The Legacy of Fossil Fuels

Currently, over 80 % of the energy used by mankind comes from fossil fuels. Harnessing coal, oil and gas, the energy resources contained in the store of our spaceship, Earth, has prompted a dramatic expansion in energy use and a substantial improvement in the quality of life of billions of individuals in some regions of the world. Powering our civilization with fossil fuels has been very convenient, but now we know that it entails severe consequences. We treat fossil fuels as a resource that anyone anywhere can extract and use in any fashion, and Earth’s atmosphere, soil and oceans as a dump for their waste products, including more than 30 Gt/y of carbon dioxide. At present, environmental legacy rather than consistence of exploitable reserves, is the most dramatic problem posed by the relentless increase of fossil fuel global demand. Harmful effects on the environment and human health, usually not incorporated into the pricing of fossil fuels, include immediate and short‐term impacts related to their discovery, extraction, transportation, distribution, and burning as well as climate change that are spread over time to future generations or over space to the entire planet. In this essay, several aspects of the fossil fuel legacy are discussed, such as alteration of the carbon cycle, carbon dioxide rise and its measurement, greenhouse effect, anthropogenic climate change, air pollution and human health, geoengineering proposals, land and water degradation, economic problems, indirect effects on the society, and the urgent need of regulatory efforts and related actions to promote a gradual transition out of the fossil fuel era. While manufacturing sustainable solar fuels appears to be a longer‐time perspective, alternatives energy sources already exist that have the potential to replace fossil fuels as feedstocks for electricity production.     

从液态阳光人工光合成淀粉

人工光合成是利用太阳能等可再生能源通过连续催化反应将水和二氧化碳转化为液态燃料的过程,是减少二氧化碳排放、实现绿色低碳发展的一种重要方法.人工光合成的目标产物不仅包括二氧化碳转化与利用得到的能源小分子,还包括淀粉和蛋白质等生物基大分子.在自然光合作用中,高等植物、绿藻和蓝细菌首先利用太阳能将水氧化放出氧气并产生还原型辅...     

Conversion of Solar Energy to Fuels by Inorganic Heterogeneous Systems

Over the last several years,the need to find clean and renewable energy sources has increased rapidly because current fossil fuels will not only eventually be depleted,but their continuous combustion leads to a dramatic increase in the carbon dioxide amount in atmosphere.Utilisation of the Sun’s radiation can provide a solution to both problems.Hydrogen fuel can be generated by using solar energy to split water,and liquid fuels can be produced via direct CO2 photoreduction.This would create an essentially free carbon or at least carbon neutral energy cycle.In this tutorial review,the current progress in fuels’ generation directly driven by solar energy is summarised.Fundamental mechanisms are discussed with suggestions for future research.     

过渡金属催化CO2/H2参与的羰基化研究进展

Ever-increasing energy demands due to rapid industrialization and urban population growth have drastically reduced petroleum reserves and increased greenhouse-gas production, and the latter has consequently contributed to climate change and environmental damage. Therefore, it is highly desirable to produce fuels and chemicals from non-petroleum feedstocks and to reduce the atmospheric concentrations of greenhouse gases. One solution has involved using carbon dioxide (CO₂), a main greenhouse gas, as a C1 feedstock for producing industrial fuels and chemicals. However, this requires high energy input from reductants or reactants with relatively high free energy (e.g., H₂ gas) because CO₂ is a highly oxidized, thermodynamically stable form of carbon. H₂ can be generated through water photolysis, making it an ideal reductant for hydrogenating CO₂ to CO. In situ generation of CO such as this has been developed for various carbonylation reactions that produce high value-added chemicals and avoid deriving CO from fossil fuels. This is beneficial because CO is toxic, and when extracted from fossil fuels it requires tedious separation and transportation. This combination of CO₂ and H₂ allows for functional molecules to be synthesized as entries into the chemical industry value chain and would generate a carbon footprint much lower than that of conventional petrochemical pathways. Based on this, CO₂/H₂ carbonylations using homogeneous transition metal-based catalysts have attracted increasing attention. Through this process, alkenes have been converted to alcohols, carboxylic acids, amines, and aldehydes. Heterogeneous catalysis has also provided an innovative approach for the carbonylation of alkenes with CO₂/H₂. Based on these alkene carbonylations, the scope of CO₂/H₂ carbonylations has been expanded to include aryl halides, methanol, and methanol derivatives, which give the corresponding aryl aldehyde, acetic acid, and ethanol products. These carbonylations revealed indirect CO₂-HCOOH-CO pathways and direct CO₂ insertion pathways. The use of this process is ever-increasing and has expanded the scope of CO₂ utilization to produce novel, high value-added or bulk chemicals, and has promoted sustainable chemistry. This review summarizes the recent advances in transition-metal-catalyzed carbonylations with CO₂/H₂ and discusses the perspectives and challenges of further research.     

金属纳米簇在CO2光催化还原中的研究进展

化石燃料的大量燃烧不仅造成能源危机，而且排放的二氧化碳（CO2）会使气候变暖。以清洁、储量丰富的太阳光作为能量来源，将CO2光催化还原为高附加值的化学产品是缓解当前环境问题和能源问题的主要方法之一。然而，CO2在常温常压下非常的稳定，因此需要设计并构筑高效光催化剂来捕捉和转化CO2，以达到高效光催化CO2还原的目的。在众多研究的光催化剂中，金属纳米簇因其具有独特的结构特点、优异的物理和化学性质，所以在光催化CO2还原领域得到了广泛的应用。基于此，我们首先对金属纳米簇进行了分类，将其分为贵金属纳米簇和非贵金属纳米簇；然后分别对贵金属和非贵金属纳米簇在光催化CO2还原中的研究进展进行了归纳与总结。本文通过及时全面概述近几年该领域的研究进展，从而为未来研究方向提供新思路。     

Der globale Kohlenstoffkreislauf im Anthropozän. Betrachtung aus meereschemischer Perspektive

By burning of fossil fuels humankind emits more than 8 billion tons of carbon (Gt C) in the form of CO₂ to the atmosphere. Since the onset of the industrial revolution the cumulative emissions have led to an increase of the atmospheric CO₂ concentration which corresponds to an additional radiative forcing in the atmosphere. Of the three reservoirs which exchange carbon on the time scale of centuries – atmosphere, terrestrial biosphere, and ocean – the ocean is by far the largest. The marine CO₂ system comprises the chemical species HCO₃^–, CO₃^2–, and CO₂(aq). This gives rise to the pH‐buffering nature of seawater as well as its high uptake capacity for anthropogenic CO₂. Four measurement parameters of the marine CO₂ system are available for an accurate analytical characterization. These parameters also provide a means of sensing the role of physical, chemical, and biological drivers for the marine carbon cycle. The marine carbon cycle features major natural processes that exchange carbon with the atmosphere and re‐distribute it throughout the ocean. These are known as “pumps” and driven by physical and biological factors. While the “physical pump” is inevitably enhanced by the oceanic uptake of anthropogenic CO₂, even the sign of the response is currently not clear for the “biological pumps”. A host of potential consequences of global change (temperature rise, ocean carbonation, ocean acidification) have been identified. These are currently studied intensively with respect to their climate sensitivity as well as the climate feedback potential.     

Non-thermal plasma technology for the conversion of CO2

The conversion of carbon dioxide is vital if we are to avoid the catastrophic consequences that will result from further global temperature rise as a result of burning fossil fuels. Current techniques, such as catalytic conversion and biochemical processes, are each associated with their own drawbacks such as catalyst deactivation and high energy input. Plasma processes are gaining increasing interest as they have the potential to reduce a greater amount of atmospheric environmental pollutants at any one time due to an increased throughput, whilst using a smaller reactor with improved energy efficiency and near-zero emissions. Non-thermal plasma can dissociate stable molecules, such as CO₂, at temperatures as low as room temperature. It is this key feature which makes plasma conversion such a promising technology in the conversion and utilisation of CO₂. Furthermore, possible products from plasma processes include fuels and chemicals, such as methanol and syngas, which have a high market value; hence potentially making the process feasible on an industrial scale. This paper discusses recent advances in the use of plasma processes for carbon dioxide conversion, along with the future outlook of this technology and the impact these techniques could have on the chemical and energy industries.     

Artificial photosynthetic antennas and reaction centers

Presently, the world is experiencing an unprecedented crisis associated with the CO₂ produced by the use of fossil fuels to power our economies. As evidenced by the increasing levels in the atmosphere, the reduction of CO₂ to biomass by photosynthesis cannot keep pace with production with the result that nature has lost control of the global carbon cycle. In order to restore control of the global carbon cycle to solar-driven processes, highly efficient artificial photosynthesis can augment photosynthesis in specific ways and places. The increased efficiency of artificial photosynthesis can provide both renewable carbon-based fuels and lower net atmospheric levels of CO₂, which will preserve land and support the ecosystem services upon which all life on Earth depends. The development of artificial photosynthetic antennas and reaction centers contributes to the understanding of natural photosynthesis and to the knowledge base necessary for the development of future scalable technologies. This review focuses on the design and study of molecular and hybrid molecular-semiconductor nanoparticle based systems, all of which are inspired by functions found in photosynthesis and some of which are inspired by components of photosynthesis. In addition to constructs illustrating energy transfer, photoinduced electron transfer, charge shift reactions and proton coupled electron transfer, our review covers systems that produce proton motive force.     

CO2催化转化为高附加值燃料：现状、挑战及其未来方向

The electrochemical reduction of CO2 into liquid fuels especially coupling with the intermittent renewable electricity offers a promising means of storing electricity in chemical form, which reduc‐es the dependence on fossil fuels and mitigates the negative impact of anthropogenic CO2 emissions on the planet. Although converting CO2 to fuels is not in itself a new concept, the field has not sub‐stantially advanced in the last 30 years primarily because of the challenge of discovery of structural electrocatalysts and the development of membrane architectures for efficient collection of reactants and separation of products. This overview summarizes recent advances in catalytic conversion of CO2 and presents the challenges and future directions in producing value‐added fuels.     

A Review of Hydrogen Production by Photosynthetic Organisms Using Whole-Cell and Cell-Free Systems

Molecular hydrogen is a promising currency in the future energy economy due to the uncertain availability of finite fossil fuel resources and environmental effects from their combustion. It also has important uses in the production of fertilizers and platform chemicals as well as in upgrading conventional fuels. Conventional methods for producing molecular hydrogen from natural gas produce carbon dioxide and use a finite resource as feedstock. However, these issues can be overcome by using light energy from the Sun combined with microorganisms and their molecular machinery capable of photosynthesis. In the presence of light, the proteins involved in photosynthesis coupled with appropriate catalysts in higher plants, algae, and cyanobacteria can produce molecular hydrogen, and optimization via genetic modifications and biomolecular engineering further improves production rates. In this review, we will discuss techniques that have been utilized to improve rates of hydrogen production in biological systems based on the protein machinery of photosynthesis coupled with appropriate catalysts. We will also suggest areas for improvement and future directions for work in the field.     

Recent progress in carbon-based materials boosting electrochemical water splitting

As environmental crises such as global warming become more and more serious due to the large amount of carbon dioxide emitted by the burning of fossil fuels, much attention has been paid to carbon neutrality. Hydrogen, with zero carbon content, is a clean and renewable energy carrier having a large energy density. It is considered as one of the most desirable alternatives to fossil fuels. Electrochemical water splitting, unlike the steam reforming process accelerating fossil fuels depletion and CO₂ emissions, can produce H₂ powered by renewable energy such as solar or wind. As a promising way to promote carbon neutralization, hydrogen production by electrolysis of water is meaningful both in terms of scientific research and practical application. In order to drive electrochemical water splitting with low power consumption, efficient, durable and affordable electrocatalysts with low overpotentials are in urgent need. Therefore, this mini-review briefly introduces the current development status and mainstream obstacles of carbon-based materials used in electrochemical water splitting.     

氧化物钙钛矿的光催化研究进展：CO2还原、水裂解、固氮

At present, more than 80% of the world's energy demand is fulfilled by the burning of fossil fuels, which has caused the production of a large amount of greenhouse gases, leading to global warming and damage to the environment. The high consumption of fossil fuels every year causes the energy crisis to become increasingly serious. Finding a sustainable and pollution-free energy source is therefore essential. Among all forms of energy sources, solar energy is preferred because of its cleanliness and inexhaustible availability. The energy provided by one year of sunlight is more than 100 times the total energy in known fossil fuel reserves worldwide; however, the extent of solar energy currently used by mankind each year is minute; thus developments in solar energy are imperative. To address the urgent need for a renewable energy supply and to solve environmental problems, a variety of technologies in the field of photocatalysis have been developed. Photocatalytic technology has attracted significant attention because of its superior ability to convert clean solar energy into chemical fuels. Among the photocatalytic materials emerging in an endless stream, perovskite oxide, with the general formula of ABO₃, has great potential in the fields of solar cells and photocatalysis as each site can be replaced by a variety of cations. Furthermore, owing to its unique properties such as high activity, robust stability, and facile structure adjustment, perovskite oxide photocatalysts have been widely used in water decomposition, carbon dioxide reduction and conversion, and nitrogen fixation. In terms of carbon dioxide reduction, oxide perovskites can achieve precise band gap and band edge tuning owing to its long charge diffusion length and flexibility in composition. For the development and utilization of solar energy in the environmental field, perovskite oxide and its derivatives (layered perovskite oxide) are used as photocatalysts for water decomposition and environmental remediation. In terms of nitrogen fixation, the conventional Haber-Bosh process for ammonia synthesis, which has been widely used in the past, requires high temperature and high energy. Therefore, we summarize the recent advances in perovskite oxide photocatalysts for nitrogen fixation from the aspect of activating the adsorbed N₂ by weakening the N $ \equiv $N triple bond, promoting charge separation, and accelerating the charge transfer to the active sites to realize the photochemical reaction. Overall, this review article presents the structure and synthesis of perovskite oxide photocatalysis, focusing on the application of photocatalysis in water splitting, carbon dioxide reduction, and nitrogen fixation. This review concludes by presenting the current challenges and future prospects of perovskite oxide photocatalysts.      

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.     

Utilisation of CO2 as a chemical feedstock: opportunities and challenges

The need to reduce the accumulation of CO(2) into the atmosphere requires new technologies able to reduce the CO(2) emission. The utilization of CO(2) as a building block may represent an interesting approach to synthetic methodologies less intensive in carbon and energy. In this paper the general properties of carbon dioxide and its interaction with metal centres is first considered. The potential of carbon dioxide as a raw material in the synthesis of chemicals such as carboxylates, carbonates, carbamates is then discussed. The utilization of CO(2) as source of carbon for the synthesis of fuels or other C(1) molecules such as formic acid and methanol is also described and the conditions for its implementation are outlined. A comparison of chemical and biotechnological conversion routes of CO(2) is made and the barriers to their exploitation are highlighted.     

二氧化碳加氢制甲醇多相催化剂研究进展

化石燃料的利用为人类社会带来了前所未有的繁荣和发展. 然而, 化石燃料燃烧引起的过量的二氧化碳(CO₂)排放导致全球气候变化和海洋酸化; 而且作为一种有限的资源, 化石燃料的消耗将迫使人们寻找其它碳源以维持可持续的发展. 利用可再生能源获取电能分解水制得的绿色氢气(H₂)与捕集后的CO₂反应制成甲醇, 不仅能有效利用工业废气中多余的CO₂, 还能获取清洁、 可再生的甲醇化学品, 该过程的技术核心是开发高效稳定的CO₂加氢制甲醇催化剂. 本文综合评述了现有研究关注较多的多相催化CO₂加氢制甲醇催化剂的反应机理和构效关系, 总结了目前多相催化CO₂加氢制甲醇催化剂(Cu基催化剂、 贵金属与双金属催化剂、 氧化物催化剂以及其它新型催化剂)的设计与合成方面的研究进展, 最后对该领域所面临的机遇和挑战进行了展望.     

可见光驱动丰产金属卟啉类配合物催化的二氧化碳选择性还原反应

随着能源短缺和环境问题日益突出, 寻找清洁和可再生能源来替代化石燃料是本世纪科学家面临的最紧迫的任务之一. 为了实现我国“双碳”战略目标, 利用太阳能将二氧化碳(CO₂)转化为清洁燃料和化学品是实现社会可持续发展的途径之一. 催化剂是CO₂光还原技术的核心组成部分, 其可以吸附气态CO₂分子, 在可见光照射下将CO₂还原为一氧化碳(CO)、 甲酸(HCOOH)、 甲醇(CH₃OH)或甲烷(CH₄)等能源小分子. 目前, 新型CO₂还原光催化体系的开发取得了很好的进展. 本文综合评述了近年来均相及非均相丰产金属卟啉类催化剂在光催化CO₂还原中的研究进展, 并对在金属卟啉均相催化剂作用下, CO₂光还原为CO或CH₄的反应机理分别进行了介绍, 还讨论了金属卟啉基多孔有机聚合物与卟啉有机金属框架在光催化CO₂方面的重要应用. 最后, 对可见光驱动卟啉类金属配合物催化的CO₂还原的发展前景进行了展望.     

Recent advances in heterogeneous catalytic conversion of glucose to 5-hydroxymethylfurfural via green routes

With concerns of diminishing fossil fuel reserves and environmental deterioration, great efforts have been made to explore novel approaches of efficiently utilizing bio-renewable feedstocks to produce chemicals and fuels. 5-Hydroxymethylfurfural(HMF),generated from dehydration of six-carbon ketose, is regarded as a primary and versatile renewable building block to realize the goal of production of these high valued products from renewable biomass resources transformation. In this review, we summarize the recent advances via green routes in the heterogeneous reaction system for the catalytic production of HMF from glucose conversion, and emphasize reaction pathways of these reaction approaches based on the fundamental mechanistic chemistry as well as highlight the challenges(such as separation and purification of products, reusing and regeneration of catalyst, recycling solvent) in this field.     

Electrochemical Oxidation of Carbon‐Containing Fuels and Their Dynamics in Low‐Temperature Fuel Cells

Fuel cells can convert the energy that is chemically stored in a compound into electrical energy with high efficiency. Hydrogen could be the first choice for chemical energy storage, but its utilization is limited due to storage and transport difficulties. Carbon‐containing fuels store chemical energy with significantly higher energy density, which makes them excellent energy carriers. The electro‐oxidation of carbon‐containing fuels without prior reforming is a more challenging and complex process than anodic hydrogen oxidation. The current understanding of the direct electro‐oxidation of carbon‐containing fuels in low‐temperature fuel cells is reviewed. Furthermore, this review covers various aspects of electro‐oxidation for carbon‐containing fuels in non‐steady‐state reaction conditions. Such dynamic investigations open possibilities to elucidate detailed reaction kinetics, to sense fuel concentration, or to diagnose the fuel‐cell state during operation. Motivated by the challenge to decrease the consumption of fossil fuel, the production routes of the fuels from renewable resources also are reviewed.     

光催化CO_2转化为碳氢燃料体系的综述

传统化石能源燃烧产生CO2引起的地球变暖和能源短缺已经成为一个严重的全球性问题.利用太阳光和光催化材料将CO2还原为碳氢燃料,不仅可以减少空气中CO2浓度,降低温室效应的影响,还可以提供碳氢燃料,缓解能源短缺问题,因此日益受到各国科学家的高度关注.本文综述了光催化还原CO2为碳氢燃料的研究进展,介绍了光催化还原CO2的反应机理,并对现阶段报道的光催化还原CO2材料体系进行了整理和分类,包括TiO2光催化材料,ABO3型钙钛矿光催化材料,尖晶石型光催化材料,掺杂型光催化材料,复合光催化材料,V、W、Ge、Ga基光催化材料及石墨烯基光催化材料.评述了各种材料体系的特点及光催化性能的一些影响因素.最后对光催化还原CO2的研究前景进行了展望.     

二氧化碳资源化利用的工业技术途径探讨

本文从CO₂来源、与CO₂反应的原料、反应过程、以及反应产物性质等多方面对二氧化碳资源化利用的工业技术途径进行了探讨。研究结果表明将工艺过程产生的CO₂直接做成目前CO₂固定量最高、工艺能耗较少、反应产物性质稳定的1,3,5均三嗪三醇(C₃H₃N₃O₃,简称三嗪醇)是最可行的二氧化碳资源化利用的工业技术途径。将化石燃料在一定工艺过程条件下生成三嗪醇,同时将过程中释放的能量和剩余氢作为能源利用是环境友好的能源技术路线。