论文发表
1. Fang-Yu Ren, Kaihong Chen, Li-Qi Qiu, Jin-Mei Chen, Donald J. Darensbourg*, Liang-Nian He*, Amphiphilic Polycarbonate Micellar Rhenium Catalysts for Efficient Photocatalytic CO2 Reduction in Aqueous Media. Angew. Chem. Int. Ed. 2022, 61, e202200751. [Link]
Abstract: A triblock amphiphilic polymer derived from the copolymerization of CO2 and epoxides containing a bipyridine rhenium complex in its backbone is shown to effectively catalyze the visible-light-driven reduction of CO2 to CO. This polymer provides uniformly spherical micelles in aqueous solution, where the metal catalyst is sequestered in the hydrophobic portion of the nanostructured micelle. CO2 to CO reduction occurs in an efficient visible-light-driven process in aqueous media with turnover numbers up to 110 (> 99% selectivity) in the absence of a photosensitizer, which is a 37-fold enhancement over the corresponding molecular rhenium catalyst in organic solvent. Notably, the amphiphilic polycarbonate micelle rhenium catalyst suppresses H2 generation, presumably by preventing deactivation of the active catalytic center by water.
2. Zhi-Wen Yang, Jin-Mei Chen, Li-Qi Qiu, Wen-Jun Xie, Liang-Nian He*, Molecular Engineering of Metal Complexes for Electrocatalytic Carbon Dioxide Reducton: From Adjustment of Intrinsic Activity to Molecular Immobilization. Angew. Chem. Int. Ed. 2022, 61, e202205301. [Link]
Abstract: Electrocatalytic CO2 reduction reaction (ECO2RR) is one promising method for storing intermittent clean energy in the chemical bonds and producing fuels. Among various kinds of catalysts for ECO2RR, molecular metal complexes with well-defined structures, thus offer convenient approaches to perform rational designing, investigation about the structure-reactivity relationship and mechanistic studies. In this review, we summarize the molecular engineering of several N-based metal complexes including Re/Mn bipyridine compounds and metal macrocycles, concluding the general modification strategies to devise novel molecular catalysts with high intrinsic activity. Through physical adsorption, covalent linking and forming periodic backbone, these active molecules could be heterogenized into immobilized catalysts with more practical prospect. In the end, significant challenges and opportunities based on molecular catalysts are put forward.
3. Shu-Mei Xia, Da-Wei Cao, Hui-Ying Zeng, Liang-Nian He*, Chao-Jun Li*, Nickel-Catalyzed Stereoselective Alkenylation of Ketones Mediated by Hydrazine. JACS Au. 2022, 2, 1929-1934. [Link]
Abstract: The direct conversion of naturally abundant carbonyl compounds provides a powerful platform for the efficient synthesis of valuable chemicals. In particular, the conversion of ketones to alkenes is a commonly encountered chemical transformation, often achieved via the multistep Shapiro reaction with tosylhydrazone and over stoichiometric organolithium or Grignard reagent. Herein, we report an earth abundant nickel-catalyzed alkenylation of naturally abundant methylene ketones to afford a wide range of alkene derivatives, mediated by hydrazine. The protocol features a broad substrate scope (including alkyl ketones, aryl ketones, and aldehydes), good functional group compatibility, mild reaction conditions, water tolerance, and only environmentally friendly N2 , H2 , and H2O as theoretical byproducts. Moreover, gram-scale synthesis with good yield and generation of pharmaceutical intermediates highlighted its practical applicability.
4. Shu-Mei Xia, Zhi-Wen Yang, Kai-Hong Chen, Ning Wang, Liang-Nian He*, Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO2. Chin. J. Catal. 2022, 43, 1642-1651. [Link]
Abstract: The role of carbodiimide as dehydrant in the chemo-, regio- and stereoselective Pd (II/0)-catalyzed hydrocarboxylation of various alkynes with HCOOH releasing CO in situ is reported for the first time to obtain α,β-unsaturated carboxylic acids. Both symmetrical and unsymmetrical monoalkynes show good reactivity. Importantly, 2,2'-(1,4-phenylene)diacrylic acid can also be synthesized in high yield through the dihydrocarboxylation of 1,4-diethynylbenzene. Besides, an excellent result in gram scale experiment and TON up to 900 can be obtained, displaying the efficiency of this protocol. Notably, regulating the types and concentrations of dehydrant can control the CO generation, avoiding directly operating toxic CO and circumventing sensitivity issue to the CO amount. On the basis of the attractive features of formic acid including easy preparation through CO2 hydrogenation and efficient liberation of CO, this protocol using formic acid as bridging reagent between CO2 and CO can be perceived as an indirect utilization of CO2, offering an alternative method for preparing acrylic acid analogues.
5. Jin-Mei Chen, Wen-Jun Xie, Zhi-Wen Yang, Liang-Nian He*,Cobalt phthalocyanine cross-linked polypyrrole for efficient electroreduction of low concentration CO2 to CO. ChemSusChem 2022, 15, e202201455. [Link]
Abstract: Cobalt phthalocyanine (CoPc) immobilized onto the electrode surface is a significant approach to performing efficient electrochemical CO2 reduction reaction (ECO2RR). Herein, sulphylphenoxy decorated CoPc cross-linked polypyrrole is prepared by in situ polymerization on the surface of carbon cloth. The synthesized N-rich catalyst exhibits above 95% FECO at -0.9 V versus reversible hydrogen electrode(RHE) at least for 10 h in aqueous solution and even enables directly electrolysis at low CO2 concentrations, being potential for coupling ECO2RR with CO2 capture. This facile in situ polymerization strategy would pave the way for developing efficient and practical electrocatalysis for ECO2RR.
6. Wei-Hang Xie, Xiangyang Yao, Heng Li, Hong-Ru Li*, Liang-Nian He*, Biomass-based N-rich Porous Carbon Materials for CO2 Capture and in situ Conversion. ChemSusChem 2022, 15, e202201004. [Link]
Abstract: Capturing CO2 and subsequently converting into valuable chemicals has attracted extensive attention. Herein, a series of biomass-based N-rich porous carbon materials with high specific surface area and pore volume were prepared using biomass waste soybean dregs as precursors. The nitrogen content was up to 4% with different forms in the carbon skeleton such as pyridine-N, pyrrole-N. The synergistic effect of ultra-micropore (pore size < 0.7 nm) and N-containing groups renders the materials exhibit a high CO2 adsorption capacity, reaching 6.3 and 3.6 mmol g-1 at 0 oC and 25 oC under atmosphere pressure respectively. In addition, the sufficient interaction between N-containing groups and CO2 was demonstrated by solid state NMR, the captured CO2 was activated in the form of carbamate possibly, which is conducive to subsequent conversion. Therefore, the supported catalyst with the as-synthetic porous carbon material as the carrier and ZnII as catalytic sites was prepared and successfully applied for carboxylative cyclization of propargylic amine with CO2 to afford the 3-benzyl-5-methyleneoxazolidin-2-one. The results validate CO2 capture and in situ conversion work effectively to produce highly value-added chemicals. In this process, the captured CO2 can be activated and fixed into chemicals in mild conditions. More importantly, the energy consumption in CO2 desorption and adsorbent regeneration can be avoided. The valorization of both solid waste and CO2 to valuable chemicals provides an elegant strategy of killing three birds with one stone.
7. Li-Qi Qiu, Zhi-Wen Yang, Xiangyang Yao, Xiao-Yang Li, Liang-Nian He*, Highly Robust Rhenium(I) Bipyridyl Complexes Containing Dipyrromethene-BF2 Chromophores for Visible Light-Driven CO2 Reduction. ChemSusChem 2022, 15, e202200337. [Link]
Abstract: New rhenium bipyridyl complexes with dipyrromethene-BF2 chromophores (A-ReBDP-CZ, A-ReBDP2, ReBDP-CZ, and ReBDP2) were developed for highly efficient photocatalytic carbon dioxide (CO2) reduction to carbon monoxide (CO). These catalysts consisted of two moderate electron-deficient groups (dipyrromethene-BF2, BDP) as the visible-light-harvesting antenna as well as both electron donor (N-phenylcarbazole, CZ) and acceptor (BDP) on Re bipyridyl framework. Among ReBDP-CZ and ReBDP2 complexes, the ReBDP2 incorporating two electron-deficient BDP chromophores had a longer-lived photoexcited state (182.4 μs) and a twofold enhanced molar absorption coefficient (ϵ=157000 m-1 cm-1) compared with ReBDP-CZ. Thus, ReBDP2 achieved the superior photocatalytic reactivity and stability with a CO turnover number (TONCO) value as high as 1323 and quantum yield (ΦCO) up to 55 %, which was the most excellent photocatalysis efficiency among the single-active-site Re catalysts without additional photosensitizer. Furthermore, the acetylene-bridged linker was detrimental to the photoactivity and durability of the catalyst. In brief, two BDP-based Re bipyridyl systems with outstanding catalytic performance and significant visible-light-harvesting capabilities in the solar spectrum offer a promising strategy for solar-to-fuel conversion schemes.
8. Wen-Feng Wang, Yong-Kang Zhang, Lie-Feng Feng, Hong-Ru Li*, Liang-Nian He*, In-plane Benzene Incorporated g-C3N4 Microtubes: Enhanced Visible Light Harvesting and Carrier Transportation for Photocatalytic CO2 Reduction. Fuel 2022, 326, 125073. [Link]
9. Zhi-Wen Yang, Jin-Mei Chen, Li-Qi Qiu, Wen-Jun Xie, Liang-Nian He*, Solar Energy-driven Electrolysis with Molecular Catalysts for Reduction of Carbon Dioxide Coupled with Oxidation of 5-hydroxymethylfurfural. Catal. Sci. Technol. 2022, 12 (18), 5495-5500. [Link]
Abstract: One paired electrolytic system was constructed with 4-(tert-butyl)phenoxy decorated cobalt phthalocyanine (TBP-CoPc) and pyrene-tethered 2,2,6,6-tetramethylpiperidin-1-oxy (Py-TEMPO), which were non-covalently immobilized on carbon nanotubes to catalyze the CO2 reduction to CO and the oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) respectively. Coupled electrolysis tests in a single electrolyzer with tri-electrode or di-electrode systems unraveled that potential change during electrolysis determined the product distribution, and 96.9% FE for CO as well as 90.8% FE for FDCA were achieved with cell voltage of 2.5 V in di-electrode mode. More importantly, sunlight-driven electrolytic system successfully drove this coupling reaction efficiently, paving the way for future developments in the production of high value-added chemicals with renewable energy source.
10. Xing He, Xiangyang Yao, Shuai-Fang Cai, Hong-Ru Li, Liang-Nian He*, Visible Light-driven Carbamoyloxylation of α-C(sp3)-H Bond of Arylacetones via Radical-initiated Hydrogen Atom Transfer. Chem. Commun. 2022, 58, 5845-5848. [Link]
Abstract: Photocatalytic synthesis has emerged as an efficient route to transform CO2 into functionalized organic carbamates by photocatalysis. Herein, a catalyst-free carbamoyloxylation of arylacetones with CO2 and amines under visible light was developed for the synthesis of O-β-oxoalkyl carbamates in yields up to 93%. This protocol proceeded smoothly with the assistance of inexpensive carbon tetrabromide at room temperature under atmospheric CO2 pressure, leading to simultaneous construction of C–O and C–N bonds. Mechanism studies suggested the photoinduced hydrogen atom transfer (HAT) pathway followed by radical addition or single electron transfer (SET).
11. Shuai-Fang Cai, Li-Qi Qiu, Wen-Bin Huang, Hong-Ru Li*, Liang-Nian He*, Palladium-Catalyzed Carboxylative Cyclization of Propargylic Amines with Aryl Iodides, CO2 and CO at Ambient Pressure. Chem. Commun. 2022, 58 (43), 6332-6335. [Link]
Abstract: A palladium-catalyzed four-component carboxylative cyclization comprising propargylic amines, aryl iodides, CO2 and CO was developed. By selecting Et3N and 1,5,7-Triazabicyclo [4.4.0] dec-5-ene (TBD) as base respectively, both terminal and internal propargylic amines proceeded well facilitated by Pd(PPh3)2Cl2, affording the functionalized 2-oxazolones in moderate yields. This protocol enlarges the the product diversity based on CO2 conversion and simultaneously provides a cooperative transformation way for both CO2 and CO.
12. Wei-Jia Wang, Yong-Kang Zhang, An-Guo Wu, Liang-Nian He*, Cost-Effective 2D Ultrathin Metal–Organic Layers with Bis-Metallic Catalytic Sites for Visible Light-Driven Photocatalytic CO2 Reduction. Chem. Eur. J. 2022, 28, e202201767. [Link] (Front Cover: [Link], Cover Profile: [Link])
Abstract: As novel generated 2D materials, metal-organic layers (MOLs) have recently emerged as a potential platform for photocatalysis CO2 reduction reaction (PCO2RR). Such 2D structures negate the blemish of low-density catalytic sites and low electron transmission efficiency on the surface of MOFs, while retaining the advantage of low expenditure when using earth-abundant metal nodes and meritorious applicability in the PCO2RR. Herein, we report that the 2D ultrathin layer material with bis-metallic catalytic sites (Ni-O metal node and the Ni-N metal site) from bidentate ligand 2,2’-bipyridine-5,5’-dicarboxylate (H2bpydc) and nickel (II) remarkably boosts the visible light-driven PCO2RR performance with a CO yield of 2400 mmol/g for 18 h and a selectivity up to 99%. Consequently, the effects of morphology, catalytic sites and intrinsic properties on PCO2RR efficiency have been investigated in detail. In this context, the ultrathin layer structrue has been elucidated as the key point to facilitate electron transfer efficiency. Notably, the bis-metallic catalytic sites with reasonable distance between two adjacent metals presumably induce synergistic effect, offering a guiding ideology for further designing high performance photocatalysts.
13. Wen-Bin Huang, Meng Yang, Liang-Nian He*, Metal-Free Hydroxymethylation of Indole Derivatives with Formic Acid as an Alternative Way to Indirect Utilization of CO2. J. Org. Chem. 2022, 87, 3775–3779. [Link]
Abstract: The selective N-alkylation of indole substrates remains an ongoing research challenge for the relative attenuated nucleophilicity toward nitrogen. Herein, we developed the hydroxymethylation of indole derivatives to afford N-alkylated indole products with formic acid. This metal-free process was promoted by the organic base 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) using phenylsilane as the reductant under mild conditions. Besides, this strategy represents an alternative way for indirect utilization of CO2, considering the facile hydrogenation of CO2 to produce HCOOH.
14. Wen-Feng Wang, Li-Qi Qiu, Kai-Hong Chen, Hong-Ru Li, Lie-Feng Feng*, Liang-Nian He*, Morphology and Element Doping Effects: Phosphorus-doped Hollow Polygonal g-C3N4 Rods for Visible Light-driven CO2 Reduction. New J. Chem. 2022, 46, 3017-3025. [Link]
Abstract: Photocatalytic CO2 reduction to valuable chemicals, especially the fuels is considered as a promising strategy to mitigate CO2 accumulation and to tackle energy crisis, among which photocatalysis is vital to achieve efficient and selective reduction of CO2. In this work, the phosphorus-doped hollow polygonal g-C3N4 rods were prepared through the phosphoric acid assisted self-assembly under hydrothermal conditions and subsequent thermal polymerization using phosphoric acid as the phosphorus source and melamine as the nitrogen-rich precursor. The resulting phosphorus-doped hollow polygonal g-C3N4 rods feature increased specific surface area, visible light absorption and photogenerated carriers separation and transfer efficiency according to the structure and photoelectric properties characterization. Coupled with earth abundant metal-based complex i.e. [Co(bpy)3]Cl2 as co-catalyst, the phosphorus-doped hollow polygonal g-C3N4 rods deliver a CO evolution rate up to 447.5 μmol·g-1·h-1 with a selectivity ca. 96%, being much higher compared to the pristine g-C3N4 (67.01 μmol·g-1·h-1 with a selectivity ca. 94%) resulting from the improved light harvest and charge transfer to co-catalyst. Remarkably, the phosphorus-doped hollow polygonal g-C3N4 rods can be reused 6 times to keep the constant catalytic activity in the photoreduction reaction. This work presents new insight into photocatalytic CO2 reduction by developing non-metal doping and hollow structural design for semiconductor photocatalysts.
15. Meng Yang, Hong-Ru Li*, Liang-Nian He*, Synthesis of Dimethyl Carbonate via Transesterification of Ethylene Carbonate and Methanol using Recyclable Li/NaY Zeolite. Asian J. Org. Chem. 2022, 11, e202200224. [Link]
Abstract: In this work, the novel solid base Li/NaY was prepared via the solid state reaction between NaY zeolite and Li2CO3 at high temperature. When applied to the dimethyl carbonate (DMC) preparation through transesterification of ethylene carbonate (EC) and methanol, up to 89% yield of DMC with 99% selectivity can be accessed. The characterization results reveal the as-synthesized Li/NaY possesses higher basicity than NaY. Furthermore, the Lewis acidity of the Li/NaY material is also enhanced due to the incorporation of lithium. Therefore, the Li/NaY can act as a dual functional catalyst in the transesterification reaction, thus leading to high efficiency. Notably, this catalyst can be easily recovered and reused for at least six times without obvious activity loss. This work provides a green synthetic route to DMC production and also sheds light on the development of solid basic catalysts.
16. Liang-Nian He, Mini-Rev. Org. Chem., 2022, 19, 271. [Link]
17. Song Gao, Fang-Yu Ren, Wei-Hang Xie, Liang-Nian He*, Hong-Ru Li*, Heterogeneous Esterification of Ricinoleic Acid with Polyol for the Synthesis of Polyol Ricinoleates as Biomass-based Lubricant Base Oil. J. Am. Oil Chem. Soc. 2022, 99, 91-99. [Link]
Abstract: Bio-derived lubricants, especially those derived from vegetable oils, are considered to be promising alternatives to mineral oil-based lubricants due to the features of sustainability and environmental friendliness. In this work, the polyol ricinoleates were prepared by esterification of ricinoleic acid with trimethylolpropane (TMP), neopentyl glycol (NPG) and pentaerythritol (PE) respectively using Lewis acidic stannous oxide as an efficient heterogeneous catalyst, affording the polyol ricinoleates up to 99.7% yield. Remarkably, the solid catalyst was readily recovered and reused at least for five cycles without significant loss of activity. The resulting polyol ricinoleates products were structurally characterized by FT-IR, 1H NMR, 13C NMR, electrospray ionization mass spectra (ESI-MS); and were stable below 300 oC through thermogravimetric analysis (TGA). Furthermore, the physicochemical and lubricating properties of as-synthesized polyol esters were also evaluated including viscosity at 40 oC and 100 oC, viscosity index (VI), pour point and flash point, thermal stability and wear scar diameter. To our delight, the performance indicators of the target products were comparable or better than the commercial lubricants, showing their potential as lubricant base oil. This work represents an alternative access to useful lubricant products via effective and selective conversion of non-edible vegetable oil.
18. Wei-Hang Xie, Heng Li, Meng Yang, Liang-Nian He*, Hong-Ru Li*, CO2 capture and utilization with solid waste. Green Chem. Eng. 2022, 3, 199-209. [Link]
Abstract: Nowadays, the massive consumption of fossil fuels and the resulting excessive emission of carbon dioxide (CO2) have broken the original carbon balance of the nature, resulting in global warming and the consequent detrimental environmental impacts. To address these issues, various initiatives have been proposed, among which CO2 capture and utilization (CCU) is considered as the direct way to mitigation the accumulation of CO2 in atmosphere. Although a plethora of CO2 capture reagents and utilization routes have been developed, the cost of CO2 capture reagents as well as the amount of CO2 utilization still encounters limitations. Recently, CO2 capture and utilization with solid wastes have attracted sustained attention due to its ability to synchronize CO2 fixation with solid wastes utilization. Especially, the huge amount and low cost of the solid wastes can promote the economic fixation of CO2 and thus contribute significantly to carbon sink. Given the tremendous utility of this strategy, this review article summarizes the state of the art of CO2 capture and utilization with solid wastes such as steel slag, concrete waste, fly ash, red mud, calcium carbide residue and biomass etc. And three parts including CO2 mineralization, solid waste-based catalyst promoted CO2 transformation and collaborative transformation of CO2 and solid waste are introduced according to the roles of solid waste in CO2 utilization. We hope this review can arouse broad concern and spur further development in this field.
19. Shoubhik Das, Valerio D’ Elia, Liang-Nian He, Arjan W. Kleij, Tohru Yamada, Carbon Dioxide Chemistry towards Carbon-neutrality. Green Chem. Eng. 2022, 3, 93-95.[Link]
20. 邱丽琪, 姚向阳, 何良年, 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. 高等学校化学学报 2022, 43, 20220064. [Link]
摘要：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，它可以吸附气态CO2分子，在可见光照射下将其还原为一氧化碳（CO）、甲酸（HCOOH）、甲醇（CH3OH）、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可喜进展。本综述总结了近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，也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。
书籍章节
1. Xiang-Yang Yao, Zhi-Wen Yang, Hong-Ru Li, Liang-Nian He, Methylation Reactions with CO2, Ch 26 in The Chemical Transformation of C1 Compounds, X-F. Wu, B. Han, K. Ding, and Z. Liu (eds) 22 MAR 2022 Wiley-VCH Verlag GmbH & Co., Weinheim, GE (Website: www.wiley-vch.de/en/) ISBN-13: 978-3527348954, 1250 pages.
专利申请和授权
1. 张啸，李红茹，赵凤革，叶峰，崔晓莹，何良年，一种蓖麻油酸甲酯加氢制备12-羟基硬脂酸的方法，专利号：ZL201910128976.X
2. 高嵩，李红茹，王庆瑞，崔晓莹，叶锋，何良年, 一种关于蓖麻油酸多元醇酯的制备方法, 申请号：202011038118.5
3. 任方煜，李红茹，叶锋，王庆瑞，崔晓莹，何良年, 一种新型蓖麻基聚氨酯涂层材料及其制备方法, 申请号：202011413213.9