A research team led by Prof. DAI Wen from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS), in collaboration with Associate Prof. ZHANG Zehui from South-Central University for Nationalities, developed a new strategy for heterogeneous catalytic successive cleavage and functionalization of C–C bonds in alcohols.Their findings were published in Chem on Mar. 25.Schematic illustrations of the manganese oxide for catalytic cleavage and functionalization of alcohols reaction (Image by HE Peipei)Given that alcohols can be broadly accessible from both fossil resources and naturally renewable biomass, the oxidative cleavage and functionalization of C–C bonds in alcohols has emerged as a powerful tool for the conversion of alcohols to a variety of value-added chemicals.Indeed, in the past decades, some homogeneous catalytic systems have been well established for the cleavage and functionalization of alcohols. However, over-reliance on stoichiometric and environmentally unfriendly oxidants, a large excess of a strong base, and/or high loading of precious metal catalysts still limit most of these reaction classes.The researchers developed a novel and efficient protocol that enables the direct synthesis of amides via heterogeneous manganese oxide catalyzed successive cleavage and amidation of C-C bonds in alcohols with oxygen as an environmentally benign oxidant and ammonia as nitrogen source.They found that a wide range of primary and secondary alcohols, 1,2-diols, and even β-O-4 and β-1 lignin model compounds could undergo C–C bond cleavage smoothly to deliver one- or multiple-carbon shorter amides. Moreover, a slight modification of the reaction conditions allowed for the cleavage and cyanation of alcohols to access sterically hindered nitriles.This protocol features good functional-group tolerance, facile scalability, a cost-effective and recyclable catalyst, the use of readily available starting materials, a broad substrate scope. It has been applied to the late-stage amidation and cyanation of bioactive alcohols, which offers an efficient way to generate natural product derivatives for drug discovery and chemical biology."Therefore, this method not only complements existing protocols for transformations of alcohols but also expands the new application of the abundant fossil resources and renewable biomass," said Prof. DAI.The above research was supported by DICP and the National Natural Science Foundation of China. (Text by HE Peipei)

Flow batteries are promising for energy storage due to their high safety, high reliability, long cycle life, and high efficiency.The development of commercial-scale flow batteries for long-duration energy storage requires to reduce the cost of flow batteries, especially the cost of ion-exchange membranes.Recently, a research group led by Prof. LI Xianfeng from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) realized pilot-scale synthesis and roll-to-roll manufacturing of hydrocarbon membranes with high-performance in alkaline-based flow batteries.This work was published in Joule on March 21.The hydrocarbon membranes for alkaline-based flow batteries with high performance (Image by YUAN Zhizhang)The researchers realized the kilogram-level synthesis of sulfonated poly(ether-ether-ketone) (SPEEK) polymer and demonstrated the pilot-scale roll-to-roll synthesis of SPEEK membrane and their applications in alkaline-based flow batteries.They found that the rigid skeleton and dispersive cation exchange groups enabled the high stability of the membrane in alkaline media, and could confine O-containing species (H2O, OH-, etc.) inside the membrane, resulting in the formation of continuous hydrogen-bonding networks. This favoured the dissociation of H+ in H–O–H (H2O) and transfer from H2O to adjacent OH- ions through a Grotthuss mechanism, thus providing a high OH- conductivity in SPEEK.The membrane was integrated in alkaline zinc-iron flow battery stack with power up to 4 kW, with a high energy efficiency of 85.5% operated at 80 mA/cm2.This work was supported by the National Natural Science Foundation of China, CAS Engineering Laboratory for Electrochemical Energy Storage, and the Youth Innovation Promotion Association of CAS. (Text by YUAN Zhizhang)

　　The world's first demonstration device for 1,000 tons/year production of gasoline from carbon dioxide (CO2) hydrogenation located in Zoucheng Industrial Park, Shandong province, China has completed its trial operation and technology assessment on March 4.
　　The project was jointly developed by the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) and Zhuhai Futian Energy Technology Co., Ltd.
　　Pilot plant for the production of 1000 tons/year gasoline from carbon dioxide (CO2) hydrogenation (Image by HOU Shoufu)
　　Hydrogenation of CO2 into liquid fuels and chemicals can not only realize the resource utilization of CO2, but also facilitate the storage and transportation of renewable energy.
　　However, the activation and selective conversion of CO2 are challenging. A technology that can selectively produce value-added hydrocarbon fuels with high energy density will provide a new route for promoting clean and low-carbon energy revolution.
　　The technology of carbon dioxide hydrogenation to gasoline was proposed by SUN Jian, GE Qingjie and WEI Jian from DICP in 2017, with a paper published in Nature Communications.
　　The demonstration device has been completed in Zoucheng Industrial Park, in 2020. In October 2021, the device passed the continuous 72-hour on-site assessment organized by China Petroleum and Chemical Industry Federation (CPCIF). It could realize both CO2 and H2 conversion of 95%, gasoline selectivity of 85% in all carbon-based products, with reduced consumption of the raw material of CO2 and H2.
　　It produced clean and green gasoline product with octane number more than 90 conforming to the Chinese national VI standard, accompanied by low energy consumption of the whole process.
　　"This technology marks a new stage of CO2 resource utilization technology in the world, and provides a new strategy for realizing the goal of carbon neutral," said Prof. SUN.
　　This work was supported by the Strategic Priority Research Program of "Key Technologies and Demonstration of Transformative Clean Energy" of CAS, the National Natural Science Foundation of China, and the Liaoning Talents Program. (Image by SUN Jian, GE Qingjie and WEI Jian)

　　The oxygen evolution reaction (OER) is significant in the development and application of clean energy. Particularly, the design of high-active and acid-stable electrocatalysts is necessary to meet large-scale requirement for water electrolysis.
　　Recently, a research group led by Prof. XIAO Jianping from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) and Prof. Ryuhei Nakamura from RIKEN synthesized Co2MnO4 spinel, which showed high stability in acid environment for electrocatalysis.
　　This study was published in Nature Catalysis on Feb. 14.
　　"Density functional theoretical calculations confirmed the high activity due to the ideal binding of key intermediates from a truncated volcano activity trend," said Prof. XIAO.
　　Moreover, the researchers established multi dissolution pathways to explain the high stability of Co2MnO4 spinel in acid environment for electrocatalysis.
　　The dissolution of either Co or O was considered. Although, it showed a thermodynamic favorable for the whole reaction of dissolution, the dissolution of lattice O was found to be the most thermodynamically unfavorable elementary step in both pathways, which is the rate-limiting step.
　　The Bader charge analysis indicated a larger electron transfer from Mn to O rather than that from Co to O, which revealed a stronger binding of Mn-O and a more stable lattice O in Co2MnO4.
　　"The truncated volcano activity trend and multi dissolution pathways provided a more accurate and effective way for the rational design of catalysts for oxygen evolution reaction," said Prof. XIAO. (Text by GUO Chenxi)

　　Poly (1,4-cyclohexylene dimethylene terephthalate-co-isophthalate) (PCTA) is an important copolyester that has been widely used in cosmetic containers, home appliances, and medical packaging.
　　Currently, PCTA is manufactured via polycondensation of cyclohexanedimethanol (CHDM), which is industrially produced from petroleum-derived xylene. To reduce the reliance on fossil energy, it's needed to develop a more sustainable alternative way.
　　Recently, a research team led by Prof. ZHANG Tao, Prof. WANG Aiqin and Prof. LI Ning, in collaboration with Prof. WANG Feng's group, from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) developed a sustainable route for the production of copolyester monomers with biomass.
　　This study was published in Angewandte Chemie International Edition on Nov. 30, and it was selected as Hot Paper.
　　A flow diagram for the production of monomers with acetaldehyde and acrylate (Image by YUAN Lin)
　　In this study, the researchers used plant-based acrylate and acetaldehyde as feedstocks, and produced PCTA monomer in an overall yield of 61%. The whole process included Morita–Baylis–Hillman (MBH) reaction, one-step dehydration/Diels–Alder reaction, and final Pd/C-catalyzed dehydrogenation.
　　Besides, they varied the final step to hydrogenation over Pd/C-Cu/Zn/Al dual-bed catalyst, and produced UNOXOLTM diol, which is another important monomer in coatings industry, in an overall yield of 67%.
　　Furthermore, the life cycle assessment implied that the newly-developed biomass-based routes had the potential to reduce carbon footprint.
　　"This study paves a new way for the production of renewable PCTA and also provides a new guidance for biomass conversion," said Prof. LI.
　　This work was supported by the Natural Science Foundation of China and Joint Fund of Yulin University and Dalian National Laboratory for Clean Energy. (Text by LIN Yuan and HU Yancheng)

　　The involvement between electron transfer (ET) and catalytic reaction at electrocatalyst surface makes electrochemical process challenging to understand and control. How to experimentally determine ET process occurring at nanoscale is important to understand the overall electrochemical reaction process at active sites.
　　Recently, a research group led by Prof. LI Can and Prof. FAN Fengtao from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) captured the electron transfer imaging in electrocatalysis process.
　　This study was published in Nano Letters on Oct. 14.
　　Electron transfer current followed the trend: corner> edge> basal plane, driven by the interfacial inner potential differences (Imaged by NIE Wei and FAN Fengtao)
　　The researchers established an in-situ electrochemical imaging method with nanoscale spatial resolution, which combined atomic force microscopy and scanning electrochemical imaging. This method can realize the three-dimensional movement of the scanning nanoprobe to map the local distribution of the generated outer-spherical electron transfer molecules and the catalytic product molecules.
　　The visual electron transfer images on metal nanoplates directly demonstrated that the electron transfer process at nanoscale presented a site-dependent heterogeneity.
　　Moreover, to decouple the interference of the mass transfer effect on the electron transfer, the researchers conducted a series of elaborate experiments and complex mathematical modeling to extract the rate constant and internal potential difference. They found that the relationship between the interfacial inner potential difference and the rate constant followed a linear fashion.
　　This work realizes the in-situ observation of electron transfer process and catalytic reaction in the electrochemical reaction, and provides new ideas for the development of in-situ imaging characterization method and the detection of the mechanism of the electrocatalytic reactions.
　　"This is a new milestone of the scanning electrochemical probe techniques, making it possible to discover the structure-performance relation of nanocatalyst from the bottom of physical and chemical principles," commented by one of the reviewers. (Text by NIE Wei and FAN Fengtao)