论文发表

1.  Chun-Shuai Cao, Shu-Mei Xia, Zhen-Jun Song, Hang Xu, Ying Shi, Liang-Nian He*, Peng Cheng, and Bin Zhao* Highly Efficient Conversion and Reaction Mechanism of Propargylic Amines and CO₂ Catalyzed by Eco-Friendly Noble-Metal-Free [Zn116] Nanocages. Angew. Chem. Int. Ed., 2020, 59, 22, 8586-8593. [link]

Abstract: The reaction of propargylic amines and CO₂ can provide high‐value‐added chemical products. However, most of catalysts in such reactions employ noble metals to obtain high yield, and it is important to seek eco‐friendly noble‐metal‐free MOFs catalysts. Here, a giant and lantern‐like [Zn₁₁₆] nanocage in zinc‐tetrazole 3D framework [Zn₂₂(Trz)₈(OH)₁₂(H₂O)₉·8 H₂O]_n Trz=(C₄N₁₂O)⁴⁻ (1) was obtained and structurally characterized. It consists of six [Zn₁₄O₂₁] clusters and eight [Zn₄O₄] clusters. To our knowledge, this is the highest‐nuclearity nanocages constructed by Zn‐clusters as building blocks to date. Importantly, catalytic investigations reveal that 1 can efficiently catalyze the cycloaddition of propargylic amines with CO₂, exclusively affording various 2‐oxazolidinones under mild conditions. It is the first eco‐friendly noble‐metal‐free MOFs catalyst for the cyclization of propargylic amines with CO₂. DFT calculations uncover that Zn^II ions can efficiently activate both C≡C bonds of propargylic amines and CO₂ by coordination interaction. NMR and FTIR spectroscopy further prove that Zn‐clusters play an important role in activating C≡C bonds of propargylic amines. Furthermore, the electronic properties of related reactants, intermediates and products can help to understand the basic reaction mechanism and crucial role of catalyst 1.

2.  Zhi-Hua Zhou, Kai-Hong Chen, Song Gao, Zhi-Wen Yang and Liang-Nian He*, Ionic Liquid-Modified Porous Organometallic Polymers as Efficient and Selective Photocatalysts for Visible-Light-Driven CO₂ Reduction, Research, 2020, 2020, 9398285. [link]

Abstract: In the photoreduction of CO₂ to CO, the competitive H₂ evolution is always inevitable due to the approximate reduction potentials of H⁺/H₂ and CO₂/CO, which results in poor selectivity for CO production. Herein, imidazolium-type ionic liquid- (IL-) modified rhenium bipyridine-based porous organometallic polymers (Re-POMP-IL) were designed as efficient and selective photocatalysts for visible-light CO₂ photoreduction to CO based on the affinity of IL with CO₂. Photoreduction studies demonstrated that CO₂ photoreduction promoted by Re-POMP-IL functioning as the catalyst exhibits excellent CO selectivity up to 95.5% and generate 40.1 mmol CO/g of Re-POMP-IL1.0 (obtained by providing equivalent [(5,5-divinyl-2,2-bipyridine)Re(CO)₃Cl] and 3-ethyl-1-vinyl-1H-imidazol-3-ium bromide) at 12 h, outperforming that attained with the corresponding Re-POMP analogue without IL, which highlights the crucial role of IL. Notably, CO₂ adsorption, light harvesting, and transfer of photogenerated charges as key steps for CO₂RR were studied by employing POMPs modified with different amounts of IL as photocatalysts, among which the CO₂ affinity as an important factor for POMPs catalyzed CO₂ reduction is revealed. Overall, this work provides a practical pathway to improve the CO₂ photoreduction efficiency and CO selectivity by employing IL as a regulator.

3.   Xing He, Li-Qi Qiu, Wei-Jia Wang, Kaihong Chen and Liang-Nian He*, Photocarboxylation with CO₂: an appealing and sustainable strategy for CO₂ fixation. Green Chem., 2020, 22(21), 7301-7320. [link]

Abstract: With the increasing awareness of sustainable chemistry and green chemistry, photochemical CO₂ fixation has drawn more and more attention in response to renewable C1 resource and inexhaustible clean energy resource. It is appealing to provide carboxylic acids and derivatives using CO₂ as renewable feedstock, which is widely used in the manufacture of pharmaceutical, pesticide, dye and other fine chemicals. Classified by the types of reaction sites, this review is to present an overview of the recent advances and achievements in photocarboxylation of C(sp³)-X (X = H, N) bond, C(sp²)-X (X = H, N, (pseudo)halide) bond and C(sp)-H bond with CO₂ with emphasis on the mechanistic aspects of the reactions and a perspective on the future prospects, hopefully further stimulating rearch and development of this appealing field.

4.   Li-Qi Qiu, Kaihong Chen, Zhi-Wen Yang, and Liang-Nian He*, Rhenium Catalyst with Bifunctional Pyrene Groups Boosts Natural Light-Driven CO₂ Reduction. Green Chem., 2020, 22, 8614-8622. [link]

Abstract: Developing effective sunlight-driven systems for CO₂ reduction is one of the most promising subjects from the perspective of sustainably producing solar fuels. Herein, we develop a strategy to boost CO₂ reduction performance by enhancing intermolecular electron transfer efficiency and visible light-absorption ability by introducing bifunctional pyrene groups on the ligand. This catalyst exhibits high-efficiency performance for natural light-powered CO₂ reduction (TON_CO up to 350 ± 36, Φ_CO up to 46.6 ± 3%). This is the first report on using a single-molecule photocatalyst for CO₂ reduction under natural conditions. Through the combination of experimental results and DFT calculations, the appending pyrene groups have been proven to promote the catalyst's ability to harness visible light as well as facilitate electron transfer (ET) through intermolecular π–π interactions. Due to the accelerated intermolecular ET, TON_CO can be further boosted up to 1367 ± 32 in the presence of the ruthenium photosensitizer. Moreover, an enhancement in CO₂ electroreduction performance can also be observed for the pyrenyl-functionalized rhenium catalyst further highlighting the versatile applications of this methodology.

5.   Kai-Hong Chen, Ning Wang, Zhi-Wen Yang, Shu-Mei Xia and Liangnian He*, Tuning of Ionic Second Coordination Sphere in Evolved Rhenium Catalyst for Efficient Visible Light-Driven CO₂ Reduction. ChemSusChem, 2020, 13(23), 6284-6289.  [link]

Abstract: Developing an efficient and easy‐to‐handle strategy in designing catalysts for CO₂ reduction into CO by harnessing sunlight is a promising project. Here, a facile strategy was developed to design a Re catalyst modified with an ionic secondary coordination sphere for photoreduction of CO₂ to CO by visible light. By adding ionic liquids or tuning a different ionic secondary coordination sphere, it was discovered that an outstanding optical property, other than CO₂ absorption ability or the ability to dissociation of chloride anion, is the prerequisite for catalyst design. Accordingly, a novel Re catalyst, {Re[BpyMe(tris(2‐hydroxyethyl)amine)](CO)₃Cl}Br (Re‐THEA), was designed, screened, and resulted in a relative high quantum yield (up to 34 %) for visible‐light‐induced CO₂ reduction with a single‐molecule system. DFT calculations, combined with experimental outcomes, suggested the pendant ionic tris(2‐hydroxyethyl)amino (THEA) group on Re‐THEA can enhance visible‐light absorption, stabilize reaction intermediates, and suppress the Re–Re dimer formation.

6.  Xiao Zhang, Kai-Hong Chen, Zhi-Hua Zhou, Liang-Nian He*, Reduced Graphene Oxide Supported Ag Nanoparticles: An Efficient Catalyst for CO₂ Conversion at Ambient Conditions. ChemCatChem, 2020, 12(19), 4825-4830. [link]

Abstract: A highly efficient carboxylative cyclization of propargylic alcohols with CO₂ under atmospheric pressure catalyzed by silver (0) nanoparticles decorated reduced graphene oxide (Ag‐rGO) is reported. Ag‐rGO was fully characterized by scanning electron microscope spectra (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT‐IR) spectra, Raman spectra and X‐ray photoelectron spectroscopy (XPS). Notably, Ag‐rGO can be also applied to the construction of other value‐added chemicals (β‐oxopropylcarbamates and 2‐oxazolidinones) from CO₂ at ambient conditions. In addition, Ag‐rGO is stable and reusable, which shows the potential for the practical application for CO₂ capture and utilization (CCU).

7. Hong-Ru Li and Liang-Nian He*, Construction of C–Cu Bond: A Useful Strategy in CO₂ Conversion. Organometallics, 2020,  39, 9, 1461-1475. [link]

Abstract: Carbon dioxide is not only one of the greenhouse gases but also an appealing renewable C1 source. To reconcile the environmental benefit with chemical industry development, conversion of CO₂ into valuable chemicals is proposed, and tremendous effort has been devoted to developing new synthetic protocols and highly efficient catalytic systems, wherein copper catalysis is attractive and features effective, inexpensive, and diverse transformation of CO₂. Considering the ubiquity of the C–Cu bond in organic chemistry and the wide application of the resulting carbocuprate species in reductive coupling with electrophiles, C–Cu formation and subsequent CO₂ insertion has been developed as an important strategy for CO₂ chemical fixation, thereby resulting in the preparation of a variety of valuable chemicals. To arouse broad interest in this strategy, we summarize recent advances and give an overview on CO₂ transformations via the carbocuprate species on the basis of the C–Cu bond formation mechanism, including copper⁻promoted alkyne and halide activation, transmetalation of some specific chemicals with copper, and hydrocupration, borocupration, and silylcupration of unsaturated substrates. It is hoped that this review can provide some clues for further exploration in this field.

8. Wen-Bin Huang, Fang-Yu Ren, Ming-Wei Wang, Li-Qi Qiu, Kai-Hong Chen and Liang-Nian He*, Cu(II)-Catalyzed Phosphonocarboxylative Cyclization Reaction of Propargylic Amines and Phosphine Oxide with CO₂, J. Org. Chem., 2020, 85(21), 14109-14120.

Abstract: Compounds bearing organophosphorus motifs and 2-oxazolidinone have found numerous applications in pharmaceutical chemistry, homogeneous catalysis, and organic materials. Here, we describe an efficient and selective protocol for straightforward access to a series of 5-((diarylphosphoryl)methyl)oxazolidin-2-ones via the copper-catalyzed difunctionalization of the C≡C bond of propargylic amines with CO₂ and phosphine oxide. Notably, copper catalysis is a sustainable and benign catalytic mode. This reaction proceeds under mild reaction conditions, which is operationally simple and scalable with a broad scope, exclusive selectivity, and good functional group compatibility. Mechanistic studies suggest a one-pot tandem cyclization/radical addition sequence, along with the phosphorylation/cyclization scheme.

9.  Xiao-Ya Li, Hong-Chen Fu, Xiao-Fang Liu, Shu-Han Yang, Kai-Hong Chen* and Liang-Nian He*, Design of Lewis base functionalized ionic liquids for the N-formylation of amines with CO₂ and hydrosilane: The cation effects. Catal. Today, 2020, 356, 563-569. [link]

Abstract: A series of functionalized ionic liquids (ILs) were developed for the reductive functionalization of CO₂ with amine and hydrosilane to afford formamides under mild conditions. It was found that 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-based IL i.e. [DBUC₁₂]Br showed high efficiency for the N-formylation reaction of amines without using any organic solvents or additives. Furthermore, control experiments suggested the cations with active hydrogen may weaken the nucleophilicity of anions through ion pairing interactions, thereby affecting the activation of hydrosilane. The reaction mechanism was then investigated by Density Functional Theory (DFT) calculations. This protocol represents a highly efficient and environmentally friendly example for catalytic conversion of CO₂ into value-added chemicals such as formamide derivatives by employing DBU functionalized ILs.

10. Wenlong Xiang, Zeyu Sun, Yurong Wu, Liang-Nian He, Chang-jun Liu*, Enhanced cycloaddition of CO₂ to epichlorohydrin over zeolitic imidazolate frameworks with mixed linkers under solventless and co-catalyst-free condition, Catal. Today, 2020, 339, 337-343. [link]

Abstract: An efficient dual-ligand zeolitic imidazolate framework ZIF-8-90 was fabricated for the synthesis of five-membered cyclic carbonate from CO₂ and epichlorohydrin (ECH) in the absence of co-catalysts and solvents. The effects of various reaction parameters were studied. The dual-ligand ZIF-8-90 showed very high selectivity (up to 99%). ZIF-8-90 exhibited better catalytic ability with lower cost than ZIF-90 and enhanced framework stability with significantly improved selectivity compared to ZIF-8. Moreover, the catalyst has been successfully reused for three cycles with negligible decrease in the catalytic activity. A plausible mechanism for the ZIF-8-90 catalyzed ECH−CO₂ cycloaddition under solvent-free and co-catalyst-free has been proposed.

11. Yu Song, Xing He, Bing Yu, Hong-Ru Li* and Liang-Nian He*, Protic ionic liquid-promoted synthesis of dimethyl carbonate from ethylene carbonate and methanol. Chin. Chem. Lett., 2020, 31(3), 667-672. [link]

Abstract: In this work, the protic ionic liquid [DBUH][Im] (1,8-diazabicyclo[5.4.0]-7-undeceniumimidazolide) was developed as an efficient catalyst for the transesterification of ethylene carbonate with methanol to produce dimethyl carbonate. At 70 °C, up to 97% conversion of ethylene carbonate and 91% yield of dimethyl carbonate were obtained with 1 mol% [DBUH][Im] (relative to ethylene carbonate) as catalyst in 2 h. Even at room temperature, the conversion of ethylene carbonate can reach 94% and the yield of dimethyl carbonate can approach 81% for 6 h. Catalytic mechanism investigation showed the high catalytic efficiency of this ionic liquid results from the synergistic activation effect, where in the cation can activate ethylene carbonate and the anion can activate methanol through hydrogen bond formation. Although the reusability of the ionic liquid need to be further improved, high efficiency and commercial availability of [DBUH][Im] render it a promising catalyst for the preparation of dimethyl carbonate.

12.  Lili Tang, Kejie Du, Bing Yu*, Liangnian He*, Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones. Chin. Chem. Lett., 2020, 31(12), 2991-2992. [link]

13.  Fei You, Xing He, Song Gao, Hong-Ru Li* and Liangnian He*, Oligomeric ricinoleic acid preparation promoted by an efficient and recoverable Brønsted acidic ionic liquid. Beilstein J. Org. Chem., 2020, 16, 351-361. [link]

Abstract: Raw material from biomass and green preparation processes are the two key features for the development of green products. As a bio-lubricant in metalworking fluids, estolides of ricinoleic acid are considered as the promising substitute to mineral oil with a favorable viscosity and viscosity index. Thus, an efficient and sustainable synthesis protocol is urgently needed to make the product really green. In this work, an environment-friendly Brønsted acidic ionic liquid (IL) 1-butanesulfonic acid diazabicyclo[5.4.0]undec-7-ene dihydrogen phosphate ([HSO₃-BDBU]H₂PO₄) was developed as the efficient catalyst for the production of oligomeric ricinoleic acid from ricinoleic acid under solvent-free conditions. The reaction parameters containing reaction temperature, vacuum degree, amount of catalyst and reaction time were optimized and it was found that the reaction under the conditions of 190 °C and 50 kPa with 15 wt % of the [HSO₃-BDBU]H₂PO₄ related to ricinoleic acid can afford a qualified product with an acid value of 51 mg KOH/g (which corresponds to the oligomerization degree of 4) after 6 h. Furthermore, the acid value of the product can be adjusted by regulating the reaction time, implying this protocol can serve as a versatile method to prepare the products with different oligomerization degree and different applications. The other merit of this protocol is the facile product separation by stratification and decantation ascribed to the immiscibility of the product and catalyst at room temperature. It is also worth mentioning that the IL catalyst can be used at least for five cycles with high catalytic activity. As a result, the protocol based on the IL catalyst, i.e. [HSO₃-BDBU]H₂PO₄ shows great potential in industrial production of oligomeric ricinoleic acid from ricinoleic acid.

14.   Liang-Nian He (Editor-in-Chief), Preface for Curr. Org. Synth., 2020, 17(1), 2. [link]

15.   陈凯宏, 李红茹, 何良年*,有机化学,2020, 40 (8), 2195-2207.  Kai-Hong Chen, Hong-Ru Li, Liang-Nian He*, Advance and Prospective on CO₂ Activation and Transformation Strategy. Chin. J. Org. Chem., 2020, 40, 2195-2207. [link]

16.   何良年, 面向可持续发展的二氧化碳化学，科学通报, 2020, 65(31), 3347-3348. [link]

17.  Changjun Li, Zhihong Xiao, Liang-Nian He, Martino Di Serio, Xinfeng Xie, Industrial Oil Plant, ISBN 978-981-15-4919-9, Nature Singapore Pte Ltd. 2020.

专利授权

王庆瑞，孟祥云，何良年，叶锋，崔晓莹，粟斌，一种氧化蓖麻油酸聚合酯制备方法。授权日期：2020.11.24，专利号：ZL201811545762.4