论文发表
1. Wei-Jia Wang, Kai-Hong Chen, Zhi-Wen Yang, Bo-Wen Peng and Liang-Nian He*, Tuning of visible light-driven CO2 reduction and hydrogen evolution activity by using POSS-modified porous organometallic polymers, J. Mater. Chem. A, 2021, 9, 16699-16705.[Link]
Abstract: Significant efforts have been devoted to the photochemical CO2 reduction reaction (CO2RR) as a significant pathway for the development of renewable energy systems. However, the competitive hydrogen evolution reaction (HER) greatly impedes the fundamental understanding and industrial application of the CO2RR. Herein, we report polyhedral oligomeric silsesquioxane (POSS)-based porous organometallic polymers (POMPs) that are able to catalyze the photochemical CO2RR to produce syngas. Their surface area, CO2 adsorption ability, visible-light harvesting capacity and photoinduced electron–hole separation efficiency can be regulated by tuning the Re-bipyridine content in POMPs. Consequently, the effects of these properties on CO2RR and HER activities have been investigated and the surface area and electron transfer efficiency of these materials have been elucidated as the key points. Importantly, we also reveal the applicability of the developed strategy in designing new catalysts for the CO2RR.
2. Yu-Xing Huang, Zhuo Xin, Liang-Nian He*, Water activated main element-based syngas surrogates for safe functionalization of unsaturated chemicals, Sci. Bull., 2021, 66, 865–867. [Link]
3. Mei-Yan Wang, Xin Jin, Xiao-Fei Wang, Shu-Mei Xia, Yue Wang, Shou-Ying Huang, Ying Li, Liang-Nian He*, Xinbin Ma*, Copper‐Catalyzed and Proton‐Directed Selective Hydroxymethylation of Alkynes with CO2, Angew. Chem. Int. Ed., 2021, 60, 3984-3988. [Link]
Abstract: An intriguing strategy for copper‐catalyzed hydroxymethylation of alkynes with CO2 and hydrosilane was developed. Switched on/off a proton source, e.g. tBuOH, direct hydroxymethylation and reductive hydroxymethylation could be triggered selectively, delivering a series of allylic alcohols and homobenzylic alcohols respectively, with high levels of Z/E, regio‐ and enantioselectivity. Such a selective synthesis is attributed to the differences in response of vinylcopper intermediate to proton and CO2 . The protonation of vinylcopper species is demonstrated to be prior to hydroxymethylation, thus allowing a diversion from direct alkyne hydroxymethylation to reductive hydroxymethylation in the presence of suitable proton.
4. Shu-Mei Xia, Zhi-Wen Yang, Xiang-Yang Yao, Kai-Hong Chen, Li-Qi Qiu, and Liang-Nian He*, Synergistic copper/ppm Pd-catalyzed hydrocarboxylation of alkynes with formic acid as CO surrogate as well as hydrogen source: an alternative indirect utilization of CO2, Green Chem., 2021, 23, 8089-8095. [Link]
Abstract: An unprecedented strategy has been developed involving earth abundant Cu-catalyzed hydrocarboxylation of alkynes with HCOOH to (E)-acrylic derivatives with high regio- and stereoselectivity by synergistic effects with ppm levels of Pd catalyst. Both symmetrical and unsymmetrical alkynes bearing various functional groups were successfully hydrocarboxylated with HCOOH and the modification of pharmaceutical molecule exemplified its practicability. This protocol employs HCOOH as both CO surrogate and hydrogen donor with 100% atom economy and can be viewed as an alternative approch for indirect CO2 utilization. Mechanistic investigations indicate a Cu/ppm Pd cooperative catalysis mechanism via alkenylcopper species as a potential intermediate formed from Cu-hydride active catalytic species with HCOOH as hydrogen source. This bimetallic system involving inexpensive Cu and trace Pd provides a reliable and efficient hydrocarboxylation way to access industrial useful acrylic derivatives with HCOOH as hydrogen source, as well as a novel clue for other Cu-H-related co-catalytic systems.
5. Shuai-Fang Cai, Hong-Ru Li * and Liang-Nian He *, Bifunctionalization of unsaturated bonds via carboxylative cyclization with CO2: a sustainable access to heterocyclic compounds. Green Chem., 2021, 23, 9334-9347. [Link]
Abstract: CO2 valorization into valuable chemicals has attracted much attention, among which carboxylative cyclization represents an appealing transformation strategy to synthesize heterocyclic compounds. Conventionally, the carboxylative cyclization comprises CO2 capture and subsequent nucleophilic attack of the resulting carboxylic anion to an unsaturated bond, by which the monofunctionalization of the unsaturated bond is realized and the heterocyclic compounds, such as 5-/6-membered cyclolactone, cyclocarbonate, and oxazolidinone, are accordingly generated. Nowadays, the CO2-participated multicomponent carboxylative cyclizations have evoked intense interest due to their ability to perform the bifunctionalization of the unsaturated bond in the ring-closing step, thus assembling complex molecules. Up to now, by activating the unsaturated bonds with functionalized reagents and designing cascade reactions of organometallic compounds, substituents including iodine, trifluoromethyl, perfluoroalkyl, alkyl, cyanoalkyl, allyl, aryl, phenoxy, allenyl, selenyl, amino, and phosphonyl groups have been incorporated into the cyclocarbonate or oxazolidinone compounds successfully through the multicomponent carboxylative cyclizations. Given the tremendous utility of this synthetic strategy in heterocyclic compound synthesis, this review summarizes the progress of multicomponent carboxylative cyclizations to spur the further development of this field.
6. Da-Gang Yu*, Liang-Nian He*, Introduction to CO2 utilisation, Green Chem., 2021, 23, 3499– 3501. [Link]
7. Xiangyang Yao, Kaihong Chen, Li-Qi Qiu, Zhi-Wen Yang, and Liang-Nian He*，Ferric Porphyrin-Based Porous Organic Polymers for CO2 Photocatalytic Reduction to Syngas with Selectivity Control, Chem. Mater., 2021, 33, 8863-8872.[Link]
Abstract: Visible light-induced photocatalytic CO2 reduction reaction (CO2RR) is a feasible and promising option to tackle the greenhouse effect and energy crisis. Herein, two ferric porphyrin-based porous organic polymer semiconductors, hereafter referred to as POPn-Fe (porous organic polymers, n=1 or 2, corresponding to a benzene/biphenyl unit as a linker between porphyrin units), are synthesized for the visible light-driven CO2RR to produce syngas. The CO/H2 evolution rates for POP2-Fe under irradiation >420 nm are found to successfully reach up to 3043 and 3753 μmol•g–1• h–1, respectively. Interestingly, the experiment results imply that the ferric porphyrin site could be responsible for CO evolution and the uncoordinated porphyrin unit in POPn or POPn-Fe semiconductors may be obligate for H2 formation. Furthermore, as evidenced by Mott–Schottky plots, the extended π-conjugation with the biphenyl linker makes POP2-Fe a lower conduction band potential, which helps the ferric porphyrin sites capture electrons from the photosensitizer, thus producing more CO to realize selectivity control. Also, the efficient catalytic activity of POP2-Fe is presumably attributed to the accelerated charge transfer as well as facilitates photogenerated electron and hole separation. This work offers an elegant strategy to design and optimize earth-abundant metal visible light photocatalysis for CO2 reduction to syngas with CO/H2 ratio control.
8. Wen-Bin Huang, Li-Qi Qiu, Fang-Yu Ren and Liang-Nian He*, Facile synthesis of α-aminophosphine oxides from diarylphosphine oxides, arynes and formamides,Chem. Commun., 2021, 57, 9578-9581. [Link]
Abstract: The straightforward synthesis of α-amino phosphine oxides via three-component reactions involving arynes, formamides and diarylphosphine oxides is disclosed. This method employs the aryne to activate formamide, without external activating reagent, which is operationally simple at mild conditions with high efficiency. Furthermore, mechanistic perception suggests a cascade sequence including formal [2+2] cycloaddition of aryne with C=O bond, a 1,4-addition of the H-P(O) compounds to the enamine intermediates.
9. Xin Jin, Hong-Chen Fu, Mei-Yan Wang, Shou-Ying Huang, Yue Wang, Liang-Nian He, and Xin-Bin Ma*, Chemodivergent Synthesis of One-Carbon-Extended Alcohols via Copper-Catalyzed Hydroxymethylation of Alkynes with Formic Acid, Org. Lett. 2021, 23, 4997−5001. [Link]
Abstract: The development of selective catalytic reactions that utilize easily available reagents for the efficient synthesis of alcohols is a long-standing goal of chemical research. Here an intriguing strategy for the chemodivergent copper-catalyzed hydroxymethylation of alkynes with formic acid and hydrosilane has been developed. By simply tuning the amount of formic acid and reaction temperature, distinct one-carbon-extended primary alcohols, that is, allylic alcohols and β-branched alkyl alcohols, were produced with high levels of Z/E-, regio-, and enantioselectivity.
10. Li-Qi Qiu, Kai-Hong Chen, Zhi-Wen Yang, Fang-Yu Ren, Liang-Nian He*, Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole-pyridine Framework for Efficient CO2 Photoreduction, Chem. - Eur. J., 2021, 27, 15536-15544. [Link]
Abstract: The photocatalytic reduction of CO2 into fuels offers the prospect for creating a new CO2 economy. Harnessing visible light-driven CO2 -to-CO reduction mediated by the long-lived triplet excited state of rhenium(I) tricarbonyl complexes is a challenging approach. We here develop a series of new mononuclear rhenium(I) tricarbonyl complexes ( Re-1 − Re-4 ) based on the imidazole-pyridine skeleton for photo-driven CO2 reduction. These catalysts are featured by combining pyridyl-imidazole with the aromatic ring and different pendant organic groups onto the N1 position of 1,3-imidazole unit, which display phosphorescence under Ar-saturated solution even at ambient conditions. By contrast, {Re[9-(pyren-1-yl)-10-(pyridin-2-yl)-9H-pyreno[4,5-d]imidazole)](CO)3Cl} ( Re-4 ) by introducing pyrene ring at the N1 position of pyrene-fused imidazole unit exhibits superior catalytic performance with a higher turnover number for CO (TONCO = 124) and >99.9% selectivity, primarily ascribed to the strong visible light-harvesting ability, long-lived triplet lifetimes (164.2 µs) and large reductive quenching constant. Moreover, the rhenium(I) tricarbonyl complexes derived from π-extended pyrene chromophore exhibit a long lifetime corresponding to its ligand-localized triplet state ( 3 IL) evidenced from spectroscopic investigations and DFT calculations.
11. Fang-Yu Ren, Fei You, Song Gao, Wei-Hang Xie, Liang-Nian He*, Hong-Ru Li*, Oligomeric ricinoleic acid synthesis with a recyclable catalyst and application to preparing non-isocyanate polyhydroxyurethane,Eur. Polym. J., 2021, 153, 110501. [Link]
Abstract: As a consequence of the great demand and extended application of polyurethanes in various fields, the development of green processes for their production and functional polyurethane materials has received widespread attention. In this regard, the biomass-derived polyurethane via the non-isocyanate route could be promising. In this work, the castor-based polyurethanes were designed and synthesized through a non-isocyanate route by employing ricinoleic acid as the starting material, in which the oligomeric ricinoleic acid (ORA) with variable average polymerization degree was used as the key intermediate. To access the ORA with different average polymerization degree, the solid Lewis acid tin(II) oxide (SnO) was developed as the efficient and recyclable catalyst and the average polymerization degree of ORA was regulated by the reaction time at 210 °C. After sequential esterification, epoxidation, cycloaddition with CO2 and polyaddition with 1,6-hexamethylene diamine (HMDA) or isophorone diamine (IPDA), a series of polyhydroxyurethanes (PHUs) with different tensile strength and elongation at break as well as the thermal stability and the glass transition temperature were obtained depending on the type of diamine and the average polymerization degree of ORA, indicating the functional role of the polymerization degree of ORA in regulating the mechanical and thermal properties of the resulting materials. This protocol for the castor-based PHUs preparation in this work not only represents a green and sustainable way to produce bio-based material, but also provides a convenient way to change the average polymerization degree of ORA and then alter the properties of resulting polyurethanes.
12. Liang-Nian He, Perface, Curr. Org. Synth., 2021, 18(1), 1-2. [Link]
13. 黄文斌, 邱丽琪, 任方煜, 何良年*, 有机化学, 2021, 41 (10), 3914-3934.
Wen-Bin Huang, Li-Qi Qiu, Fang-Yu Ren and Liang-Nian He*, Advances on Transition-Metal Catalyzed CO2 Hydrogenation.Chin. J. Org. Chem., 2021, 41 (10), 3914-3934. [Link]
摘要：二氧化碳(CO2)作为主要的温室气体, 由于人类过度使用化石资源导致大气中CO2浓度增加, 进而引发全球环境问题。另一方面, CO2是一种理想的C1资源, 具有安全、储量丰富、廉价易得等优点。因此, 如何将CO2应用于有机合成以获得化工产品与燃料, 已成为当前研究热点。其中, 过渡金属催化的CO2氢化反应是CO2资源化利用重要途径, 反应可以在温和条件下选择性地生成2e、4e和6e还原产物, 例如甲酸、甲酰胺、甲酸酯、甲醛、甲醇以及C2+醇等产物, 具有广阔的应用前景; 因此, 引人注目。本文系统总结了近来过渡金属配合物催化CO2加氢反应的研究进展, 主要对催化剂的种类和结构、活性及其产物选择性等进行总结。并对近来所发展的与CCU策略(CO2 capture and utilization)相关的CO2原位催化氢化反应进行了分析与讨论。此外, 对本领域中存在的挑战及展望进行了分析。
14. Xiao Zhang, Hong-Ru Li, Feng-Ge Zhao, Xiao-Ying Cui, Feng Ye, Liang-Nian He*, Green Process for Hydrogenation of Methyl Ricinoleate to Methyl 12-Hydroxystearate Over Diatomite Supported Cu-Ni Bimetallic Catalyst, Green Chem. Eng., 2021, 2 (2), 187-196. [Link]
Abstract: A series of diatomite supported Cu–Ni bimetallic catalysts were prepared using the co-impregnation method to improve the efficiency and selectivity toward methyl 12-hydroxystearate in the hydrogenation of methyl ricinoleate. The catalysts were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (H2-TPR). All the characterization results verified the formation of highly dispersed Ni–Cu alloy on support. Moreover, by subtly regulating the Ni/Cu molar ratio as well as the reaction parameters, the hydrogenation of methyl ricinoleate to methyl 12-hydroxystearate proceeded efficiently and selectively, affording 97% yield of methyl 12-hydroxystearate and nearly equivalent conversion of methyl ricinoleate under 2 MPa H2 pressure and at 130 °C in 4 h with only 1 wt% of the catalyst Ni7Cu1/diatomite (based on methyl ricinoleate). Besides, the supported Cu–Ni bimetallic catalyst is stable during recycle and reuse. After five cycles of reuse, much catalytic activity is still preserved. Therefore, this low-cost and stable bimetallic catalyst would be promising for the hydrogenation of methyl ricinoleate to methyl 12-hydroxystearate, representing an example of green catalysis for efficiently conversion of biomass to value-added chemicals and materials.
15. Liang-Nian He, Carbon dioxide chemistry: Carbon capture, activation and utilization,科学通报, 2021, 66 (7), 713-715.[Link]
书籍章节
1. Yu-Nong Li, Hong-Ru Li, Liang-Nian He, “Chapter 5. CO2 Fixation into Organic Molecules via Carbon–Heteroatom Bond Formation” in CO2 as a Building Block in Organic Synthesis, Edited by Shoubhik Das. First edition, Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA. [Link]
专利授权
1. 李雪冬，李红茹，夏书梅，何良年，一种由配体调控的二氧化碳和胺类选择性还原制备甲酰胺和N-甲基胺类的方法，授权公告日：2021.3.16，专利号：ZL 201810729182.4
2. 游飞，李红茹，陈凯宏，赵凤革，叶锋，崔晓莹，何良年，一种低聚蓖麻油酸酯的制备方法，授权公告日：2021.10.26，专利号：ZL201811438980.8
3. 宋禹，李红茹，何兴，叶锋，崔晓莹，何良年，一种离子液体催化合成碳酸二甲酯的方法，授权公告日：2021.10.15，专利号：ZL201910128418.3
4. 游飞，高嵩，何兴，李红茹，何良年，叶锋，崔晓莹，一种可实现低聚蓖麻油酸酯制备和原位分离的方法，授权公告日：2021.9.10，专利号：ZL202010124194.1
5. 王庆瑞，孟祥云，何良年，叶锋，崔晓莹，粟斌，一种自由活塞式线性发电机润滑油添加剂及其制备方法，授权日期：2021.7.6，专利号：ZL201811438546.X