya I.P.

• Zn-based MOFs in the presence tetrabutylammonium bromide (TBAB) selectively catalyse conversion of CO 2 to cyclic carbonates. • Good to quantitative yields are obtained on aromatic, aliphatic epoxides, including fluorinated, di-substituted epoxides and bicyclic. • The MOF catalyst has been reused in five cycles. A series of microporous metal-organic frameworks, NIIC-10, based on 2,5-thiophendicarboxylate (tdc 2– ), 1,4-diazabicyclo[2.2.2]octane (dabco), polyol ligands and Zn-ions were investigated in carboxylation of mono-, di and tri-substituted epoxides in the presence of tetrabuthylammonium bromide (TBAB). Reactions were carried out in solventless media under CO 2 atmosphere and 80°C. All resulting mono- and disubstituted cyclic carbonates were obtained in good to excellent yields. Furthermore, the catalyst also showed good selectivity and recyclability for five cycles without a significant loss of activity.

Merzliakov D.A., Alexeev M.S., Topchiy M.A., Yakhvarov D.G., Kuznetsov N.Y., Maximov A.L., Beletskaya I.P.

In this study, the homogeneous carboxylation of potassium, sodium, and lithium phenolates in DMSO solution at 100 °C by the Kolbe–Schmitt reaction was investigated. The impact of water, phenolate concentration, and cation nature on the yield of products and reaction selectivity was demonstrated. Based on the patterns observed, it was concluded that a complex cluster mechanism governs the carboxylation reaction in the solution. The use of a homogeneous reaction medium allowed for convenient testing of various additives to assess their impact on the reaction. Basic additives such as sodium salts of mesitol, tert-butylcalix[4]arene, sodium isopropyl, and tert-butyl cabonates were found to enhance the reaction, increasing the yield of hydroxybenzoic acids by 20% (to 61.6%). The main product in the DMSO solution was identified as 4-hydroxybenzoic acid, in contrast to the classical Kolbe–Schmitt method which typically yields 2-hydroxybenzoic (salicylic) acid. The use of 13C NMR spectroscopy enabled the observation of a “carbonate complex” in the solution for the first time, with the carbonate carbon displaying a chemical shift value of 142 ppm, an unusual finding for stable carbonates, and located between the signals of free dissolved CO2 and carboxylate derivatives.

Grushevenko Е.А., Solkolov S.Е., Kholodkov D.N., Arzumanyan А.V., Kuznetsov N.Y., Nikul'shin P.V., Bazhenov S.D., Volkov A.V., Borisov I.L., Maksimov A.L.

Batkin A.M., Tedeeva M.A., Kalmykov K.B., Leonov A.V., Davshan N.A., Pribytkov P.V., Dunaev S.F., Beletskaya I.P., Kustov A.L.

The catalytic properties of Cu–Zn catalysts are investigated on such commercial supports as Al2O3, SiO2, ZrO2(La), TiO2, ZnO, and activated carbon in the reaction of CO2 hydrogenation with the production of methanol. CuZn/Al2O3 catalyst displays the highest conversion of CO2. The highest selectivities toward methanol (99 and 97.5%) are observed for CuZn/ZrO2(La) and CuZn/SiO2 catalysts, respectively, while high values of selectivity toward CH3OH (90–95%) are achieved in the 175–275°C range of temperatures. The highest methanol productivity is 547 g/(kgkat h) on catalyst CuZn/ZrO2(La). The synthesized catalysts are studied via low-temperature nitrogen adsorption, X-ray diffraction, and SEM-EDX.

Kuznetsov Nikolai Yu., Maximov Anton L., Beletskaya Irina P.

The development of atom-economical and efficient processes for obtaining a variety of chemical products using CO2 as C1-synthon plays an increasingly important role in modern scientific and technological research. Due to the inertness of CO2 many extremely attractive routes to valuable chemical products turn out to be impossible to implement, particularly for thermodynamic reasons, leaving one only dreaming about them as something unattainable. This review demonstrates how the catalytic coupling of ethylene and CO2 into acrylic acid, once considered a "dream reaction" has not only become a reality, but has also evolved into the category of technological processes. The key stages of the long-term development of this unique reaction from the discovery of metal activation of CO2 and stoichiometric preparation of metallalactones to catalytic synthesis using a variety of metal-catalysts (Ni, Pd, Ru, Rh) showcase the ingenuity and skill of researchers as well as an example of consistent development in this field of chemistry. We believe that this remarkably successful example will inspire scientists to tackle any "impossible" problems.The bibliography includes 117 references.

Tedeeva M.A., Kustov A.L., Batkin A.M., Garifullina C., Zalyatdinov A.A., Yang D., Dai Y., Yang Y., Kustov L.M.

Sedlova D.V., Osipova E.S., Gutsul E.I., Godovikov I.A., Filippov O.A., Shubina E.S., Belkova N.V.

The interaction of bimetallic (ButPCP)Pd···(OC)M(CO)2 Cp (M = Mo, W) complexes with PhSiH3 leads to an efficient heterolytic splitting of Si–H bond that is a primary step in catalytic hydrosilylation of CO2. The reaction can be stopped at the formate level in the presence of the above complexes while proceeds further when catalyzed by (ButPCP)PdH.

Maximov Anton L., Beletskaya Irina P.

Development of the "methanol" economy may be a way to establish the new chemistry under decarbonization conditions. Methanol here is used as a raw material for production of a wide range of chemicals, conventionally obtained from oil. The key process for the "methanol" economy is the reduction of CO2, which, along with renewable energy, is the main carbon-containing resource in the low-carbon industry. This review summarizes recent data on the main approaches to methanol production from CO2: catalytic hydrogenation of CO2 with hydrogen on heterogeneous or homogeneous catalysts; electrochemical reduction of CO2 to methanol; and CO2 conversion using photocatalysis. The main advantages and disadvantages of each method, the mechanisms of CO2 conversion taking into account the features of each type of catalysis, and the main approaches to the efficient catalysts are discussed.The bibliography includes 542 references.

Kuznetsov N.Y., Beletskaya I.P.

CO2 composes cheap, easily available and practically inexhaustible source of synthetic carbon (C1-synthon). Among the various transformations of carbon dioxide, synthesis of cyclic carbonates from epoxides and carbamates from aziridines can be referred to the priority areas in the development of contemporary chemical synthesis and catalysis. Cyclic carbonates found wide application in modern industry (electrolytes, solvents, reagents, polymers) and their use and production will be constantly increased. At the forefront of research appears the development of effective catalytic processes, allowing carry out the synthesis of carbonates under mild conditions (atmospheric pressure of CO2 or lower, temperature - 25°С) with low catalyst loads, which sustains its high activity for a long time and is affordable. In the current review we analyze the existing directions of research and catalytic systems based on salts of cheap and earth-abundant metals Al3+, Fe2+(3+) and Zn2+ for the preparation of cyclic carbonates from epoxides and carbamates from aziridines.

Kuznetsov N.Y., Beletskaya I.P.

Carbon dioxide is a cheap, easily available, and practically inexhaustible source of synthetic carbon (C1-synthon). Among various transformations of CO2, the synthesis of cyclic carbonates from epoxides and cyclic carbamates from aziridines can be referred to as priority areas in the development of contemporary chemical synthesis and catalysis. Cyclic carbonates found wide application in modern industry (electrolytes, solvents, reagents, polymers) and their use and production will be constantly increased. The development of effective catalytic processes that would allow the synthesis of carbonates under mild conditions (atmospheric pressure of CO2 or lower, temperature 25°C) and low loads of durable and affordable catalysts is at the forefront of research. In the present review we analyze the existing directions of research on the catalytic systems based earth-abundant metals Al3+, Fe2+(3+), and Zn2+ for the synthesis of cyclic carbonates from epoxides and cyclic carbamates from aziridines.