Biography
Academician Li Yadong is mainly engaged in the synthesis, structure, properties and application research of inorganic functional nanomaterials, and is committed to challenging metal clusters and single-atom catalysts in order to realize the replacement of noble metal catalysts by non-precious metals, explore and realize new catalytic reactions, and solve the technical problems of homogeneous catalytic heterogeneous catalyst laboratory and industrialization. Today, we will list the important research results achieved by Academician Li Yadong's team in 2023 (Note: This article only lists some of the papers with Academician Li Yadong as the corresponding author).
1Nature: CO2-mediated organocatalytic chlorine evolution under industrial conditions
Since the 19th century, the chlor-alkali process has been producing chlorine and sodium hydroxide, both of which are essential for chemical production. However, the process is so energy-intensive that 4% of global electricity production (about 150 TWh) is used in the chlor-alkali industry. As a result, increasing the efficiency of the chlor-alkali process can result in significant cost and energy savings. The chlorine evolution reaction is a critical step in the chlor-alkali process, and its state-of-the-art electrocatalyst is still a dimensionally stable anode developed decades ago. Although some novel catalysts for chlorine evolution have been reported, they are mainly composed of precious metals. The study demonstrates an organocatalyst with an amide functional group that can enable efficient chlorine evolution reactions. In the presence of carbon dioxide, the catalyst exhibits a current density of 10 kA m-2 and a selectivity of 99.6%, requiring only an overpotential of 89 mV, which is comparable to a dimensionally stable anode. The researchers found that the reversible binding of CO2 to amide nitrogen promotes the formation of free radicals, which is essential for the production of Cl2 and may play an important role in Cl-cells and organic synthesis. Although organocatalysts are often considered hopeless in demanding electrochemical applications, this study demonstrates their broader potential and the opportunities they offer for the development of new industrial-relevant processes and the exploration of new electrochemical mechanisms. This research provides new ideas for the improvement and sustainable development of chlor-alkali processes, and also provides new perspectives and opportunities for the application of organocatalysts in the field of electrochemistry.
DOI : 10.1038/s41586-023-05886-z
JACS: Upcycling of mixed plastic waste using a highly stable single-atom Ru catalyst
The work has led to a breakthrough in the use of innovative single-atom catalysts to convert mixed plastic waste into a single chemical product. The disposal of mixed plastic waste has always been a significant challenge due to its complex composition and high sorting costs. However, in this study, researchers have made a breakthrough in converting mixed plastic waste into a single chemical product for the first time using an innovative single-atom Ru catalyst. The monoatomic Ru catalyst is able to efficiently convert 90% of the actual mixed plastic waste into methane products with a selectivity of more than 99%. This is due to the unique electronic structure of the Ru site, which regulates the adsorption energy of the hybrid plastic intermediates, enabling the rapid decomposition of the hybrid plastics. In addition, single-atom catalysts have higher cycling stability compared to conventional nanocatalysts. The researchers also assessed the global warming potential of the entire process, demonstrating the environmental sustainability of the method. By proposing a carbon reduction process using a single-atom catalyst, this research has ushered in a new era of value-based hybrid plastic waste. This innovative research provides a new way to solve the problem of mixed plastic waste disposal, and is expected to promote sustainable waste management and resource recovery.
DOI : 10.1021/jacs.3c09338
JACS: a versatile bimetallic nanocrystalline dissociation strategy for the generation of robust, high-temperature, stable aluminum-supported single-atom catalysts
This work presents a study on the design of noble metal single-atom catalysts (SACs) with high heat resistance. The researchers have proposed a general strategy to use bimetallic nanocrystals (NCs) as accelerators to spontaneously convert a series of noble metals into individual atoms on the surface of alumina. In this process, the metal single atom is trapped by cationic defects on the surface of the antispinel (AB2O4) structure, providing anchor anchor sites, facilitating the generation of isolated metal atoms and providing it with extraordinary thermodynamic stability. In this way, the researchers successfully prepared a Pd1/AlCo2O4-Al2O3 catalyst that not only improved low-temperature activity, but also exhibited unprecedented (water) thermal stability to CO and propane oxidation under harsh aging conditions. In addition, by simply physically mixing a commercial metal oxide polymer with Al2O3, the researchers demonstrated a small amplification effect. These ionic palladiums have good regenerative properties between the oxidizing and reducing atmospheres, making this catalyst system potentially relevant in terms of emission control. This study provides a general strategy for the preparation of noble metal single-atom catalysts with high heat resistance and demonstrates their superiority in terms of activity and thermal stability. This discovery has potential implications for the development of more efficient catalyst systems as well as for environmental protection and emission control.
TWO : 10.1021/jacs.3c02909
4JACS: MOF-derived Ru1Zr1/Co diatomic site catalyst improves the performance of Fischer-Tropsch synthesis
This work presents a study on the design of a catalyst for Fischer-Tropsch synthesis (FTS). Cobalt-based catalysts are widely used in FTS in the industrial sector, but designing catalysts at the atomic level to achieve higher activity and more long-chain hydrocarbon products remains an attractive but difficult challenge. The researchers designed a Ru1Zr1/Co catalyst with Ru and Zr diatomic sites on the surface of cobalt nanoparticles (NPs) through a metal-organic framework-mediated synthesis strategy. This design significantly increases the activity of FTS (with a high conversion rate of 3.8 × 10-2 s-1 at 200°C) and C5+ selectivity (80.7%). Comparative experiments show that there is a synergistic effect between the Ru and Zr single-atom sites on cobalt nanoparticles. Further density functional theory calculations revealed the chain growth process from C1 to C5. The designed Ru/Zr diatomic site greatly reduces the rate-limiting obstacle by significantly weakening the C-O bond and promotes the chain growth process, thereby significantly improving the FTS performance. Therefore, this study demonstrates the effectiveness of the diatomic site design in promoting FTS performance and provides new opportunities for the development of efficient industrial catalysts. This discovery is expected to promote the further development of the FTS field and provide new methods and strategies for the synthesis of more long-chain hydrocarbon products. DOI : 10.1021/jacs.2c09168
5Angew: Continuous regulation of the electrocatalytic oxygen reduction activity of a single-atom catalyst by p-n junction rectification
This work presents a study on the fine-tuning of single-atom catalysts (SACs) beyond the limits of atomic-scale activity. The researchers took advantage of the p-type semiconductor properties of a single-atom catalyst with a metal center coordinated with a nitrogen donor (MeNx) and corrected its local charge density with an n-type semiconductor support. In the SAC modeled by ferric phthalocyanine (FePc), n-type gallium monosulfide with a low work function is introduced into the junction interface to form a space charge region, resulting in the deformation of FeN4 molecules and the spin state transition of FeII center. The oxygen reduction activity of this catalyst is more than twice as high as that of the original FePc. The researchers further used three other n-type metal chromides with different work functions as supports, and found that there was a linear relationship between the activity of the support FeN4 and the degree of rectification. This is a clear indication that SAC can be continuously adjusted with this rectification strategy. This study demonstrates a method to fine-tune the activity of a single-atom catalyst using the properties of p-type and n-type semiconductors, as well as supports for different work functions. By adjusting the local charge density and spin state transition, the researchers succeeded in increasing the specific oxygen reduction activity of the catalyst. This discovery provides a new idea and strategy for the development of more efficient SAC catalysts, and provides a feasible way to go beyond the limit of catalytic activity at the atomic scale.
DOI : 10.1002/anie.202212335
6Angew: Diatomic support promotes nickel-catalyzed electrooxidation of urea
Urea oxidation is an important electrocatalytic reaction, and nickel-based catalysts are considered to be one of the most promising electrocatalysts. However, the activity of nickel-based catalysts is largely limited by the unavoidable autooxidation of nickel species (NSOR) during urea oxidation reactions. To solve this problem, researchers propose an interfacial chemistry regulation strategy. They constructed a 2D/2D heterostructure consisting of ultra-thin NiO-anchored Ru-Co diatomic support (Ru-Co DAS/NiO) that triggered the occurrence of urea oxidation before NSOR. Spectral characterization of operating conditions confirms this unique triggering mechanism on the surface of Ru-Co DAS/NiO. The catalysts prepared by this modulation strategy exhibit excellent urea oxidation reactivity. At 10 mA cm-2, the catalyst has a low potential (1.288 V) and has a long-term durability of more than 330 hours. The results of density functional theory calculations and spectral characterization show that the favorable electronic structure induced by this unique heterogeneous interface makes the catalyst more energetically conducive to urea oxidation than NSOR. This study demonstrates an interfacial chemical modulation strategy to improve catalyst activity for urea oxidation reaction by constructing a special 2D/2D heterostructure. By triggering the occurrence of urea oxidation and inhibiting the auto-oxidation of nickel species, the prepared catalyst exhibits excellent activity and long-term durability. This discovery provides a new idea and strategy for the development of more efficient catalysts for urea oxidation reactions, and provides valuable contributions to the research in the field of electrocatalysis.
TWO : 10.1002/anie.202217449
7Adv. Mater.: High persistence of oxygen reduction reactions in alkaline media with Fe-N-C single-atom catalysts with carbon vacancies
This study proposes the application of carbon-vacancy modified single-atom catalysts (SACs) in oxygen reduction reactions (ORR). The catalytic ORR of SACs in fuel cells and metal-air batteries has attracted a lot of attention, but the development of SACs with high selectivity and long-term stability is a great challenge. In this study, carbon-vacancy-modified Fe-N-C SACs (FeH-N-C) were successfully designed and synthesized through microenvironment modulation, and the efficient utilization of active sites and the optimization of electronic structure were realized. The FeH-N-C catalyst has a half-wave potential (E1/2) of 0.91 V, a durability of 100,000 voltage cycles, and an E1/2 loss of 29 mV. Density functional theory (DFT) calculations confirm that the vacancies around the metal-N4 site reduce the adsorption free energy of OH*, hinder the dissolution of the metal center, and significantly improve the ORR kinetics and stability. As a result, FeH-N-C SAC exhibits high power density and long-term stability of more than 1200 hours in rechargeable zinc-air batteries (ZABs). The results of this study will not only guide the development of highly active and stable SACs by rational modulation of the metal-N4 site, but also provide important insights into optimizing the electronic structure to improve electrocatalytic performance. This discovery is of great significance for promoting the application of SACs in the energy field, and provides new ideas and methods for research in related fields. DOI : 10.1002/adma.202210714
8Nano Letters: Atomically strained metal bits for efficient and selective photooxidation
Strain engineering has a wide range of applications in heterogeneous catalysts. Strain engineering is an attractive strategy to improve the intrinsic catalytic performance of catalysts, but it is still challenging to manipulate the local structure of catalytic sites at the short-range atomic scale. In this study, an ingenious intercalation chemistry method was used to successfully achieve atomic strain modulation of ultra-thin layered vanadium oxide nanoribbons. By introducing trace sodium ions (Na+-V2O5) between the V2O5 layers, the V-O bond is stretched by the vanadium position of the atomic strain, redistributing the local charge. Na+-V2O5 exhibits excellent photooxidation performance, which is about 12 times and 14 times higher than that of the original V2O5 and VO2, respectively. Through complementary spectroscopic analysis and theoretical calculations, the researchers confirmed that the atomically strained Na+-V2O5 has a high surface charge density, which improves the activation ability of oxygen molecules and exhibits excellent photocatalytic performance. This study provides a new approach for the rational design of strain-type catalysts for selective photooxidation reactions. By cleverly manipulating the local structure of the catalyst, especially at the short-range atomic scale, the researchers succeeded in improving the photooxidation performance of vanadium oxide nanoribbons. This discovery is of great significance for the development of efficient photocatalysts and other strain-type catalysts, and provides new ideas and methods for research in related fields. DOI : 10.1021/acs.nanolett.3c00256
9Sci. Adv.: A key oxygen radical intermediate in which the Ir-Sn atom parasite triggers the effective oxidation of acidic water
This study mitigates anodic corrosion by constructing a heterostructured Ir-Sn atom-parasite catalyst. In this catalyst, the formation of Ir-Sn dual sites and the initiation of strong electronic interaction successfully reduce the d-band holes of Ir in the synthesis and oxygen evolution reactions, inhibit excessive oxidation, and significantly improve the corrosion resistance of the catalyst. The optimized catalyst exhibits high-quality activity at an overpotential of 320 mV, reaching 4.4 A mgIr-1, and has good long-term stability. The proton exchange membrane water electrolyzer using this catalyst has a current density of 2 A cm-2 at 1.711 V and exhibits a low degradation rate in accelerated aging tests. Theoretical calculations suggest that oxygen radicals induced by the π* interaction between Ir-5d-O-2p may be responsible for the increased activity and durability. This study proposes a new strategy to solve the problem of corrosion of catalysts in harsh acidic and oxidizing environments. By constructing a heterostructure and taking advantage of strong electronic interactions, the researchers succeeded in mitigating the dissolution and excessive oxidation of the catalyst, thereby significantly improving its corrosion resistance. This discovery is of great significance for the development of catalysts with high activity and durability, which is of great significance in the field of water electrolysis, and provides new ideas and methods for research in related fields. DOI : 10.1126/sciadv.adi8025
10Energy Environ. Sci.: Recent advances in carbon dioxide conversion with single-atom catalysts
The catalytic conversion of carbon dioxide into valuable fuels or chemicals has great prospects and economic benefits. This process can replace fossil raw materials and enable large-scale conversion and recycling of carbon dioxide. Cost-effective catalysts are important to reduce the cost of CO2 utilization, so a large number of catalyst design studies have been conducted. Traditional metal nanoparticle catalysts still need to improve the utilization efficiency, catalytic activity and selectivity of active metals. Single-atom catalysis (SACs) have attracted great interest from researchers as a promising strategy to improve catalytic efficiency and long-term stability due to their maximum atom utilization, unique electronic structure, and strong metal-support interactions. The unique design and well-structured SACs provide the necessary research advantages for revealing the underlying mechanisms and active sites in the CO2 utilization process. In this review, recent advances in advanced SACs for electrocatalysis, photocatalysis, and thermocatalysis to convert CO2 into a variety of products, such as CO, CH4, CH3OH, HCOOH, and C2+ products, are summarized and highlighted. In addition, the general principles of SAC design and the structure-performance relationship are also systematically and constructively studied, which provides a way to explore the key parameters that determine the catalytic performance. At the same time, the catalytic efficiency of different SACs for CO2 conversion was demonstrated recently published for an in-depth evaluation of these catalysts. Finally, the main challenges and future application prospects of SAC in CO2 conversion are prospected. This review provides an update on the design of catalysts for the conversion of CO2 into valuable products and highlights the potential of SACs in this area. By studying the structure and performance relationship of SACs, we can provide guidance for the development of efficient CO2 conversion catalysts and provide new ways to achieve sustainable energy and chemical production. DOI : 10.1039/D3EE00037K