论文发表

1. Li-Qi Qiu, Hong-Ru Li,* and Liang-Nian He*, Incorporating Catalytic Units into Nanomaterials: Rational Design of Multipurpose Catalysts for CO2 Valorization, Acc. Chem. Res. 2023, 56 (16), 2225-2240. [Link]

Abstract: CO2 conversion to valuable chemicals is effective at reducing CO2 emissions. We previously proposed valorization strategies and developed efficient catalysts to address thermodynamic stability and kinetic inertness issues related to CO2 conversion. Earlier, we developed molecular capture reagents and catalysts to integrate CO2 capture and conversion, i.e., in situ transformation. Based on the mechanistic understanding of CO2 capture, activation, and transformation at a molecular level, we set out to develop heterogeneous catalysts by incorporating catalytic units into nanomaterials via the immobilization of active molecular catalysts onto nanomaterials and designing nanomaterials with intrinsic catalytic sites. In thermocatalytic CO2 conversion, carbonaceous and metal−organic framework (MOF)- based catalysts were developed for nonreductive and reductive CO2 conversion. Novel Cu- and Zn-based MOFs and carbon-supported Cu catalysts were prepared and successfully applied to the cycloaddition, carboxylation, and carboxylative cyclization reactions with CO2, generating cyclic carbonates, carboxyl acids, and oxazolidinones as respective target products. Reductive conversion of CO2, especially reductive functionalization with CO2, is a promising transformation strategy to produce valuable chemicals, alleviating chemical production that relies on petrochemistry. We explored the hierarchical reductive functionalization of CO2 using organocatalysts and proposed strategies to regulate the CO2 reduction level, triggering heterogeneous catalyst investigation. Introducing multiple active sites into nanomaterials opens possibilities to develop novel CO2 transformation strategies. CO2 capture and in situ conversion were realized with an N-doped carbon-supported Zn complex and MOF materials as CO2 adsorbents and catalysts. These nanomaterial-based catalysts feature high stability and excellent efficiency and act as shape-selective catalysts in some cases due to their unique pore structure. Nanomaterial-based catalysts are also appealing candidates for photocatalytic CO2 reduction (PCO2RR) and electrocatalytic CO2 reduction (ECO2RR), so we developed a series of hybrid photo-/electrocatalysts by incorporating active metal complexes into different matrixes such as porous organic polymers (POPs), metal−organic layers (MOLs), micelles, and conducting polymers. By introducing Re-bipyridine and Fe-porphyrin complexes into POPs and regulating the structure of the polymer chain, catalyst stability and efficiency increased in PCO2RR. PCO2RR in aqueous solution was realized by designing the Re-bipyridine-containing amphiphilic polymer to form micelles in aqueous solution and act as nanoreactors. We prepared MOLs with two different metallic centers, i.e., the Ni-bipyridine site and Ni-O node, to improve the efficiency for PCO2RR due to the synergistic effect of these metal centers. Sulfylphenoxy-decorated cobalt phthalocyanine (CoPc) cross-linked polypyrrole was prepared and used as a cathode, achieving the electrocatalytic transformation of diluted CO2 benefiting from the CO2 adsorption capability of polypyrrole. We fabricated immobilized 4-(t-butyl)-phenoxy cobalt phthalocyanine and Bi-MOF as cathodes to promote the paired electrolysis of CO2 and 5-hydroxymethylfurfural (HMF) and obtained CO2 reductive products and 2,5-furandicarboxylic acid (FDCA) efficiently.

2. Liqi Qiu, Honggen Peng, Zhenzhen Yang*, Juntian Fan, Meijia Li, Shize Yang, Darren M. Driscoll, Lei Ren, Shannon M. Mahurin, Liang-Nian He*, Sheng Dai*, Revolutionazing Porous Liquids: Stabilization an Structural Engineering Achieved by A Surface Deposition strategy. Adv. Mater. 2023, 35 (32), 2302525. [Link]

Abstract: Facile approaches capable of constructing stable and structurally diverse porous liquids (PLs) that can deliver high-performance applications are a long-standing, captivating, and challenging research area that requires significant attention. Herein, a facile surface deposition strategy was demonstrated to afford diverse type III-PLs possessing ultra-stable dispersion, external structure modification, and enhanced performance in gas storage and transformation by leveraging the expeditious and uniform precipitation of selected metal salts. The Ag(I) species-modified zeolite nanosheets were deployed as the porous host to construct type III-PLs with ionic liquids (ILs) containing bromide anion as the liquid phase, leading to stable dispersion driven by the formation of AgBr nanoparticles. The as-afforded type-III PLs displayed promising performance in CO2 capture/conversion and ethylene/ethane separation. Property and performance of the as-produced PLs could be tuned by the cation structure of the ILs, which can be harnessed to achieve polarity reversal of the porous host via ionic exchange. The surface deposition procedure could be further extended to produce PLs from Ba(II)-functionalized zeolite and ILs containing [SO4]2− anion driven by the formation and coating of BaSO4 salts. The as-produced PLs were featured by well-maintained crystallinity of the porous host, good fluidity and stability, enhanced gas uptake capacity, and attractive performance in small gas melecule utilization.

3. Qing-Wen Song*, Ran Ma, Ping Liu, Kan Zhang and Liang-Nian He*, Recent progress in CO2 conversion into organic chemicals by molecular catalysis. Green Chem., 2023, 25 (17), 6538–6560. [Link]

Abstract：The chemical conversion of carbon dioxide (CO2) into high-value chemicals or fuels is exceedingly attractive due to its green and sustainable features. However, practical technologies on scale utilization of CO2 are few, and nearly no new industrial processes on the topic have emerged over the years. The current bottlenecks, e.g., low efficiency and atom economy, seriously restrict the process development. In recent studies, the catalytic activation of CO2 and/or substrate has been revealed to play a significant role in the promotion of CO2 functionalization to valuable chemicals, including the representative reactions of epoxides/propargyl alcohols/propargylamines with CO2, multicomponent cascade reactions, N-formylation of amines with CO2 and hydrosilanes, and unactivated C–H bond carboxylation. Herein, recent significant advances (2017–2022) on the effective chemical fixation of CO2 through molecular activation or synergistic activation strategies in homogeneous systems are presented. The superiority of molecular activation in thermochemical catalysis is shown in a wide range of CO2 transformations. Through CO2/substrate activation and catalysis with well-developed metal or organocatalysts, valuable chemicals are successfully attained with great efficiency. The new progress will provide significant guidance to promote the effective and sustainable utilization of CO2.

4. Wen-Jun Xie, Jin-Mei Chen, Zhi-Wen Yang, Liang-Nian He*, Cobalt Macrocyclic Complexes-Catalyzed Selective Electroreduction of CO₂ to CO. Green Chem. 2023, 25 (24), 10366-10371. [Link]

Abstract: Cobalt 5,15-diazaporphyrin, as a novel molecular catalyst onto carbon nanotubes was developed for highly efficient electrocatalytic CO₂ reduction to CO with the Faradaic efficiency reached above 99% at -0.7 V and -0.8 V versus reversible hydrogen electrode. Compared to cobalt phthalocyanine, diminution of electronegative nitrogen atoms at the meso position effectively increases the electron density of the central metal, making it easier to react with Lewis acidic CO₂.

5. Wen-Jun Xie, Olga M. Mulina,Alexander O. Terent’ev, Liang-Nian He*, Metal–Organic Frameworks for Electrocatalytic CO2 Reduction into Formic Acid. Catalysts 2023, 13 (7), 1109-1134. [Link]

Abstract: Metal–organic frameworks (MOFs) are used in catalysis due to their high specific surface area and porous structure. The dispersed active sites and limited reaction space that render MOFs have the potential for highly selective electrocatalytic CO2 reduction reaction (ECO2RR). Meanwhile, formic acid (HCOOH) is attracting attention as a liquid product with high economic benefits. This review summarizes the MOFs and their derivatives applied for ECO2RR into HCOOH products. The preparation methods of MOFs as electrocatalysts and their unique advantages are discussed. A series of MOFs and MOF derivatives obtained by electrochemical reduction or carbonization processes are highlighted, including metal nanomaterials, carbon-based nanocomposites, single-atom catalysts, and bimetallic nanocomposites. Depending on the MOF building units (metal ions and organic linkers) and the reaction conditions of derivatization, MOF-based catalysts exhibit rich diversity and controllable modulation of catalytic performance. Finally, the challenges encountered at this stage and the future research directions of MOF-based catalysts are proposed.

6. Zhi-Wen Yang, Jin-Mei Chen, Ze-Long Liang, Wen-Jun Xie, Bin Zhao, Liang-Nian He*, Anodic Product-Derived Bi-MOF as Pre-catalyst for Cathodic CO₂ Reduction: A Novel strategy for Paired Electrolysis. ChemCatChem 2023, 15 (2), e202201321. [Link]

Abstract: The paired electrolysis coupling the reduction of CO₂ to value-added molecules like HCOOH with the oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is one promising strategy of great economic and environmental benefits. Herein, a Ni(OH)₂ anode for the selective oxidation of HMF to FDCA was fabricated, revealing the significant part of the membrane in electrocatalytic procedure. With the FDCA product as a di-carboxylic acid ligand, one new bismuth-based metal-organic framework material was synthesized, which is capable of catalyzing the reduction of CO₂ to HCOOH with over 95% Faradaic efficiency (FE) and an average current density of 19.6 mA cm⁻² at −1.2 V vs. reversible hydrogen electrode (RHE). With this inner relationship, paired electrolysis was conducted with cathodic potential fixed at −1.2 V vs. RHE, producing the HCOOH with 95.6% FE and FDCA with 75% FE in one single electrolyzer.

7. Olga M. Mulina, Mikhail M. Doronin, Liang-Nian He, Alexander O. Terent'ev, Disulfides as Versatile Starting Reagents: Effective Sulfonylation of Alkenes with Disulfides under Electrochemical Conditions. Org. Chem. Front. 2023, 10 (14), 3559-3566. [Link]

Abstract: Electrochemically induced sulfonylation of alkenes with disulfides as the starting reagents is developed. This transformation is a quite rare example of disulfides usage as S-partners in electrochemical C–S coupling. In many cases, disulfides are inert in electrochemical coupling, and their formation in reactions starting from thiols (their synthetic precursors) is a dead-end pathway. In the discovered process, vinyl sulfones are formed exclusively, which is surprising. Previously, in reactions involving disulfides, only sulfenylation took place, resulting in sulfides, which could be transformed into the corresponding sulfones only through oxygenation with mCBPA or other similar oxygen donors. The developed reaction is carried out under constant current conditions in an experimentally convenient undivided electrochemical cell equipped with a platinum anode and a stainless-steel cathode. KI acts in this process as a supporting electrolyte and redox catalyst, which enables the formation of sulfonylating species from the starting disulfides. Taking into account the results of control experiments, a CV study, and literature data, we propose that both radical and ionic pathways could be involved in the formation of the desired products.

8. Li-Qi Qiu, Xiang-yang Yao, Yong-Kang Zhang, Hong-Ru Li*, Liang-Nian He*, Advancements and Challenges in Reductive Conversion of Carbon Dioxide via Thermo-/Photocatalysis . J. Org. Chem. 2023, 88 (8), 4942–4964. [Link]

Abstract: Carbon dioxide (CO2) is the major greenhouse gas and also an abundant and renewable carbon resource. Therefore, its chemical conversion and utilization are of great attraction for sustainable development. Especially, reductive conversion of CO2 with energy input has become a current hotspot due to its ability to access fuels and various important chemicals. Nowadays, the controllable CO2 hydrogenation to formic acid and alcohols using sustainable H2 resources has been regarded as an appealing solution to hydrogen storage and CO2 accumulation. In addition, photocatalytic CO2 reduction to CO also provides a potential way to utilize this greenhouse gas efficiently. Besides direct CO2 hydrogenation, CO2 reductive functionalization integrates CO2 reduction with subsequent C–X (X = N, S, C, O) bond formation and indirect transformation strategies, enlarging the diverse products derived from CO2 and promoting CO2 reductive conversion into a new stage. In this Perspective, the progress and challenges of CO2 reductive conversion, including hydrogenation, reductive functionalization, photocatalytic reduction, and photocatalytic reductive functionalization are summarized and discussed along with the key issues and future trends/directions in this field. We hope this Perspective can evoke intense interest and inspire much innovation in the promise of CO2 valorization.

9. Heng Li, Fang-Yu Ren, Hong-Ru Li*, Liang-Nian He*, Modification of ricinoleic acid based nonisocyanate polyurethane using polyamine containing polyhedral oligomeric silsesquioxane. Polym. Eng. Sci. 2023, 63 (5), 1507-1515.  [link]

Abstract: Biomass-based polymers and their property regulation using functional materials have attracted much interest. In this work, ricinoleic acid-derived cyclic carbonate was prepared and applied to the synthesis of nonisocyanate polyurethane (NIPU) with aliphatic diamine, in which octa(aminopropyl) polyhedral oligomeric silsesquioxane (OAP-POSS) was incorporated as polyamine to partially or totally substitutes for the diamine to introduce POSS units into the polymer thus regulating the properties of the resultant material. In the curing process, Fourier transform infrared spectroscopy (FT-IR) was used to track the reaction and curing at 50°C for 12 h was found to be sufficient for the polymerization. A series of POSS modified NIPUs were obtained by altering the molar fraction of OAP-POSS in total amine components and the material with the highest thermal stability, shore hardness and water resistance was accessed with 100% substitution of OAP-POSS for diamine.

专利申请和授权

1. 李恒，李红茹，何良年，一种新型蓖麻基非异氰酸酯聚氨酯的制备方法，申请号：2023101742934

2. 魏梦歌，李红茹，何良年, 一种基于新型固体碱催化剂催化合成碳酸二甲酯的方法，申请号：2023117989458