Electrochemical Carbon Dioxide Reduction to Ethylene:From Mechanistic Understanding to Catalyst Surface Engineering

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides a promising way to convert CO_(2)to chemicals.The multicarbon(C_(2+))products,especially ethylene,are of great interest due to their versatile industrial applications.However,selectively reducing CO_(2)to ethylene is still challenging as the additional energy required for the C–C coupling step results in large overpotential and many competing products.Nonetheless,mechanistic understanding of the key steps and preferred reaction pathways/conditions,as well as rational design of novel catalysts for ethylene production have been regarded as promising approaches to achieving the highly efficient and selective CO_(2)RR.In this review,we first illustrate the key steps for CO_(2)RR to ethylene(e.g.,CO_(2)adsorption/activation,formation of~*CO intermediate,C–C coupling step),offering mechanistic understanding of CO_(2)RR conversion to ethylene.Then the alternative reaction pathways and conditions for the formation of ethylene and competitive products(C_1 and other C_(2+)products)are investigated,guiding the further design and development of preferred conditions for ethylene generation.Engineering strategies of Cu-based catalysts for CO_(2)RR-ethylene are further summarized,and the correlations of reaction mechanism/pathways,engineering strategies and selectivity are elaborated.Finally,major challenges and perspectives in the research area of CO_(2)RR are proposed for future development and practical applications.

China Academy of Strategy on Aerospace Engineering Science and Technology Inaugurated

China Academy of Strategy on Aerospace Engineering Science and Technology (CAEST) was formally established on December 31,2011.The academy was jointly established by Chinese Academy of Engineering (CAE),China Aerospace Science

Engineering transition metal-based nanomaterials for high-performance electrocatalysis

Transition metal(TM)based electrocatalysts attract increasing attention in energy conversion reactions,and current effects focus on material engineering strategies to tailor physicochemical properties of TM based electrocatalysts for improved performance.This review provides a summary about the recent advances of engineering TM based nanomaterials for electrocatalytic reactions,which include hydrogen evolution reaction(HER),oxygen evolution reaction(OER),CO2 reduction reaction(CO2RR),and nitrate reduction reaction(NO3RR).We highlight four engineering strategies,namely,size engineering,facet engineering,composition engineering,and crystal structure engineering for TM based electrocatalysts,and pay a special emphasis on exploring the relationship between their physicochemical properties and catalytic activities.We outline the opportunities in this research field,in particular,the strategy of rationally combining in-situ and operando techniques and theoretical predication to design efficient electrocatalysts.Finally,issues that deserve attention and consideration for practical applications are discussed.

Emerging material engineering strategies for amplifying photothermal heterogeneous CO_(2)catalysis

Closing the carbon loop,through CO_(2)capture and utilization,is a promising route to mitigate climate change.Solar energy is a sustainable energy source which can be exploited to drive catalytic reactions for utilizing CO_(2),including converting the CO_(2)into useful products.Solar energy can be harnessed through a range of different pathways to valorize CO_(2).Whilst using solar energy to drive CO_(2)reduction has vast potential to promote catalytic CO_(2)conversions,the progress is limited due to the lack of understanding of property-performance relations as well as feasible material engineering approaches.Herein,we outline the various driving forces involved in photothermal CO_(2)catalysis.The heat from solar energy can be utilized to induce CO_(2)catalytic reduction reactions via the photothermal effect.Further,solar energy can act to modify reaction pathways through light-matter interactions.Light-induced chemical functions have demonstrated the ability to regulate intermediary reaction steps,and thus control the reaction selectivity.Photothermal catalyst structures and specific catalyst design strategies are discussed in this context.This review provides a comprehensive understanding of the heat-light synergy and guidance for rational photothermal catalyst design for CO_(2)utilization.

A construction strategy for a tunnel with big deformation

By integrating literature reviews, site observa- tion, field monitoring, theoretical analysis, summarization, etc., a construction strategy was proposed and verified for tunneling with big deformation in this paper. The tunnel was in phyllite, shotcrete cracks and steel arch distortion were observed, and a big deformation with a maximum of 2.0 m was monitored during the initial stage of the construction. Through carefully examining the site observation and laboratory test results, a construction principle was established for the tunneling on the basic concept of maintaining the rock strength/stiffness and keeping the rock dry, by providing confinement pressure to the rock, reducing the rock exposure time, keeping water out of the tunnel, etc. To achieve the construction principle, a set of specific construction measures with 11 items was further proposed and applied to the construction. To check the effectiveness of the construction measures, field monitoring was carried out, which showed that the rock deformation was well controlled and the tunnel became stable. An allowable deformation was then determined using the Fenner formulae and the monitored data in order to guide further construction, which received a good result. From this study, it can be concluded that providing quick strong initial support and reserving core soil at the working faceare extremely important to control the rock deformation and keep the tunnel stable.

Engineering Colloidal Metal-Semiconductor Nanorods Hybrid Nanostructures for Photocatalysis

Emerging engineering strategies of colloidal metal-semiconductor nanorod hybrid nanostructures spanning from type,size,dimension,and location of both metal nanoparticles and semiconductors,co-catalyst,band gap structure,surface ligand to hole scavenger are elaborated symmetrically to rationalize the design of this type of intriguing materials for efficient photocatalytic applications.

Metabolic engineering strategies for microbial utilization of methanol

The increasing shortage of fossil resources and environmental pollution has renewed interest in the synthesis of value-added biochemicals from methanol.However,most of native or synthetic methylotrophs are unable to assimilate methanol at a sufficient rate to produce biochemicals.Thus,the performance of methylotrophs still needs to be optimized to meet the demands of industrial applications.In this review,we provide an in-depth discussion on the properties of natural and synthetic methylotrophs,and summarize the natural and synthetic methanol assimilation pathways.Further,we discuss metabolic engineering strategies for enabling microbial utilization of methanol for the bioproduction of value-added chemicals.Finally,we highlight the potential of microbial engineering for methanol assimilation and offer guidance for achieving a low-carbon footprint for the biosynthesis of chemicals.

Metabolic engineering strategies for microbial utilization of C1 feedstocks

The use of abundant and cheap one carbon(C1)feedstocks to produce value-added chemicals is an important approach for achieving carbon neutrality and tackling environmental problems.The conversion of C1 feedstocks to high-value chemicals is dependent on efficient C1 assimilation pathways and microbial chassis adapted for efficient incorporation.Here,we opted to summarize the natural and synthetic C1 assimilation pathways and their key factors for metabolizing C1 feedstock.Accordingly,we discussed the metabolic engineering strategies for enabling the microbial utilization of C1 feedstocks for the bioproduction of value-added chemicals.In addition,we highlighted future perspectives of C1-based biomanufacturing for achieving a low-carbon footprint for the biosynthesis of chemicals.

Engineering of electrospun nanofiber scaffolds for repairing brain injury

Patients with brain injury can suffer disability and accompanying complications.Current clinical treatments have significant limitations to successful repair due to the complexity of the pathological processes and the inhibitory microenvironment that follows brain injury.Here,we conclude recent research progresses in engineering strate-gies based on electrospun nanofibers for promoting neural repair and functional recovery after brain injury.Firstly,we introduce the main pathological mechanisms of current brain injuries,pointing out the prospect of the application of electrospun nanofiber scaffolds compared to current clinical treatment strategies.We then discuss the repair strategies combining the structure and the morphology of nanofiber scaffolds with load therapeutic factors such as cells,drugs and growth factors.All of these strategies show potential for improving the repair of brain injury.Finally,we point out the challenges facing the effective treatment of brain injury,aiming to provide insights into the development of repairing scaffolds for brain function recovery from the perspective of clinical treatment.

Materials Engineering toward Durable Ru-Based Electrocatalysts for Acidic Oxygen Evolution Reaction

Proton exchange membrane water electrolysis(PEMWE)is considered one of the most promising pathways for producing green hydrogen(H2).However,the sluggish kinetic of the anodic oxygen evolution reaction(OER)hinders the overall efficiency of PEMWE.In the past few decades,ruthenium(Ru)-based materials have been developed as highly active and cost-effective OER catalysts while faced with significant durability challenges.To this end,addressing the durability issues of Ru catalysts is imperative for their practical employment in PEMWE.In this review,state-of-the-art advances in understanding the degradation mechanisms of Ru catalysts in acidic conditions are comprehensively discussed.Then,materials engineering strategies to mitigate degradation through the rational design of stable Ru-catalysts are highlighted.Finally,some prospects are provided in terms of exploring the long-term stability of Ru-based catalysts.This review is anticipated to foster a better understanding of Ru-based catalysts in acidic OER and work on novel strategies for the design of stable Ru-based materials.

Tailoring crystallization zinc hydroxide sulfates growth towards stable zinc deposition chemistry

The unstable zinc anode/electrolyte interface induced by corrosion,interfacial water splitting reaction,and dendrite growth seriously degrades the performances of metal Zn anode in aqueous electrolyte.Herein,the nucleation and growth of zinc hydroxide sulfate(ZHS),an interfacial by-product,has been tailored by Tween 80 in the electrolyte,which thereby assists in in-situ forming a dense solid electrolyte interphase(SEI)with small-sized ZHS and evenly distributed Tween 80.This SEI has high corrosion resistance and uniform distribution of zinc ions,which not only contributes to blocking the interfacial side reactions but also induces stable and calm zinc plating/stripping.Consequently,the modified electrolyte can confer the assembled Zn||Zn symmetric cell with a stable operation life over 1500 h at 1 mA·cm^(−2)and 1 mAh·cm^(−2)as well as the practical Zn||NH4V4O10 full battery with a high-rate capacity of 120 mAh·g^(−1)at the current density of 5 A·g^(−1).This work provides a way for regulating and reusing interfacial by-products,and a new sight on stabilization electrodes/electrolyte interfaces.

光电化学水分解中基于半导体的界面工程策略和载流子动力学表征技术的研究进展

为了缓解能源危机和环境问题,太阳能的应用受到了人们的广泛关注.光电化学水分解是一种极有前景的、可以将清洁可再生太阳能转化为清洁燃料的技术.提高能量转换效率无疑是光电化学水分解技术的关键.光生载流子的分离和转移速率是影响光电化学性能的主要因素之一.本综述简要介绍了一些界面工程策略以增强光阳极中光生载流子的分离和传输.此外,总结了近期在原位量化光生载流子传输动力学研究中的进展.我们的目的是帮助读者了解这一领域的最新发展,并为理解动态空穴转移提供一个独特的视角.最后,我们对发展微纳尺度电极界面光生载流子分离和转移动力学表征手段中面临的重大挑战和未来前景进行了展望.

OpNAC1 transcription factor regulates the biosynthesis of the anticancer drug camptothecin by targeting loganic acid O-methyltransferase in Ophiorrhiza pumila

Camptothecin(CPT) is an anticancer pentacyclic quinoline alkaloid widely used to treat cancer patients worldwide. However, the biosynthetic pathway and transcriptional regulation of camptothecin are largely unknown. Ophiorrhiza pumila, the herbaceous plant from the Rubiaceae family, has emerged as a model plant for studying camptothecin biosynthesis and regulation. In this study, a high-quality reference genome of O. pumila with estimated size of ~456.90Mb was reported, and the accumulation level of camptothecin in roots was higher than that in stems and leaves. Based on its spatial distribution in the plant, we examined gene functions and expression by combining genomics with transcriptomic analysis.Two loganic acid O-methyltransferase(OpLAMTs)were identified in strictosidine-producing plant O.pumila, and enzyme catalysis assays showed that OpLAMT1 and not OpLAMT2 could convert loganic acid into loganin. Further knock-out of OpL AMT1expression led to the elimination of loganin and camptothecin accumulation in O. pumila hairy roots.Four key residues were identified in OpLAMT1 protein crucial for the catalytic activity of loganic acid to loganin. By co-expression network, we identified a NAC transcription factor, OpNAC1, as a candidate gene for regulating camptothecin biosynthesis.Transgenic hairy roots and biochemical assays demonstrated that OpNAC1 suppressed OpLAMT1 expression. Here, we reported on two camptothecin metabolic engineering strategies paving the road for industrial-scale production of camptothecin in CPT-producing plants.

Recent advances on N-acetylneuraminic acid:Physiological roles,applications,and biosynthesis

N-Acetylneuraminic acid(Neu5Ac),the most common type of Sia,generally acts as the terminal sugar in cell surface glycans,glycoconjugates,oligosaccharides,lipo-oligosaccharides,and polysaccharides,thus exerting numerous physiological functions.The extensive applications of Neu5Ac in the food,cosmetic,and pharmaceutical industries make large-scale production of this chemical desirable.Biosynthesis which is associated with important application potential and environmental friendliness has become an indispensable approach for large-scale synthesis of Neu5Ac.In this review,the physiological roles of Neu5Ac was first summarized in detail.Second,the safety evaluation,regulatory status,and applications of Neu5Ac were discussed.Third,enzyme-catalyzed preparation,whole-cell biocatalysis,and microbial de novo synthesis of Neu5Ac were comprehensively reviewed.In addition,we discussed the main challenges of Neu5Ac de novo biosynthesis,such as screening and engineering of key enzymes,identifying exporters of intermediates and Neu5Ac,and balancing cell growth and biosynthesis.The corresponding strategies and systematic strategies were proposed to overcome these challenges and facilitate Neu5Ac industrial-scale production.

Development of organic redox-active materials in aqueous flow batteries: Current strategies and future perspectives

Aqueous redox flow batteries,by using redox-active molecules dissolved in nonflammable water solutions as electrolytes,are a promising technology for grid-scale energy storage.Organic redox-active materials offer a new opportunity for the construction of advanced flow batteries due to their advantages of potentially low cost,extensive structural diversity,tunable electrochemical properties,and high natural abundance.In this review,we present the emergence and development of organic redox-active materials for aqueous organic redox flow batteries(AORFBs),in particular,molecular engineering concepts and strategies of organic redox-active molecules.The typical design strategies based on organic redox species for high-capacity,high-stability,and high-voltage AORFBs are outlined and discussed.Molecular engineering of organic redox-active molecules for high aqueous solubility,high chemical/electrochemical stability,and multiple electron numbers as well as satisfactory redox potential gap between the redox pair is essential to realizing high-performance AORFBs.Beyond molecular engineering,the redoxtargeting strategy is an effective way to obtain high-capacity AORFBs.We further discuss and analyze the redox reaction mechanisms of organic redox species based on a series of electrochemical and spectroscopic approaches,and succinctly summarize the capacity degradation mechanisms of AORFBs.Furthermore,the current challenges,opportunities,and future directions of organic redox-active materials for AORFBs are presented in detail.

Molecular mechanisms underlying phosphate sensing, signaling, and adaptation in plants

As an essential plant macronutrient, the low availability of phosphorus （P） in most soils imposes serious limitation on crop production. Plants have evolved complex responsive and adaptive mechanisms for acquisition, remobilization and recycling of phosphate （Pi） to maintain P homeostasis. Spatio-temporal molecular, physiological, and biochemical Pi deficiency responses developed by plants are the consequence of local and systemic sensing and signaling pathways. Pi deficiency is sensed locally by the root system where hormones serve as important signaling components in terms of developmental reprogramming, leading to changes in root system architecture. Root-to-shoot and shoot-to-root signals, delivered through the xylem and phloem, respectively, involving Pi itself, hormones, miRNAs, mRNAs, and sucrose, serve to coordinate Pi deficiency responses at the whole-plant level. A combination of chromatin remodeling, transcriptional and posttranslational events contribute to globally regulating a wide range of Pi deficiency responses. In this review, recent advances are evaluated in terms of progress toward developing a comprehen- sive understanding of the molecular events underlying control over P homeostasis. Application of this knowledge, in terms of developing crop plants having enhanced attributes for P use efficiency, is discussed from the perspective of agricultural sustainability in the face of diminishing global P supplies.

Methods to Make Conductive Covalent Organic Frameworks for Electrocatalytic Applications

Covalent organic frameworks(COFs) represent a new class of crystalline organic polymer materials with the characteristics of high specific surface area, uniform pore distribution, high porosity, low density, devisable chain structures and good structural stability. These collective features play an important role in creating highly efficient electrocatalysts for energy conversion and fuel generation. Recent years have witnessed considerable advances in COF-based electrocatalysts for major electrocatalytic reactions such as oxygen reduction, oxygen evolution, hydrogen evolution, and reduction of carbon dioxide and nitrogen. However, it has been widely accepted that the poor electrical conductivity of most pristine COFs limits the further progress in electrocatalytic field. In this review, recent structural engineering strategies are summarized toward improving the electrical conductivity of COFs for achieving high performance. The researches of conductive COFs and their derivatives are described in detail. The structure-activity relationship between molecular structures of COFs and their electrocatalytic performance is emphasized. Lastly, current challenges and future perspectives on fabricating COFs as promising electrocatalysts are discussed. The purpose of this review is to provide guidelines for the preparation of highly efficient COF-based electrocatalytic materials with a view to replacing the commercially available noble metal-based electrocatalysts.

Engineered microorganisms-based delivery systems for targeted cancer therapy:a narrative review

Microorganisms with innate and artificial advantages have been regarded as intelligent drug delivery systems for cancer therapy with the help of engineering technology.Although numerous studies have confirmed the promising prospects of microorganisms in cancer,several problems such as immunogenicity and toxicity should be addressed before further clinical applications.This review aims to investigate the developments of engineered microorganisms-based delivery systems for targeted cancer therapy.The main types and characteristics of microorganisms such as bacteria,viruses,fungi,microalgae,and their components are introduced in detail.Moreover,the engineering strategies and biomaterials design of microorganisms are further discussed.Most importantly,we discussed the innovative attempts and therapeutic effects of engineered microorganisms in cancer.Taken together,engineered microorganisms-based delivery systems hold tremendous prospects for biomedical applications in targeted cancer therapy.