The hydrogenic donor impurity states and intersubband optical absorption spectra in monolayer transition metal dichalcogenides(ML TMDs) under dielectric environments are theoretically investigated based on a two-dimen...The hydrogenic donor impurity states and intersubband optical absorption spectra in monolayer transition metal dichalcogenides(ML TMDs) under dielectric environments are theoretically investigated based on a two-dimensional(2D)nonorthogonal associated Laguerre basis set. The 2D quantum confinement effect together with the strongly reduced dielectric screening results in the strong attractive Coulomb potential between electron and donor ion, with exceptionally large impurity binding energy and huge intersubband oscillator strength. These lead to the strong interaction of the electron with light in a 2D regime. The intersubband optical absorption spectra exhibit strong absorption lines of the non-hydrogenic Rydberg series in the mid-infrared range of light. The strength of the Coulomb potential can be controlled by changing the dielectric environment. The electron affinity difference leads to charge transfer between ML TMD and the dielectric environment, generating the polarization-electric field in ML TMD accompanied by weakening the Coulomb interaction strength. The larger the dielectric constant of the dielectric environment, the more the charge transfer is, accompanied by the larger polarization-electric field and the stronger dielectric screening. The dielectric environment is shown to provide an efficient tool to tune the wavelength and output of the mid-infrared intersubband devices based on ML TMDs.展开更多
The potentials of phenolic productions from lignin and black liquor(BL)via hydrothermal technology with the aids of alkalis and hydrogen donors were investigated,by conducting batch experiments in micro-tube reactors ...The potentials of phenolic productions from lignin and black liquor(BL)via hydrothermal technology with the aids of alkalis and hydrogen donors were investigated,by conducting batch experiments in micro-tube reactors with 300℃ sub-critical water as the solvent.The results showed that all the employed alkalis improved lignin degradation and thus phenolics production,and the strong alkalis additionally manifested deoxygenation to produce more phenolics free of methoxyl group(s).Relatively,hydrogen donors more visibly facilitated phenolics formation.Combination of strong alkali and hydrogen donors exhibited synergistically positive effects on producing phenolics(their total yield reaching 22 wt%)with high selectivities to phenolics,among which the yields of catechol and cresols respectively peaked 16 and 3.5 wt%.BL could be hydrothermally converted into phenolics at high yields(approaching 10 wt%with the yields of catechol and cresols of about 4 and 2 wt%,respectively)with the aids of its inherent alkali and hydrogen donors,justifying its cascade utilization.展开更多
Transfer hydrogenation(TH) with in situ generated hydrogen donor is of great importance in reduction reactions, and an alternative strategy to traditional hydrogenation processes involving pressurized molecular hydrog...Transfer hydrogenation(TH) with in situ generated hydrogen donor is of great importance in reduction reactions, and an alternative strategy to traditional hydrogenation processes involving pressurized molecular hydrogen. Ammonia borane(NH3BH3, AB) is a promising material of hydrogen storage, and it has attracted much attention in reductive organic transformations owing to its high activity, good atom economy, nontoxicity, sustainability, and ease of transport and storage. This review focuses on summarizing the recent progress of AB-mediated TH reactions of diverse substrates including nitro compounds, nitriles, imines, alkenes, alkynes, carbonyl compounds(ketones and aldehydes), carbon dioxide,and N-and O-heterocycles. Syntheses protocols(metal-containing and metal-free), the effect of reaction parameters, product distribution, and variation of reactivity are surveyed, and the mechanism of each reaction involving the action mode of AB as well as structure-activity relationships is discussed in detail. Finally, perspectives are presented to highlight the challenges and opportunities for AB-enabled TH reactions of unsaturated compounds.展开更多
遗传因子的施主杂质在方形、塑造 V 、抛物线的量井说的浅水疗院用飞机波浪基础在有效团的信封功能理论的框架被学习。开始的四个杂质精力层次和扎根的状态的有约束力的精力比与变化方法更容易计算。当井宽度是小的时，计算结果显示杂...遗传因子的施主杂质在方形、塑造 V 、抛物线的量井说的浅水疗院用飞机波浪基础在有效团的信封功能理论的框架被学习。开始的四个杂质精力层次和扎根的状态的有约束力的精力比与变化方法更容易计算。当井宽度是小的时，计算结果显示杂质精力快速随井宽度和减少的增加铺平减少。状态增加直到它的地面的有约束力的精力到达最大的值，然后当井宽度增加，减少。结果是有意义的并且能广泛地在各种各样的 optoelectronic 设备的设计被使用。展开更多
In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron don...In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron donors can decrease or even cease the monoene hydrogenation and thereby keep the high monoene selectivity after reaching its maximum.展开更多
Cleavage of aromatic ether bonds through hydrogenolysis is one of the most promising routes for depolymerisation and transformation of lignin into value-added chemicals. Instead of using pressurized hydrogen gas as hy...Cleavage of aromatic ether bonds through hydrogenolysis is one of the most promising routes for depolymerisation and transformation of lignin into value-added chemicals. Instead of using pressurized hydrogen gas as hydrogen source, some reductive organic molecules, such as methanol, ethanol, isopropanol as well as formates and formic acid, can serve as hydrogen donor is the process called catalytic transfer hydrogenolysis. This is an emerging and promising research field but there are very few reports. In this paper, a comprehensive review of the works is presented on catalytic transfer hydrogenolysis of lignin and lignin model compounds aiming to breakdown the aromatic ethers including a-O-4, b-O-4 and 4-O-5 linkages, with focus on reaction mechanisms. The works are organised regarding to different hydrogen donors used, to gain an in-depth understanding of the special role of various hydrogen donors in this process. Perspectives on current challenges and opportunities of future research to develop catalytic transfer hydrogenolysis as a competitive and unique strategy for lignin valorisation are also provided.展开更多
文摘The hydrogenic donor impurity states and intersubband optical absorption spectra in monolayer transition metal dichalcogenides(ML TMDs) under dielectric environments are theoretically investigated based on a two-dimensional(2D)nonorthogonal associated Laguerre basis set. The 2D quantum confinement effect together with the strongly reduced dielectric screening results in the strong attractive Coulomb potential between electron and donor ion, with exceptionally large impurity binding energy and huge intersubband oscillator strength. These lead to the strong interaction of the electron with light in a 2D regime. The intersubband optical absorption spectra exhibit strong absorption lines of the non-hydrogenic Rydberg series in the mid-infrared range of light. The strength of the Coulomb potential can be controlled by changing the dielectric environment. The electron affinity difference leads to charge transfer between ML TMD and the dielectric environment, generating the polarization-electric field in ML TMD accompanied by weakening the Coulomb interaction strength. The larger the dielectric constant of the dielectric environment, the more the charge transfer is, accompanied by the larger polarization-electric field and the stronger dielectric screening. The dielectric environment is shown to provide an efficient tool to tune the wavelength and output of the mid-infrared intersubband devices based on ML TMDs.
基金acknowledge the Natural Science Foundation of Shandong Province(ZR2016BL24)the financial support from the China-Japanese Research Cooperative Program-China(NO.2016YFE0118000)Natural Science Foundation of Hebei Province(B2018208127).
文摘The potentials of phenolic productions from lignin and black liquor(BL)via hydrothermal technology with the aids of alkalis and hydrogen donors were investigated,by conducting batch experiments in micro-tube reactors with 300℃ sub-critical water as the solvent.The results showed that all the employed alkalis improved lignin degradation and thus phenolics production,and the strong alkalis additionally manifested deoxygenation to produce more phenolics free of methoxyl group(s).Relatively,hydrogen donors more visibly facilitated phenolics formation.Combination of strong alkali and hydrogen donors exhibited synergistically positive effects on producing phenolics(their total yield reaching 22 wt%)with high selectivities to phenolics,among which the yields of catechol and cresols respectively peaked 16 and 3.5 wt%.BL could be hydrothermally converted into phenolics at high yields(approaching 10 wt%with the yields of catechol and cresols of about 4 and 2 wt%,respectively)with the aids of its inherent alkali and hydrogen donors,justifying its cascade utilization.
基金financially supported by the National Natural Science Foundation of China (21908033,21576059,21666008)Fok Ying-Tong Education Foundation (161030)+1 种基金the Program of Introducing Talents of Discipline to Universities of China (111 Program,D20023)Guizhou Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules ([2020]004)。
文摘Transfer hydrogenation(TH) with in situ generated hydrogen donor is of great importance in reduction reactions, and an alternative strategy to traditional hydrogenation processes involving pressurized molecular hydrogen. Ammonia borane(NH3BH3, AB) is a promising material of hydrogen storage, and it has attracted much attention in reductive organic transformations owing to its high activity, good atom economy, nontoxicity, sustainability, and ease of transport and storage. This review focuses on summarizing the recent progress of AB-mediated TH reactions of diverse substrates including nitro compounds, nitriles, imines, alkenes, alkynes, carbonyl compounds(ketones and aldehydes), carbon dioxide,and N-and O-heterocycles. Syntheses protocols(metal-containing and metal-free), the effect of reaction parameters, product distribution, and variation of reactivity are surveyed, and the mechanism of each reaction involving the action mode of AB as well as structure-activity relationships is discussed in detail. Finally, perspectives are presented to highlight the challenges and opportunities for AB-enabled TH reactions of unsaturated compounds.
基金Supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (PRC)Foundation of Qufu Normal University under Grant No. XJ0622
文摘遗传因子的施主杂质在方形、塑造 V 、抛物线的量井说的浅水疗院用飞机波浪基础在有效团的信封功能理论的框架被学习。开始的四个杂质精力层次和扎根的状态的有约束力的精力比与变化方法更容易计算。当井宽度是小的时，计算结果显示杂质精力快速随井宽度和减少的增加铺平减少。状态增加直到它的地面的有约束力的精力到达最大的值，然后当井宽度增加，减少。结果是有意义的并且能广泛地在各种各样的 optoelectronic 设备的设计被使用。
文摘In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron donors can decrease or even cease the monoene hydrogenation and thereby keep the high monoene selectivity after reaching its maximum.
文摘Cleavage of aromatic ether bonds through hydrogenolysis is one of the most promising routes for depolymerisation and transformation of lignin into value-added chemicals. Instead of using pressurized hydrogen gas as hydrogen source, some reductive organic molecules, such as methanol, ethanol, isopropanol as well as formates and formic acid, can serve as hydrogen donor is the process called catalytic transfer hydrogenolysis. This is an emerging and promising research field but there are very few reports. In this paper, a comprehensive review of the works is presented on catalytic transfer hydrogenolysis of lignin and lignin model compounds aiming to breakdown the aromatic ethers including a-O-4, b-O-4 and 4-O-5 linkages, with focus on reaction mechanisms. The works are organised regarding to different hydrogen donors used, to gain an in-depth understanding of the special role of various hydrogen donors in this process. Perspectives on current challenges and opportunities of future research to develop catalytic transfer hydrogenolysis as a competitive and unique strategy for lignin valorisation are also provided.
