Login In
2019 Volume 40 Issue s1
2019, 40(s1):
Abstract:
2019, 40(s1): 1-5
Abstract:
Catalysis and surface/interface chemistry is one of the key basic disciplines supported by National Natural Science Foundation of China (NSFC), which plays significant roles on promoting fundamental research and accelerating discipline development. To improve further catalysis and surface/interface chemistry as well as enhance its influence the economic construction, the Department of Chemical Sciences of NSFC held a seminar on the frontier and development strategy of catalysis and surface/interface chemistry in Dalian at the end of October, 2018. The seminar focused on the research frontier, status and developing bottleneck of catalysis and surface/interface chemistry. Moreover, the subjects about talent training and discipline integration were discussed systematically, and the encouraged research frontier topics in the future were proposed.
Catalysis and surface/interface chemistry is one of the key basic disciplines supported by National Natural Science Foundation of China (NSFC), which plays significant roles on promoting fundamental research and accelerating discipline development. To improve further catalysis and surface/interface chemistry as well as enhance its influence the economic construction, the Department of Chemical Sciences of NSFC held a seminar on the frontier and development strategy of catalysis and surface/interface chemistry in Dalian at the end of October, 2018. The seminar focused on the research frontier, status and developing bottleneck of catalysis and surface/interface chemistry. Moreover, the subjects about talent training and discipline integration were discussed systematically, and the encouraged research frontier topics in the future were proposed.
2019, 40(s1): 6-10
Abstract:
In 2017, Department of Chemical Sciences of National Natural Science Foundation of China (NSFC) re-organized the divisions and the new discipline codes were employed to conduct funding and management. The new code B02 corresponds to the field of catalysis and surface/interface chemistry. In this paper, the funding scope of B02 code was introduced briefly first. Then the application and funding of B02 code in 2018, as well as the actions which were taken to optimize the peer review processes were summarized and analyzed. At last, some suggestions on improving the proposals were proposed.
In 2017, Department of Chemical Sciences of National Natural Science Foundation of China (NSFC) re-organized the divisions and the new discipline codes were employed to conduct funding and management. The new code B02 corresponds to the field of catalysis and surface/interface chemistry. In this paper, the funding scope of B02 code was introduced briefly first. Then the application and funding of B02 code in 2018, as well as the actions which were taken to optimize the peer review processes were summarized and analyzed. At last, some suggestions on improving the proposals were proposed.
2019, 40(s1): 11-16
Abstract:
The development of electrochemical energy technology is of great significance for solving the energy and environment problems. Investigating the processes of electrocatalytic reactions on the electrode surface at the atomic and molecular scale benefits reaction mecha-nisms studies, and provides the fundamental guideline for designing high-efficient and stable electrocatalysts. This review summarizes recent studies on investigating surface processes in electrocatalysis by scanning tunneling microscopy, including non-reactive processes such as surface adsorption, surface diffusion, reactants binding, and reaction processes such as structure changes and contrast transformations of catalysts, as well as distinguishing active sites. The key scientific issues and future developments in the field are also outlined.
The development of electrochemical energy technology is of great significance for solving the energy and environment problems. Investigating the processes of electrocatalytic reactions on the electrode surface at the atomic and molecular scale benefits reaction mecha-nisms studies, and provides the fundamental guideline for designing high-efficient and stable electrocatalysts. This review summarizes recent studies on investigating surface processes in electrocatalysis by scanning tunneling microscopy, including non-reactive processes such as surface adsorption, surface diffusion, reactants binding, and reaction processes such as structure changes and contrast transformations of catalysts, as well as distinguishing active sites. The key scientific issues and future developments in the field are also outlined.
2019, 40(s1): 17-25
Abstract:
Nanoconfined chemical reactions in different dimensions generally exhibit enhanced performance, as a consequence of nanoconfinement, yet the inherent mechanism of this nanoconfinement-enhanced performance remains elusive. Here, our perspectives on nanoconfined chemical reactions are first provided, followed by nanoconfined pre-assembled reactions. Then, ultrafast mass transport behaviors in biological and artificial nanochannels are discussed and the quantum-confined superfluid concept is introduced. Inspired by the pro-grammed-assembly reaction in living organisms, a new concept of ordered-assembly reaction is proposed through combining quan-tum-confined superfluid with frontier molecular orbital theory, to understand the inherent mechanism of high-performance nanoconfined chemical reactions. Finally, the prospective for future development of the ordered-assembly reaction concept is presented.
Nanoconfined chemical reactions in different dimensions generally exhibit enhanced performance, as a consequence of nanoconfinement, yet the inherent mechanism of this nanoconfinement-enhanced performance remains elusive. Here, our perspectives on nanoconfined chemical reactions are first provided, followed by nanoconfined pre-assembled reactions. Then, ultrafast mass transport behaviors in biological and artificial nanochannels are discussed and the quantum-confined superfluid concept is introduced. Inspired by the pro-grammed-assembly reaction in living organisms, a new concept of ordered-assembly reaction is proposed through combining quan-tum-confined superfluid with frontier molecular orbital theory, to understand the inherent mechanism of high-performance nanoconfined chemical reactions. Finally, the prospective for future development of the ordered-assembly reaction concept is presented.
2019, 40(s1): 26-29
Abstract:
Zeolites as highly efficient catalysts have been widely applied in conversion of oils and production of chemicals, which are normally prepared from hydrothermal routes. Because a large amount of water solvent is employed for the hydrothermal synthesis of zeolites in the presence of organic templates, it is usually formed a large amount of wastes such as polluted water and gases. To solve these issues, we have developed green routes for synthesis of zeolites, including zeolite organotemplate-free synthesis, solvent-free synthesis, use of low-cost templates, and Ge-free synthesis. These approaches offer a good opportunity for sustainable production of zeolites at an industrial scale. Among them, organotemplate-free synthesis of Al-rich Beta zeolite has been commercialized in BASF.
Zeolites as highly efficient catalysts have been widely applied in conversion of oils and production of chemicals, which are normally prepared from hydrothermal routes. Because a large amount of water solvent is employed for the hydrothermal synthesis of zeolites in the presence of organic templates, it is usually formed a large amount of wastes such as polluted water and gases. To solve these issues, we have developed green routes for synthesis of zeolites, including zeolite organotemplate-free synthesis, solvent-free synthesis, use of low-cost templates, and Ge-free synthesis. These approaches offer a good opportunity for sustainable production of zeolites at an industrial scale. Among them, organotemplate-free synthesis of Al-rich Beta zeolite has been commercialized in BASF.
2019, 40(s1): 30-35
Abstract:
The application of solid-state NMR spectroscopy spans multidisciplinary areas of physics, chemistry and materials science. Solid-state NMR has been fully integrated into catalysis science and played a critical role in the study of heterogeneous catalysis by providing a powerful tool to tackle important problems. The increasing of the complexity of heterogeneous catalytic systems brings about new challenges on the one hand, and also opens up new opportunities on the other hand for solid-state NMR. In this article, the recent progress of solid-state NMR development and its application in heterogeneous catalysis is briefly reviewed. The obstacles for the development of solid-state NMR are discussed and the status of the research of solid-state NMR in heterogeneous catalysis in China is introduced. Based on the comparison with the world-class level, the technologies which are in the "cut-throat competition" position are summarized. Finally, the major opportunities and future research directions for solid-state NMR are highlighted.
The application of solid-state NMR spectroscopy spans multidisciplinary areas of physics, chemistry and materials science. Solid-state NMR has been fully integrated into catalysis science and played a critical role in the study of heterogeneous catalysis by providing a powerful tool to tackle important problems. The increasing of the complexity of heterogeneous catalytic systems brings about new challenges on the one hand, and also opens up new opportunities on the other hand for solid-state NMR. In this article, the recent progress of solid-state NMR development and its application in heterogeneous catalysis is briefly reviewed. The obstacles for the development of solid-state NMR are discussed and the status of the research of solid-state NMR in heterogeneous catalysis in China is introduced. Based on the comparison with the world-class level, the technologies which are in the "cut-throat competition" position are summarized. Finally, the major opportunities and future research directions for solid-state NMR are highlighted.
2019, 40(s1): 36-42
Abstract:
This paper briefly reviews four main research directions of lubrication discipline, as biomimetic hydrophilic lubrication, biomimetic lubrication drag-reduction, solid lubricant materials & technology, and liquid lubricants. We summarize the international frontiers, domestic research situation, existing problems and future development trends for each direction. The suggested research contents in future are as follows:(1) After Studying the relationship between interface hydration and lubrication along with its regulation mechanism, aim to developing biomimetic hydrophilic lubrication materials with high load bearing, low friction & anti-wear properties, and key wa-ter-lubricating coating technologies suitable for modification of high-end implanted biomedical devices, by using innovative design ideas such as layering, gradient and soft & hard composition; (2) After studying on the relationship between interface wetting and drag reduction along with its regulation mechanism, aim to developing effective gas-film stabilization technology on super-hydrophobic surfaces and elastic drag-reduction technology on super-hydrophilic surfaces to achieve efficient drag-reduction under turbulent flow condition by the bionic design of surface structures and components; (3) Applying the concept of supramolecular assembly to design new liquid lubricants and study its interaction mechanism, aim to developing new liquid lubricants with anti-irradiation, anti-aging, anti-climbing, anti-corrosion, environ-ment friendly and reusable characteristics, by precisely designing molecular structures and controlling the preparation technique; (4) Developing solid lubrication materials with excellent friction-reduction, anti-wear, long serving-lifetime, radiation resistance, corrosion resistance, strain resistance and wide temperature-range adaptation characteristics, by adopting novel concepts of surface and interface physichemistry, such as layered, soft/hard composition, multi-component coupling, gradient and in situ healing.
This paper briefly reviews four main research directions of lubrication discipline, as biomimetic hydrophilic lubrication, biomimetic lubrication drag-reduction, solid lubricant materials & technology, and liquid lubricants. We summarize the international frontiers, domestic research situation, existing problems and future development trends for each direction. The suggested research contents in future are as follows:(1) After Studying the relationship between interface hydration and lubrication along with its regulation mechanism, aim to developing biomimetic hydrophilic lubrication materials with high load bearing, low friction & anti-wear properties, and key wa-ter-lubricating coating technologies suitable for modification of high-end implanted biomedical devices, by using innovative design ideas such as layering, gradient and soft & hard composition; (2) After studying on the relationship between interface wetting and drag reduction along with its regulation mechanism, aim to developing effective gas-film stabilization technology on super-hydrophobic surfaces and elastic drag-reduction technology on super-hydrophilic surfaces to achieve efficient drag-reduction under turbulent flow condition by the bionic design of surface structures and components; (3) Applying the concept of supramolecular assembly to design new liquid lubricants and study its interaction mechanism, aim to developing new liquid lubricants with anti-irradiation, anti-aging, anti-climbing, anti-corrosion, environ-ment friendly and reusable characteristics, by precisely designing molecular structures and controlling the preparation technique; (4) Developing solid lubrication materials with excellent friction-reduction, anti-wear, long serving-lifetime, radiation resistance, corrosion resistance, strain resistance and wide temperature-range adaptation characteristics, by adopting novel concepts of surface and interface physichemistry, such as layered, soft/hard composition, multi-component coupling, gradient and in situ healing.
2019, 40(s1): 43-50
Abstract:
Carbonyl chemistry involves the catalytic construction and conversion of carbonyl compounds, which plays an important tool in clean and economic synthesis of fine chemicals. This perspective highlights the recent research progresses on the topic includes the carbonyl compounds construction via catalytic carbonylation and selective oxidation, and the further catalytic conversion of carbonyl compounds to functional molecules and materials. Based on our own understanding, the frontiers and future of the topic are also presented.
Carbonyl chemistry involves the catalytic construction and conversion of carbonyl compounds, which plays an important tool in clean and economic synthesis of fine chemicals. This perspective highlights the recent research progresses on the topic includes the carbonyl compounds construction via catalytic carbonylation and selective oxidation, and the further catalytic conversion of carbonyl compounds to functional molecules and materials. Based on our own understanding, the frontiers and future of the topic are also presented.
2019, 40(s1): 51-56
Abstract:
Heteroatom-containing zeolites or metallosilicates have been widely used in the environment-friendly selective oxidation processes for producing oxygen-containing chemicals and fine chemicals, which is changing the backwardness of conventional oxidation processes. However, the conventional metallosilicates usually possess only small-sized pore channels, which induce severe diffusion constrains. Moreover, the traditional hydrothermal synthesis processes of metallosilicates are complicated and time-consuming. To address these problems, a series of novel metallosilicates with larger pores have been developed to release the diffusion constrains, and several new synthesis routes have been proposed to shorten the synthesis duration and to increase the content of heteroatom active sites as well. Last but not the least, we have also been working on the chemical modification of the micro-environment of heteroatom active sites as well as the exploration of novel catalytic oxidation reaction processes, which is expectable to provide practically usable technologies for the development of selective oxidation processes.
Heteroatom-containing zeolites or metallosilicates have been widely used in the environment-friendly selective oxidation processes for producing oxygen-containing chemicals and fine chemicals, which is changing the backwardness of conventional oxidation processes. However, the conventional metallosilicates usually possess only small-sized pore channels, which induce severe diffusion constrains. Moreover, the traditional hydrothermal synthesis processes of metallosilicates are complicated and time-consuming. To address these problems, a series of novel metallosilicates with larger pores have been developed to release the diffusion constrains, and several new synthesis routes have been proposed to shorten the synthesis duration and to increase the content of heteroatom active sites as well. Last but not the least, we have also been working on the chemical modification of the micro-environment of heteroatom active sites as well as the exploration of novel catalytic oxidation reaction processes, which is expectable to provide practically usable technologies for the development of selective oxidation processes.
2019, 40(s1): 57-63
Abstract:
Ammonia synthesis process has a great impact on food production, energy security and environmental protection. The industrial ammonia synthesis based on the Haber-Bosch process, however, is an energy consuming and high emission process. Increasing efforts have been devoted to the development of new technologies and processes for "green" ammonia synthesis driven by renewable energies under mild conditions. In recent years, encouraging progresses have been made in the fields of heterogeneous catalysis, chemical looping, electro-and photo-chemical ammonia production, with significant advancements in fundamental understanding and breakthroughs. In this paper, the research status and challenges in this field are analyzed, and the recent achievements are highlighted.
Ammonia synthesis process has a great impact on food production, energy security and environmental protection. The industrial ammonia synthesis based on the Haber-Bosch process, however, is an energy consuming and high emission process. Increasing efforts have been devoted to the development of new technologies and processes for "green" ammonia synthesis driven by renewable energies under mild conditions. In recent years, encouraging progresses have been made in the fields of heterogeneous catalysis, chemical looping, electro-and photo-chemical ammonia production, with significant advancements in fundamental understanding and breakthroughs. In this paper, the research status and challenges in this field are analyzed, and the recent achievements are highlighted.
2019, 40(s1): 64-74
Abstract:
The problem of environmental pollution is one of the most important challenges for mankind in the 21st century. The treatment of environmental pollutions has become an extremely urgent and challenging task. Environmental catalysis technology has been regarded as one of the most effective ways to solve the serious environmental pollution problems that we are facing. In this paper, the present status for the developing of environmental catalysis in recent years was summarized from the standpoint of purifying different pollutants. The challenges of environmental catalysis research were discussed and its future developments were also proposed. Finally, the application prospect of environmental catalysis was outlooked.
The problem of environmental pollution is one of the most important challenges for mankind in the 21st century. The treatment of environmental pollutions has become an extremely urgent and challenging task. Environmental catalysis technology has been regarded as one of the most effective ways to solve the serious environmental pollution problems that we are facing. In this paper, the present status for the developing of environmental catalysis in recent years was summarized from the standpoint of purifying different pollutants. The challenges of environmental catalysis research were discussed and its future developments were also proposed. Finally, the application prospect of environmental catalysis was outlooked.
2019, 40(s1): 75-89
Abstract:
As the science of catalysis develops with an unprecedented pace in recent years, the quest for new characterization techniques and methodologies to detect physicochemical properties of catalysts related to their catalytic performance and so attain insightful understanding of structure-activity relationship has become of crucial importance in both fundamental research and industrial applications. This review briefly summaries the developments of environmental transmission electron microscopy and in-situ X-ray spectroscopy techniques with emphasis on their applications in the characterization of nanocatalysts and complex surfaces and interfaces in heterogeneous catalysis. These examples confirm the pivotal importance of in-situ techniques in understanding the structure-activity relationship in catalysis and also in facilitating the design of highly efficient catalysts.
As the science of catalysis develops with an unprecedented pace in recent years, the quest for new characterization techniques and methodologies to detect physicochemical properties of catalysts related to their catalytic performance and so attain insightful understanding of structure-activity relationship has become of crucial importance in both fundamental research and industrial applications. This review briefly summaries the developments of environmental transmission electron microscopy and in-situ X-ray spectroscopy techniques with emphasis on their applications in the characterization of nanocatalysts and complex surfaces and interfaces in heterogeneous catalysis. These examples confirm the pivotal importance of in-situ techniques in understanding the structure-activity relationship in catalysis and also in facilitating the design of highly efficient catalysts.
2019, 40(s1): 90-97
Abstract:
The development of electrochemistry theory dates back more than a century, from the Gouy-Chapman-Stern (GCS) double layer, phenomenological Tafel kinetics to the classical charge transfer Marcus theory and to the First-Principles simulations. The recent years have seen the rapid development in the application of first principles density functional theory (DFT) simulation on the solid/liquid interface. This article reviews the current theoretical methods for electrochemistry modelling, i.e simple thermodynamic method, periodic continuum solvation method (DFT/CM-MPB) and quantum mechanics molecular dynamics (QMMD). These methods have been applied to provide the atomic level insights into the nature of electrochemical double layer, charge transfer and the potential~current curve of electrocatalytic reaction. Despite these progresses, there is plenty of room for the new design and the improvement of theoretical methods for better describing the complex solid/liquid interface and the reaction therein.
The development of electrochemistry theory dates back more than a century, from the Gouy-Chapman-Stern (GCS) double layer, phenomenological Tafel kinetics to the classical charge transfer Marcus theory and to the First-Principles simulations. The recent years have seen the rapid development in the application of first principles density functional theory (DFT) simulation on the solid/liquid interface. This article reviews the current theoretical methods for electrochemistry modelling, i.e simple thermodynamic method, periodic continuum solvation method (DFT/CM-MPB) and quantum mechanics molecular dynamics (QMMD). These methods have been applied to provide the atomic level insights into the nature of electrochemical double layer, charge transfer and the potential~current curve of electrocatalytic reaction. Despite these progresses, there is plenty of room for the new design and the improvement of theoretical methods for better describing the complex solid/liquid interface and the reaction therein.
2019, 40(s1): 98-103
Abstract:
This perspective focuses on the development and key scientific issues of colloidal quantum dot spectroscopy. Quantum dots are potential optical and optoelectronic materials. Spectroscopy is not only a necessary means to understand properties of quantum dots, but also directly determines the development of the field. The example of colloidal quantum dots tells us that physical chemistry, especially spectroscopy, can play a key role in the development of new materials.
This perspective focuses on the development and key scientific issues of colloidal quantum dot spectroscopy. Quantum dots are potential optical and optoelectronic materials. Spectroscopy is not only a necessary means to understand properties of quantum dots, but also directly determines the development of the field. The example of colloidal quantum dots tells us that physical chemistry, especially spectroscopy, can play a key role in the development of new materials.
2019, 40(s1): 104-110
Abstract:
Nuclear quantum effects (NQEs), including quantum tunneling and zero-point motion, are mostly relevant to hydrogen-bonded (H-boned) systems and other light elements materials. In particular, the quantum behavior of protons is quite prominent at room temperature or higher and has significant effects on chemical reactions. However, the accurate and quantitative description of NQEs on surface chemistry at the atomic scale has proven to be experimentally challenging. This review will first summarize the behaviors of NQEs and its influences on a wide range of scientific disciplines. Then, we will introduce the conventional spectroscopic and diffraction techniques and the emerging scanning probe microscopy (SPM), which allows the access to the degree of freedom of protons at atomic scale both in real and energy space. We will also review the research advances of NQEs of surface water based on these techniques and highlight how the quantum motion of protons influences and assists the surface heterogeneous catalysis of H-rich systems. What's more, the role of quantum tunneling of other elements besides hydrogen in on-surface reaction is also summarized. At last, further challenges and perspective directions of NQEs in surface chemistry are remarked.
Nuclear quantum effects (NQEs), including quantum tunneling and zero-point motion, are mostly relevant to hydrogen-bonded (H-boned) systems and other light elements materials. In particular, the quantum behavior of protons is quite prominent at room temperature or higher and has significant effects on chemical reactions. However, the accurate and quantitative description of NQEs on surface chemistry at the atomic scale has proven to be experimentally challenging. This review will first summarize the behaviors of NQEs and its influences on a wide range of scientific disciplines. Then, we will introduce the conventional spectroscopic and diffraction techniques and the emerging scanning probe microscopy (SPM), which allows the access to the degree of freedom of protons at atomic scale both in real and energy space. We will also review the research advances of NQEs of surface water based on these techniques and highlight how the quantum motion of protons influences and assists the surface heterogeneous catalysis of H-rich systems. What's more, the role of quantum tunneling of other elements besides hydrogen in on-surface reaction is also summarized. At last, further challenges and perspective directions of NQEs in surface chemistry are remarked.
2019, 40(s1): 111-119
Abstract:
The ever-increasing consumption of finite resources of fossil fuels and global environmental concerns have accelerated the efforts to develop efficient and affordable electrochemical energy storage and electricity generation devices. Electrochemical reduction of oxides to fuels in molten salts using renewable energy sources such as solar and wind power is an effective way for converting electrical energy to chemical energy in fuel itself; this energy can be converted back to electricity when the fuel is electrochemically re-oxidized in fuel cells. These processes can be related with the molten salts enabled electrochemical cycling between oxides and solid fuels. Because solid fuels are of high density and stable in air, they are suitable for long term storage and long distance transportation. Therefore, we anticipate that the realization of "seasonal energy storage" (SES) and "regional energy storage" (RES). The purpose of SES is to store energy harvested in the sunny summer and reuse it in cold winter, whilst the RES aims to collect energy from remote desserts (sunlight to electricity) or mountains (wind to electricity) to urban areas. Preparation and application of the regenerative fuels via electrochemical process in molten salts are discussed.
The ever-increasing consumption of finite resources of fossil fuels and global environmental concerns have accelerated the efforts to develop efficient and affordable electrochemical energy storage and electricity generation devices. Electrochemical reduction of oxides to fuels in molten salts using renewable energy sources such as solar and wind power is an effective way for converting electrical energy to chemical energy in fuel itself; this energy can be converted back to electricity when the fuel is electrochemically re-oxidized in fuel cells. These processes can be related with the molten salts enabled electrochemical cycling between oxides and solid fuels. Because solid fuels are of high density and stable in air, they are suitable for long term storage and long distance transportation. Therefore, we anticipate that the realization of "seasonal energy storage" (SES) and "regional energy storage" (RES). The purpose of SES is to store energy harvested in the sunny summer and reuse it in cold winter, whilst the RES aims to collect energy from remote desserts (sunlight to electricity) or mountains (wind to electricity) to urban areas. Preparation and application of the regenerative fuels via electrochemical process in molten salts are discussed.
2019, 40(s1): 120-123
Abstract:
Designing catalysts at atomic scale would benefit to achieve a high efficiency for the transformation of chemical molecules, requiring a precise control in the geometric and electronic features of the active sites and their surroundings. In situ characterizations would identify the dynamic behavior of the working catalysts under reactive atmospheres and at elevated temperature, giving a whole picture from the construction of catalytically active architecture to the evolution upon reacting with molecules. A quantitative description at atomic and molecular levels for the interaction between the active center and the reactive molecules would not only favor an in-depth understanding in the catalytic mechanism but also have a profound consequence for the rational design and structure control of the the surface coordination environment on the catalyst particles, including the active sites, the adjacent sites and the far-away units that contribute to catalysis simultaneously.
Designing catalysts at atomic scale would benefit to achieve a high efficiency for the transformation of chemical molecules, requiring a precise control in the geometric and electronic features of the active sites and their surroundings. In situ characterizations would identify the dynamic behavior of the working catalysts under reactive atmospheres and at elevated temperature, giving a whole picture from the construction of catalytically active architecture to the evolution upon reacting with molecules. A quantitative description at atomic and molecular levels for the interaction between the active center and the reactive molecules would not only favor an in-depth understanding in the catalytic mechanism but also have a profound consequence for the rational design and structure control of the the surface coordination environment on the catalyst particles, including the active sites, the adjacent sites and the far-away units that contribute to catalysis simultaneously.
2019, 40(s1): 124-128
Abstract:
Catalysis is one of the most important disciplines in the field of chemistry and chemical engineering. Almost all the important processes related to energy, environment and chemical manufacture belong to the category of catalysis. In the past decades, theoretical catalysis based on quantum chemical computation has made amazing progresses both quantitively and qualitatively, which significantly enriched our knowledge on catalysis and promoted the development of the whole chemical science. Consequently, it has become an indispensable research technique to understand catalytic activity, selectivity and explore improved catalysts. In this contribution, recent progresses in theoretical catalysis are presented from three aspects of catalytic materials structures, catalytic reaction mechanisms and catalytic kinetic properties. For each part of the content, we summarized the current researches and potential trends in both domestic and foreign communities and analyzed the characteristic research domains and remaining problems in China. In closing, the current status of theoretical catalysis is evaluated from a general perspective, and the directions and efforts for future development are suggested, in order to better serve the national scientific strategies and policies.
Catalysis is one of the most important disciplines in the field of chemistry and chemical engineering. Almost all the important processes related to energy, environment and chemical manufacture belong to the category of catalysis. In the past decades, theoretical catalysis based on quantum chemical computation has made amazing progresses both quantitively and qualitatively, which significantly enriched our knowledge on catalysis and promoted the development of the whole chemical science. Consequently, it has become an indispensable research technique to understand catalytic activity, selectivity and explore improved catalysts. In this contribution, recent progresses in theoretical catalysis are presented from three aspects of catalytic materials structures, catalytic reaction mechanisms and catalytic kinetic properties. For each part of the content, we summarized the current researches and potential trends in both domestic and foreign communities and analyzed the characteristic research domains and remaining problems in China. In closing, the current status of theoretical catalysis is evaluated from a general perspective, and the directions and efforts for future development are suggested, in order to better serve the national scientific strategies and policies.
2019, 40(s1): 129-142
Abstract:
Selective oxidation is an important type of chemical reactions and is playing vital roles in the chemical industry. Following the changing trend in resources and the requirements from sustainable and green chemistry, the pursuit of 100% selectivity to abate CO2 emission, the substitution of deplete resources with abundant or renewable ones, the use of air/O2/H2O2 as an oxidant instead of organic peroxides and the use of H2O to replace organic solvents have become major research directions in selective oxidation catalysis. The selective oxidation of methane and other alkanes, the epoxidation of propylene and the oxidation of benzene to phenol remain as the most challenging subjects in selective oxidation catalysis. The selective oxidation of specific functional groups in biomass-derived molecules has become a new growing research direction. The harnessing of photocatalysis and electrocatalysis has offered new opportunities for selective oxidation catalysis. This article highlights recent advances in selective oxidation of lower alkanes, in particular methane, epoxidation of propylene, benzene to phenol and selective oxidation of biomass-derived molecules. The key factors that control the catalytic activity and selectivity, and the fundamental issues related to active sites and reaction mechanisms for selective oxidation are discussed. This present article also touches new catalytic materials and methods for selective oxidation, and provides perspectives for future studies in the area.
Selective oxidation is an important type of chemical reactions and is playing vital roles in the chemical industry. Following the changing trend in resources and the requirements from sustainable and green chemistry, the pursuit of 100% selectivity to abate CO2 emission, the substitution of deplete resources with abundant or renewable ones, the use of air/O2/H2O2 as an oxidant instead of organic peroxides and the use of H2O to replace organic solvents have become major research directions in selective oxidation catalysis. The selective oxidation of methane and other alkanes, the epoxidation of propylene and the oxidation of benzene to phenol remain as the most challenging subjects in selective oxidation catalysis. The selective oxidation of specific functional groups in biomass-derived molecules has become a new growing research direction. The harnessing of photocatalysis and electrocatalysis has offered new opportunities for selective oxidation catalysis. This article highlights recent advances in selective oxidation of lower alkanes, in particular methane, epoxidation of propylene, benzene to phenol and selective oxidation of biomass-derived molecules. The key factors that control the catalytic activity and selectivity, and the fundamental issues related to active sites and reaction mechanisms for selective oxidation are discussed. This present article also touches new catalytic materials and methods for selective oxidation, and provides perspectives for future studies in the area.
2019, 40(s1): 143-148
Abstract:
Molecular assembly is an important frontier research in chemistry, physics, biology and material. Biomolecular motors are natural molecular machines that exist in nearly all the biological systems. These biomolecular motors play crucial roles in life activities and participate in a series of important life activities such as intracellular transport, energy transfer and muscle contraction and so on. Rotating molecular motor ATP synthase is one of the most studied biomolecular machines. The recombination of ATP synthase in vitro not only helps to better understand its working mechanism in biological processes, but also promotes the development of biomolecular motor-based devices and synthetic molecular motors. In this paper, we mainly introduce our latest progress on the design and construction of ATP synthase-based biomimetic system. Inspired by photophosphorylation in plants, we fabricated a series of light-responsive ATP synthesis systems by co-assembling ATP synthase and photosystem Ⅱ (PSⅡ) within layer-by-layer assembled cell-like structures. These systems effectively simulated the transformation process from light energy to biological energy in natural photosynthesis. Besides, we also constructed artificial hybrid chloroplasts by introducing functional components into natural chloroplasts. Compared to natural chloroplasts, these hybrid chloroplasts showed remarkable improvement of photophosphorylation efficiency for ATP synthesis. These composite assemblies well simulate the chemical reaction process of photosynthesis in nature, and provide a new way for the effective utilization of light.
Molecular assembly is an important frontier research in chemistry, physics, biology and material. Biomolecular motors are natural molecular machines that exist in nearly all the biological systems. These biomolecular motors play crucial roles in life activities and participate in a series of important life activities such as intracellular transport, energy transfer and muscle contraction and so on. Rotating molecular motor ATP synthase is one of the most studied biomolecular machines. The recombination of ATP synthase in vitro not only helps to better understand its working mechanism in biological processes, but also promotes the development of biomolecular motor-based devices and synthetic molecular motors. In this paper, we mainly introduce our latest progress on the design and construction of ATP synthase-based biomimetic system. Inspired by photophosphorylation in plants, we fabricated a series of light-responsive ATP synthesis systems by co-assembling ATP synthase and photosystem Ⅱ (PSⅡ) within layer-by-layer assembled cell-like structures. These systems effectively simulated the transformation process from light energy to biological energy in natural photosynthesis. Besides, we also constructed artificial hybrid chloroplasts by introducing functional components into natural chloroplasts. Compared to natural chloroplasts, these hybrid chloroplasts showed remarkable improvement of photophosphorylation efficiency for ATP synthesis. These composite assemblies well simulate the chemical reaction process of photosynthesis in nature, and provide a new way for the effective utilization of light.
2019, 40(s1): 149-157
Abstract:
Hydrogen is a highly efficient green chemical. It is widely used as a feedstock for ammonia synthesis, petroleum catalytic hydrogenation, and methanol synthesis. As a green energy source, hydrogen has high combustion heat value, clean combustion products, and also act as gas source for anode of fuel cell. Hydrogen plays a pivotal role in human society. Natural gas is considered as the best raw material for hydrogen production, whose hydrogen production paths include partial oxidation,steam reforming, catalytic cracking, adiabatic conversion, dry reforming with carbon dioxide, and thermal reforming. Methane steam reforming is an efficient and economical method for hydrogen production and has been utilized on an industrialscale, which covers about half of the world's hydrogen production. However, as to the current process, challenges still exhist, such as reducing production costs, reducing carbon deposits, understanding the reaction mechanism, reducing heat transfer consumption, and reducing reaction temperature. Especially since the rise of fuel cell technology, the purity of H2 is demanding, and the CO content in methane steam reforming gas must be as low as 10 ppm or less to avoid poisoning of fuel cell Pt electrode, which puts new requirements on the field of hydrogen production from methane steam reforming. Direct dehydrogenation of methane by catalytic cracking can directly decompose methane into solid carbon and hydrogen. The process is simple and high-purity hydrogen can be obtained. This process consumes less energy and has no pollution to the environment. It is the most promising high-purity hydrogen preparation process. Methane can also be used directly as a hydrogen source for coal-gas co-transformation or even oil-gas co-refining. This paper briefly introduces the background of hydrogen production from methane steam reforming, direct dehydrogenation of methane through catalytic cracking, summarizes the papers of international mainstream journals from January 20 to March 2019, and the international frontiers and development trends, and points out the key issues. This paper also introduces the research status and research characteristics in China and the status of the research team, points out the "strangulation" problem in China, and suggests the research fields and directions for key development in the future. By the way, the concept of coal-methane co-transformation and the idea of oil-methane co-refining are briefly introduced. It should be noted that due to the rather vast of the research fields, this modest review is not intended to be comprehensive.
Hydrogen is a highly efficient green chemical. It is widely used as a feedstock for ammonia synthesis, petroleum catalytic hydrogenation, and methanol synthesis. As a green energy source, hydrogen has high combustion heat value, clean combustion products, and also act as gas source for anode of fuel cell. Hydrogen plays a pivotal role in human society. Natural gas is considered as the best raw material for hydrogen production, whose hydrogen production paths include partial oxidation,steam reforming, catalytic cracking, adiabatic conversion, dry reforming with carbon dioxide, and thermal reforming. Methane steam reforming is an efficient and economical method for hydrogen production and has been utilized on an industrialscale, which covers about half of the world's hydrogen production. However, as to the current process, challenges still exhist, such as reducing production costs, reducing carbon deposits, understanding the reaction mechanism, reducing heat transfer consumption, and reducing reaction temperature. Especially since the rise of fuel cell technology, the purity of H2 is demanding, and the CO content in methane steam reforming gas must be as low as 10 ppm or less to avoid poisoning of fuel cell Pt electrode, which puts new requirements on the field of hydrogen production from methane steam reforming. Direct dehydrogenation of methane by catalytic cracking can directly decompose methane into solid carbon and hydrogen. The process is simple and high-purity hydrogen can be obtained. This process consumes less energy and has no pollution to the environment. It is the most promising high-purity hydrogen preparation process. Methane can also be used directly as a hydrogen source for coal-gas co-transformation or even oil-gas co-refining. This paper briefly introduces the background of hydrogen production from methane steam reforming, direct dehydrogenation of methane through catalytic cracking, summarizes the papers of international mainstream journals from January 20 to March 2019, and the international frontiers and development trends, and points out the key issues. This paper also introduces the research status and research characteristics in China and the status of the research team, points out the "strangulation" problem in China, and suggests the research fields and directions for key development in the future. By the way, the concept of coal-methane co-transformation and the idea of oil-methane co-refining are briefly introduced. It should be noted that due to the rather vast of the research fields, this modest review is not intended to be comprehensive.
2019, 40(s1): 158-164
Abstract:
Understanding catalysis from the molecular scale to the materials scale rely on the combined effort of the experimental characterization and theoretical modelling. Currently, there is a significant development for the in-situ and in particular operando experimental techniques that calls for the simultaneous development of methodologies for theoretical modelling. In fact, several promising methods have been developed and applied in the theoretical modelling of heterogeneous catalysis under the operando conditions. Here we provide a brief overview of these methods addressing their advances as well as the challenges. In particular, the microkintics is required to bridge the microscopic information and the macroscopic properties, which is the most important to the catalyst rational design. However, the accurate and efficient microkinetic method is still lacking. Recently, we propose a method, namely XPK, to extend the phenomenological kinetics for the accurate and efficient microkinetic modeling of heterogeneous catalysis. The advance of such methods will promote the development of the predictive theoretical modelling under operando conditions and will be beneficial to the computation-based rational design of catalysts.
Understanding catalysis from the molecular scale to the materials scale rely on the combined effort of the experimental characterization and theoretical modelling. Currently, there is a significant development for the in-situ and in particular operando experimental techniques that calls for the simultaneous development of methodologies for theoretical modelling. In fact, several promising methods have been developed and applied in the theoretical modelling of heterogeneous catalysis under the operando conditions. Here we provide a brief overview of these methods addressing their advances as well as the challenges. In particular, the microkintics is required to bridge the microscopic information and the macroscopic properties, which is the most important to the catalyst rational design. However, the accurate and efficient microkinetic method is still lacking. Recently, we propose a method, namely XPK, to extend the phenomenological kinetics for the accurate and efficient microkinetic modeling of heterogeneous catalysis. The advance of such methods will promote the development of the predictive theoretical modelling under operando conditions and will be beneficial to the computation-based rational design of catalysts.
2019, 40(s1): 165-168
Abstract:
In heterogeneous catalysis rational design of advanced catalysts and development of new catalysis theory strongly rely on fundamental understanding of surface catalytic mechanism at atomic and molecular level and building catalytic structure-performance relationship. It has been well demonstrated that such studies require well-defined model catalysts and state-of-the-art characterization techniques, which can be greatly promoted by recent innovations in construction of model catalysts and development of in-situ surface and interface techniques. In the present work we introduce the frontiers and tendencies in this field and discuss some key challenges. Furthermore, typical research pro-gresses and related labs in China have been highlight. Finally, the priority research directions have been suggested.
In heterogeneous catalysis rational design of advanced catalysts and development of new catalysis theory strongly rely on fundamental understanding of surface catalytic mechanism at atomic and molecular level and building catalytic structure-performance relationship. It has been well demonstrated that such studies require well-defined model catalysts and state-of-the-art characterization techniques, which can be greatly promoted by recent innovations in construction of model catalysts and development of in-situ surface and interface techniques. In the present work we introduce the frontiers and tendencies in this field and discuss some key challenges. Furthermore, typical research pro-gresses and related labs in China have been highlight. Finally, the priority research directions have been suggested.
2019, 40(s1): 169-177
Abstract:
In the field of carbocatalysis, the main challenges include (1) the quantitative determination of active sites, and the unveiling of the nature and mechanism of the catalysis process; (2) the controllable and scalable preparation of carbon-based catalysts with high density active sites; (3) the catalyst engineering and catalysis process design remain in its infancy, the integrated process on adsorption-catalysis and cataly-sis-separation, aiming to upgrading catalysis process and improving catalysis efficiency, needs to be strengthened. In this minireview, we briefly overviewed the latest advances on carbon materials and carbocatalysis, which include structural design of nanostructured car-bon-based catalysts, their applications in typical thermocatalysis and electrocatalysis as well as the analysis of active sites and disclosure of catalytic mechanisms. Finally, our perspectives on the research trend of future carbocatalysis was given.
In the field of carbocatalysis, the main challenges include (1) the quantitative determination of active sites, and the unveiling of the nature and mechanism of the catalysis process; (2) the controllable and scalable preparation of carbon-based catalysts with high density active sites; (3) the catalyst engineering and catalysis process design remain in its infancy, the integrated process on adsorption-catalysis and cataly-sis-separation, aiming to upgrading catalysis process and improving catalysis efficiency, needs to be strengthened. In this minireview, we briefly overviewed the latest advances on carbon materials and carbocatalysis, which include structural design of nanostructured car-bon-based catalysts, their applications in typical thermocatalysis and electrocatalysis as well as the analysis of active sites and disclosure of catalytic mechanisms. Finally, our perspectives on the research trend of future carbocatalysis was given.
2019, 40(s1): 178-186
Abstract:
Biomass is the only known renewable organic carbon resource in nature that can be used as an alternative to fossil resources for sustainable production of liquid fuels and chemicals. In the past decades, the valorization of biomass, especially the most abundant non-edible lignocellulose, has drawn great attention from both academy and industry worldwide. Here, we attempt to bring together some of the recent advances in the catalytic transformation of lignocellulose and its derived platform molecules to liquid fuels and chemicals. Furthermore, we tentatively propose some topics for further attentions and studies, including the development of new methods for pretreatment, fractionation, and depolymerisation of lignocellulose, the exploration of new catalytic routes to valued-added chemicals from lignocellulose-based platform molecules, the understanding of reaction mechanism and site requirements, and the establishment of comprehensive reaction engineering for catalytic conversion of lignocellulose.
Biomass is the only known renewable organic carbon resource in nature that can be used as an alternative to fossil resources for sustainable production of liquid fuels and chemicals. In the past decades, the valorization of biomass, especially the most abundant non-edible lignocellulose, has drawn great attention from both academy and industry worldwide. Here, we attempt to bring together some of the recent advances in the catalytic transformation of lignocellulose and its derived platform molecules to liquid fuels and chemicals. Furthermore, we tentatively propose some topics for further attentions and studies, including the development of new methods for pretreatment, fractionation, and depolymerisation of lignocellulose, the exploration of new catalytic routes to valued-added chemicals from lignocellulose-based platform molecules, the understanding of reaction mechanism and site requirements, and the establishment of comprehensive reaction engineering for catalytic conversion of lignocellulose.
2019, 40(s1): 187-199
Abstract:
With increasing demand of clean energy, electrochemical energy storage technologies have attracted intensive research interest. In-situ electrochemical characterization with high temporal and spatial resolutions has become increasingly important for investigation of the electrochemical processes in close-to-real electrochemical energy storage devices. This paper reviews the progress of in-situ electrochemical characterization methodology, including in-situ transmission electron microscopy, synchrotron radiation X-ray spectroscopy, and sum frequency generation spectroscopy. The challenges facing in-situ electrochemical characterization and the prospects for further methodological development are presented.
With increasing demand of clean energy, electrochemical energy storage technologies have attracted intensive research interest. In-situ electrochemical characterization with high temporal and spatial resolutions has become increasingly important for investigation of the electrochemical processes in close-to-real electrochemical energy storage devices. This paper reviews the progress of in-situ electrochemical characterization methodology, including in-situ transmission electron microscopy, synchrotron radiation X-ray spectroscopy, and sum frequency generation spectroscopy. The challenges facing in-situ electrochemical characterization and the prospects for further methodological development are presented.
2019, 40(s1): 200-208
Abstract:
To bridge the "pressure gap" in catalytic research, continuous efforts have been made over the past several decades towards achieving photoelectron spectroscopy measurements at elevated pressures. With the help of bright synchrotron light sources, the ambient-pressure X-ray photoelectron spectroscopy (APXPS) endstation based on synchrotron radiation facility is widely used in researches on energy, environment and materials. Here, we will briefly summarize the application and development of in-situ APXPS characterization technique in the field of catalysis. Also, we will give our perspective on the development of APXPS in the future.
To bridge the "pressure gap" in catalytic research, continuous efforts have been made over the past several decades towards achieving photoelectron spectroscopy measurements at elevated pressures. With the help of bright synchrotron light sources, the ambient-pressure X-ray photoelectron spectroscopy (APXPS) endstation based on synchrotron radiation facility is widely used in researches on energy, environment and materials. Here, we will briefly summarize the application and development of in-situ APXPS characterization technique in the field of catalysis. Also, we will give our perspective on the development of APXPS in the future.
2019, 40(s1): 209-216
Abstract:
Catalytic hydrogenation is a widely applied reaction technology in chemistry and chemical engineering. This paper has very briefly summarized the recent progresses on the study of catalytic hydrogenation used for manufactures in scalable industries such as C2/C3 olefins from naphta cracking, pure terephthalic acid, polyethylene, alkylbenzene, hydrodesulfurization of fuels and for preparations of fine chemicals such as the hydrogenation of nitro-, aldehyde, ketone, ester and α,β-unsaturated aldehydes and ketones and so on. A briefly discussion on the hydrogenation of CO/CO2 is also involved. With these preliminary views and comments, the author hopes to master the development trend of catalysis with colleagues in the field of catalytic research.
Catalytic hydrogenation is a widely applied reaction technology in chemistry and chemical engineering. This paper has very briefly summarized the recent progresses on the study of catalytic hydrogenation used for manufactures in scalable industries such as C2/C3 olefins from naphta cracking, pure terephthalic acid, polyethylene, alkylbenzene, hydrodesulfurization of fuels and for preparations of fine chemicals such as the hydrogenation of nitro-, aldehyde, ketone, ester and α,β-unsaturated aldehydes and ketones and so on. A briefly discussion on the hydrogenation of CO/CO2 is also involved. With these preliminary views and comments, the author hopes to master the development trend of catalysis with colleagues in the field of catalytic research.
2019, 40(s1): 217-226
Abstract:
Due to their high theoretical energy density, rechargeable Li-O2 (or Li-air) batteries have attracted extensive attention since they were first proposed in 1996. During the past two decades, researches about Li-O2 batteries have developed and achieved great progress, Li-O2 battery is also regarded as one of the next generation energy storage systems. However, there are still many urgent problems to be settled for Li-O2 batteries, such as the poor cycle performance, instability of electrolyte and security issues of Li anode. So far, researchers have proposed a series of solutions for the main technical problems of Li-O2 batteries. Herein, relevant technical problems and corresponding research methods about electrode materials, electrolytes and mechanism analysis will be introduced, as well as some unresolved issues and suggestions to the development of Li-O2 batteries.
Due to their high theoretical energy density, rechargeable Li-O2 (or Li-air) batteries have attracted extensive attention since they were first proposed in 1996. During the past two decades, researches about Li-O2 batteries have developed and achieved great progress, Li-O2 battery is also regarded as one of the next generation energy storage systems. However, there are still many urgent problems to be settled for Li-O2 batteries, such as the poor cycle performance, instability of electrolyte and security issues of Li anode. So far, researchers have proposed a series of solutions for the main technical problems of Li-O2 batteries. Herein, relevant technical problems and corresponding research methods about electrode materials, electrolytes and mechanism analysis will be introduced, as well as some unresolved issues and suggestions to the development of Li-O2 batteries.
Recent Progress on Photoelectrochemical Water Splitting Based on Molecular Water Oxidation Catalysts
2019, 40(s1): 227-234
Abstract:
Solar water splitting into hydrogen and oxygen has been considered as a promising method for production of solar fuel. A key challenge in overall water splitting is the catalytic water oxidation. And the emergence of molecular water oxidation catalysts (WOCs) has provided an opportunity to mimic the function of the oxygen-evolving complex (OEC) of photosystem Ⅱ in nature and an alternative way for artificial photosynthesis. Despite progress made on molecular approaches to solar energy conversion, construction of molecularly-based artificial photosynthetic devices that enable simultaneous oxygen and hydrogen evolution remains a significant challenge. This paper reviews recent progress in electrochemical and photoelectrochemical water splitting based on molecular WOCs. Strategies and principles for hybrid anodes and photoanodes design were summarized. And these results show great promise for improving the efficiency of artificial photosynthesis by taking advantage of molecular engineering.
Solar water splitting into hydrogen and oxygen has been considered as a promising method for production of solar fuel. A key challenge in overall water splitting is the catalytic water oxidation. And the emergence of molecular water oxidation catalysts (WOCs) has provided an opportunity to mimic the function of the oxygen-evolving complex (OEC) of photosystem Ⅱ in nature and an alternative way for artificial photosynthesis. Despite progress made on molecular approaches to solar energy conversion, construction of molecularly-based artificial photosynthetic devices that enable simultaneous oxygen and hydrogen evolution remains a significant challenge. This paper reviews recent progress in electrochemical and photoelectrochemical water splitting based on molecular WOCs. Strategies and principles for hybrid anodes and photoanodes design were summarized. And these results show great promise for improving the efficiency of artificial photosynthesis by taking advantage of molecular engineering.
