Article
Chemistry, Physical
Li Ji, Tianhua Cui, Xufeng Nie, Yanling Zheng, Xueli Zheng, Haiyan Fu, Maolin Yuan, Hua Chen, Jiaqi Xu, Ruixiang Li
Summary: Unsymmetric Ru-CNP and Ru-CN(H)P complexes were synthesized and applied in the hydrogenation of CO2 to formate, showing excellent stability and high activity. The TON reached around 170,000 after 48 hours at 200 degrees C, which is a relatively high record value among all the Ru complexes.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Xin Liu, Thomas Werner
Summary: A manganese pincer complex is reported as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes, leading to the corresponding alcohols, amines, and methanol. This method represents an approach to the indirect reduction of CO2 and shows the first examples of reduction of carbamates and urea derivatives as well as C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is demonstrated by successful reduction of various compounds with good to excellent yields.
Article
Chemistry, Physical
Abhishek Kumar, Ritu Bhardwaj, Sanajit Kumar Mandal, Joyanta Choudhury
Summary: Progress has been made in the application of transfer hydrogenation strategy for CO2 reduction in the past decade. The use of biomass-derived alcohols as hydride donors shows promise in replacing traditional hydrogenation process. However, finding efficient and stable homogeneous catalysts under harsh reaction conditions remains a challenge.
Article
Chemistry, Physical
Alex S. Tossaint, Christophe Rebreyend, Vivek Sinha, Manuela Weber, Stefano Canossa, Evgeny A. Pidko, Georgy A. Filonenko
Summary: Activation is crucial for the efficient operation of homogeneous catalysts. Most pincer catalysts rely on metal ligand cooperative chemistry for activation, but we report an exception here. We demonstrate that a Ru-(PNP)-P-3 aminopyridine pincer catalyst can show hydrogen activation through a sequential two-step activation, which is critical for CO2 hydrogenation catalysts.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Editorial Material
Chemistry, Multidisciplinary
Joakim B. Jakobsen, Magnus H. Ronne, Kim Daasbjerg, Troels Skrydstrup
Summary: The reduction of carbon dioxide is crucial for producing non-fossil-fuel-based feedstocks and mitigating greenhouse gas emissions. Amines play a critical role in these transformations, acting as CO2 trapping agents, proton shuttles, electron donors, and facilitators of CO2 reductions through formamide derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Chandan Das, Jagrit Grover, Tannu, Ayon Das, Debabrata Maiti, Arnab Dutta, Goutam Kumar Lahiri
Summary: This article discusses the frontier research and potential future directions of CO2 hydrogenation to methanol and formic acid using transition metal complexes as catalysts.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Zhaofu Zhang, Shuaishuai Liu, Minqiang Hou, Guangying Yang, Buxing Han
Summary: This study presents a method for continuous-flow formic acid production via the hydrogenation of carbon dioxide, using water as the solvent without any base, and obtaining a 2.5 mol/L formic acid aqueous solution. The TON of the reaction can reach 35,000.
Article
Chemistry, Physical
Ziliang Yuan, Guanghui Wang, Xun Li, Yurong He, Pan Wang, Francesco Mauriello, Zehui Zhang
Summary: Ni nanoparticle catalysts supported on Vulcan carbon (VCX) were prepared and used for the acceptorless dehydrogenation of primary amines to secondary amines. The best performance was achieved with Ni(A)/VXC with Ni particle size of 11.9 nm at 150 degrees C. This work provides inspiration for further investigation into acceptorless dehydrogenation using non-noble metal catalysts.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Jiehong He, Shaoshuai Chang, Haoran Du, Bo Jiang, Wenzhao Yu, Zhenwu Wang, Weiwei Chu, Lanfang Han, Jian Zhu, Hexing Li
Summary: This study introduces a reliable amorphous NiRu0.1B catalyst with high catalytic activity for the hydrogenation of CO2 into formic acid. The synergistic effect of amorphous structure and electron donation allows this catalyst to exhibit higher activity and stability at low temperatures compared to other catalysts.
JOURNAL OF CO2 UTILIZATION
(2021)
Article
Energy & Fuels
Baicheng Feng, Zichen Zhang, Jiaqiang Wang, Donglin Yang, Qun Li, Yaping Liu, Hengjun Gai, Tingting Huang, Hongbing Song
Summary: In this study, two novel hydrophobic poly(ionic liquid)s were designed to catalyze the activation of CO2, and the synergistic effect of NEt3 was utilized to efficiently produce formic acid under mild conditions.
Article
Chemistry, Organic
James D. Grayson, Francesca M. Dennis, Craig C. Robertson, Benjamin M. Partridge
Summary: In this study, a Chan-Lam coupling reaction of benzylic and allylic boronic esters with primary and secondary anilines was reported to form valuable alkyl amine products. Both secondary and tertiary boronic esters were used as coupling partners, resulting in selective mono-alkylation of the aniline. This rare example demonstrated a transition-metal-mediated transformation of a tertiary alkylboron reagent, with initial investigation suggesting a single-electron transmetalation mechanism from B to Cu.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xin Liu, Wen-Zhe Dong, Yang Li, Xiaoqiang Yu, Wan-Hui Wang, Yuichiro Himeda, Ming Bao
Summary: In this study, an efficient and selective strategy for the synthesis of α-substituted ketones via borrowing hydrogen was reported. β-Alkylation of secondary alcohols to α-substituted ketones was catalyzed by an amidato Ir(III) complex in water. The method showed high yields and good tolerance to various substrates.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Luca Piccirilli, Brenda Rabell, Rosa Padilla, Anders Riisager, Shoubhik Das, Martin Nielsen
Summary: High catalytic activities were achieved by using Ru-PNP complexes in ionic liquids for the reversible hydrogenation of CO2 and dehydrogenation of formic acid (FA) under mild conditions without sacrificial additives. The Ru-PNP/IL system showed high conversion rates and space-time yield (STY) for FA, with the potential to be used as a FA/CO2 battery, H2 releaser, and hydrogenative CO2 converter.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Caterina Damiano, Paolo Sonzini, Gabriele Manca, Emma Gallo
Summary: The TPPH2/TBACl binary catalytic system efficiently promotes the cycloaddition of CO2 to N-alkyl aziridines, resulting in the synthesis of N-alkyl oxazolidin-2-ones with high yields and excellent regioselectivity. The proposed mechanism suggests the formation of an adduct between TPPH2 and TBACl as the active catalytic species.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Tsuyoshi Yamada, Kwihwan Park, Chikara Furugen, Jing Jiang, Eisho Shimizu, Naoya Ito, Hironao Sajiki
Summary: The research has developed flow reaction methods to selectively synthesize tertiary, secondary, and primary amines from nitriles using heterogeneous platinum-group metal catalysts under catalytic hydrogenation conditions. By controlling the metal catalyst and flow parameters, a wide variety of aliphatic and aromatic nitriles can be highly selectively transformed into the corresponding amines. The continuous-flow methodologies can be applied for at least 72 hours to produce three different types of amines in high yields without decreasing catalytic activities.
Article
Chemistry, Organic
Wen-Bin Huang, Meng Yang, Liang-Nian He
Summary: In this study, a selective method for the synthesis of N-alkylated indole products was developed via hydroxymethylation using formic acid. This metal-free process under mild conditions, using an organic base as the catalyst, represents an alternative strategy for the indirect utilization of CO2. This method has significant practical value.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Zhi-Wen Yang, Jin-Mei Chen, Ze-Long Liang, Wen-Jun Xie, Bin Zhao, Liang-Nian He
Summary: This study presents a paired electrolysis strategy for reducing CO2 to HCOOH and oxidizing HMF to FDCA, which has great economic and environmental benefits. A Ni(OH)(2) anode was fabricated, showing the significant role of the membrane in the electrocatalytic process. A novel bismuth-based metal-organic framework material was synthesized, which effectively catalyzed the reduction of CO2 to HCOOH. By fixing the cathodic potential, high FE of HCOOH and FDCA can be simultaneously produced in a single electrolyzer.
Article
Chemistry, Organic
Li-Qi Qiu, Xiangyang Yao, Yong-Kang Zhang, Hong-Ru Li, Liang-Nian He
Summary: Chemical conversion and utilization of CO2 are crucial for sustainable development. Reductive conversion and photocatalytic reduction provide effective methods for utilizing CO2. Indirect transformation strategies and CO2 reductive functionalization can enhance the diverse products derived from CO2 and promote CO2 reductive conversion into a new stage.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Energy & Fuels
Heng Li, Song Gao, Wei-Hang Xie, Liang-Nian He, Hong-Ru Li
Summary: A magnetic catalyst (Fe3O4@SiO2-IM-SO3H) was developed for the efficient synthesis of polyol ricinoleates via esterification. The catalyst showed good magnetic properties and sulfonic groups, which promoted the esterification reaction and facilitated catalyst separation. The polyol ricinoleates yield reached 99.5% and the catalyst could be recycled for multiple times without significant reduction in activity, demonstrating its potential for sustainable and green product development.
BIOMASS CONVERSION AND BIOREFINERY
(2023)
Article
Engineering, Chemical
Heng Li, Fang-Yu Ren, Hong-Ru Li, Liang-Nian He
Summary: Biomass-based polymers have attracted significant attention due to their ability to be regulated using functional materials. This study focused on the synthesis of nonisocyanate polyurethane (NIPU) using ricinoleic acid-derived cyclic carbonate and aliphatic diamine, with the incorporation of octa(aminopropyl) polyhedral oligomeric silsesquioxane (OAP-POSS) as a poly-amine for introducing POSS units and regulating the properties of the material. The curing process was monitored using Fourier transform infrared spectroscopy, and it was found that a curing time of 12 hours at 50 degrees Celsius was sufficient for polymerization. Different NIPUs modified with various molar fractions of OAP-POSS were obtained, and the material with 100% substitution of OAP-POSS for diamine showed the highest thermal stability, shore hardness, and water resistance.
POLYMER ENGINEERING AND SCIENCE
(2023)
Review
Chemistry, Multidisciplinary
Li-Qi Qiu, Hong-Ru Li, Liang-Nian He
Summary: CO2 conversion to valuable chemicals is an effective way to reduce CO2 emissions. We developed carbonaceous and metal-organic framework (MOF)-based catalysts for nonreductive and reductive CO2 conversion, and explored novel strategies for CO2 capture and in situ transformation. Nanomaterial-based catalysts show high stability and efficiency, and are also promising in photocatalytic CO2 reduction and electrocatalytic CO2 reduction.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Review
Chemistry, Physical
Wen-Jun Xie, Olga M. Mulina, Alexander O. Terent'ev, Liang-Nian He
Summary: Metal-organic frameworks (MOFs) are used for catalysis due to their high surface area and porous structure. They show potential for selective electrocatalytic CO2 reduction reaction (ECO2RR) into formic acid (HCOOH). This review discusses the preparation methods of MOFs as electrocatalysts and their advantages. Various MOFs and their derivatives, including metal nanomaterials, carbon-based nanocomposites, single-atom catalysts, and bimetallic nanocomposites, are highlighted. The diversity and controllable modulation of catalytic performance of MOF-based catalysts are dependent on the building units and reaction conditions. Challenges and future research directions of MOF-based catalysts are proposed.
Review
Chemistry, Multidisciplinary
Qing-Wen Song, Ran Ma, Ping Liu, Kan Zhang, Liang-Nian He
Summary: The chemical conversion of CO2 into valuable chemicals or fuels is highly attractive for its green and sustainable features. However, practical technologies for CO2 utilization are limited, and there have been no significant industrial developments in this area. Recent studies have shown that catalytic activation of CO2 and/or substrates plays a significant role in promoting CO2 functionalization. Advances in molecular activation and synergistic activation strategies have led to the successful production of valuable chemicals with high efficiency.
Article
Chemistry, Organic
Olga M. Mulina, Mikhail M. Doronin, Liang-Nian He, Alexander O. Terent'ev
Summary: Electrochemical sulfonylation of alkenes using disulfides as starting reagents is demonstrated. This reaction is a rare example of disulfides as S-partners in electrochemical C-S coupling reactions. Previously, only sulfenylation reactions occurred with disulfides, leading to sulfides that required further oxidation to form sulfones. In this newly discovered process, vinyl sulfones are selectively formed. The reaction is carried out in an undivided electrochemical cell with a platinum anode and stainless-steel cathode under constant current conditions using KI as a supporting electrolyte and redox catalyst. Both radical and ionic pathways are proposed to be involved in the formation of the desired products based on control experiments, CV study, and literature data.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Wen-Jun Xie, Jin-Mei Chen, Zhi-Wen Yang, Liang-Nian He
Summary: A novel molecular catalyst, cobalt 5,15-diazaporphyrin, was developed and immobilized onto carbon nanotubes for highly efficient electrocatalytic CO2 reduction to CO. The catalyst exhibited a faradaic efficiency above 99% at -0.7 V and -0.8 V versus a reversible hydrogen electrode. The decrease in electronegative nitrogen atoms at the meso position effectively increased the electron density of the central metal, facilitating the reaction with Lewis acid CO2.
Article
Chemistry, Multidisciplinary
Jin-Mei Chen, Wen-Jun Xie, Zhi-Wen Yang, Liang-Nian He
Summary: In this study, molecular engineering of copper phthalocyanines (CuPc) was carried out to modify the electron-withdrawing groups (EWGs) and electron-donating groups (EDGs). PPy-coated CuPc catalysts were prepared and found to effectively catalyze the electrochemical reduction of CO2 to methane. The introduction of EWGs significantly improved the selectivity towards methane, while modification with EDGs reduced the selectivity. This research provides a facile and effective molecular engineering approach for the preparation of electrocatalysts for CO2 reduction.
Article
Chemistry, Physical
Zhi-Wen Yang, Jin-Mei Chen, Li-Qi Qiu, Wen-Jun Xie, Liang-Nian He
Summary: A paired electrolytic system was constructed for the catalytic reduction of CO2 to CO and the oxidation of HMF to FDCA. Coupled electrolysis experiments and a sunlight-driven system demonstrated efficient coupling reactions, providing a new direction for the production of high value-added chemicals using renewable energy sources.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Shumei Xia, Dawei Cao, Huiying Zeng, Liang-Nian He, Chao-Jun Li
Summary: In this study, we report an earth abundant nickel-catalyzed alkenylation of naturally abundant methylene ketones to efficiently synthesize a wide range of alkene derivatives. The protocol offers a broad substrate scope, good functional group compatibility, mild reaction conditions, water tolerance, and produces only environmentally friendly theoretical byproducts N-2, H-2, and H2O. Additionally, gram-scale synthesis with high yield and generation of pharmaceutical intermediates highlight its practical applicability.
Article
Chemistry, Multidisciplinary
Shuai-Fang Cai, Li-Qi Qiu, Wen-Bin Huang, Hong-Ru Li, Liang-Nian He
Summary: A palladium-catalyzed four-component carboxylative cyclization was developed to synthesize functionalized 2-oxazolones. This method provides a cooperative transformation route for both CO2 and CO.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xing He, Xiangyang Yao, Shuai-Fang Cai, Hong-Ru Li, Liang-Nian He
Summary: Photocatalytic synthesis is an efficient method for transforming CO2 into functionalized organic carbamates. In this study, a catalyst-free carbamoyloxylation reaction was developed to synthesize O-beta-oxoalkyl carbamates from arylacetones using CO2 and amines under visible light. The reaction proceeded smoothly with the assistance of inexpensive carbon tetrabromide and achieved high yields, while simultaneously constructing C-O and C-N bonds. Mechanistic studies indicated that the reaction pathway involves photoinduced hydrogen atom transfer (HAT) followed by radical addition or single electron transfer (SET).
CHEMICAL COMMUNICATIONS
(2022)