UST High Sensitivity/Nanjing Technology Lans Nature Catalysis: "Disorder is better than order" metal glass fuel cell anode catalyst
[Article information]
"Disorder is better than order" metal glass fuel cell anode catalyst
First author: Gao Feiyue, Liu Sinan, Ge Jiacheng, Zhang Xiaolong, Zhu Li
Corresponding author: Gao Minrui*, Lansi*
Unit: University of Science and Technology of China, Nanjing University of Science and Technology
[Research background]
Hydrogen oxyfuel cell will play an important role in the future energy structure due to its advantages of higher energy and green pollution-free. The dependence of proton exchange membrane fuel cells on platinum group catalysts leads to excessive system costs. In contrast, the alkaline environment of alkaline membrane fuel cells makes it possible to use non-precious metal electrocatalysts and can reduce the cost of battery separators, bipolar plates and other components, which is expected to gain market advantages. However, at the hydrogen oxidation reaction (HOR) end of the alkaline membrane fuel cell anode, the reaction kinetic rate of the catalyst is about two orders of magnitude lower than under acidic conditions; at the same time, the current stability window of nickel-based catalysts is less than 0.3 V, facing the problem of oxidative inactivation. Therefore, designing and creating new anode catalysts with high activity and high oxidation resistance is a challenge that needs to be solved in the practical use of alkaline membrane fuel cells.
[Article Introduction]
Recently, Professor Gao Minrui's team from the University of Science and Technology of China and Professor Lansi of Nanjing University of Technology jointly designed and developed a ternary nickel-molybdenum-niobium metal glass structure catalyst for the anode hydroxide reaction of alkaline membrane fuel cell, greatly increasing the oxidation resistance potential of the nickel-based catalyst to a level similar to 0.8 V, and achieving a catalytic activity comparable to platinum. The relevant results of were published online on October 27, 2022 in the internationally renowned academic journal "Nature Catalysis" (Nature Catalysis) .
[Key points of this article]
Key points one: Amorphous metal glass structure realizes HOR high oxidation resistance window
Professor Gao Minrui's team worked with Professor Lansi of Nanjing University of Science and Technology to design and create a ternary nickel-molybdenum-niobium metal glass structure catalyst for the anode hydroxide reaction of alkaline membrane fuel cell, greatly increasing the oxidation resistance potential of the nickel-based catalyst to a level similar to 0.8 VRHE similar to platinum, and achieving catalytic activity comparable to platinum. The researchers used the rapid cooling process of melt spinning to effectively inhibit the metal crystallization process and successfully prepared a series of amorphous metallic glass structure catalysts (Figure 1). Electrochemical analysis of different samples found that the Ni52Mo13Nb35 metal glass catalyst can reach an ultra-high oxidation resistance potential of 0.8 VRHE, which is the highest value of non-precious metal catalysts at present; at the same time, the catalyst exhibits catalytic activity comparable to Pt. On the other hand, this new metal glass structure has good anti-CO toxicity properties. Experimental results show that even if 2% CO gas is added to the hydrogen fuel, the Ni52Mo13Nb35 catalyst still exhibits high HOR catalytic activity, while the Pt catalyst is completely inactivated (Fig. 2).
Figure 1. Preparation and characterization of NiMoNb metallic glass strips.
Figure 2. Analysis and comparison of electrochemical activity of NiMoNb metal glass strips of different components.
Point 2: The unique atomic structure and intermediate adsorption energy of amorphous metallic glass catalysts
High-energy synchronous radiation test results show that the atomic-scale cluster connectivity mode provides important guarantees for the stability and high activity of amorphous structures.The point connection and line connection mode that occupy a larger proportion between short-program clusters make Ni52Mo13Nb35 metal glass have richer reaction sites on the atomic scale. The molecular dynamics simulation and first-principle calculation results also show that Ni52Mo13Nb35 metal glass has more optimized intermediate adsorption energy (Figure 3). The above analysis results theoretically give the source of excellent HOR catalytic activity of Ni52Mo13Nb35 metal glass.
Figure 3. Comparison of cluster connectivity of NiMoNb metal glass strips of different components and their effects on electrochemical activity.
Key points 3: In-situ spectrometry technology explores the oxidation resistance of metal glass catalysts
electrochemical stability test results show that under room temperature, Ni52Mo13Nb35 metal glass catalyst operates continuously at a potential of 0.8 VRHE for 18 hours, and its current attenuation is almost negligible. At the same time, the catalyst also exhibits excellent stability at a higher operating temperature (45 °C). Elemental analysis results show that after the reaction of Ni52Mo13Nb35 catalyst for more than 17 hours, there was no obvious sign of active elements (Ni and Nb) precipitation, while only a small amount of Mo elements precipitated (5%). In contrast, the crystalline Ni52Mo13Nb35 alloy showed severe loss of Mo element (about 11%) after 5 hours of stability testing. The results of in situ Raman spectroscopy also show that compared with crystalline catalysts, the surface of metallic glass structures is not easy to form oxidized species (Figure 4). Researchers speculate that during the synthesis of metal glass, rapid cooling makes the metal glass have good chemical uniformity and lacks crystal defects that are prone to local corrosion. These two reasons work together to achieve excellent stability of the Ni52Mo13Nb35 metal glass catalyst under high oxidation potential.
Figure 4. Research on the stability evaluation and spectral mechanism of Ni52Mo13Nb35 metal glass.
Key points 4: Performance test in actual fuel cells
Go further, the researchers ground Ni52Mo13Nb35 metal glass strips into powder through mechanical ball milling method to test the performance of the new catalyst in membrane electrode assembly. The study found that the optimized hydroxide fuel cell can obtain a current density of 338 mA cm-2 and a peak power density of 390 mW cm-2 at a voltage of 0.65 V. In hydrogen-air fuel cells, the catalyst also performs outstandingly: it can provide a current density of 201 mA cm-2 and a maximum power density of 253 mW cm-2 at 0.65 V, representing the highest performance of current non-precious metal alkaline membrane fuel cells.
The corresponding authors of this paper are Professor Gao Minrui and Lansi; the first authors are Gao Feiyue, Liu Sinan, Ge Jiacheng, Zhang Xiaolong, and Zhu Li. The collaborators of this work also include Academician Yu Shuhong of the University of Science and Technology of China and Academician Yan Yushan of the University of Delaware in the United States. At the same time, Professor Chen Shengli of Wuhan University gave a lot of useful discussions on this work. Related research is funded by projects such as the National Natural Science Foundation of China, the National Key R&D Program, and the Anhui Province Key Research and Development Program.
paper link:
https://www.nature.com/articles/s 41929-022-00862-8
High-sharp/Professor Lansi Introduction:
High-sharp , professor at the University of Science and Technology of China, and winner of the National Outstanding Youth Fund. In 2012, he received his Ph.D. from the University of Science and Technology of China and studied under Academician Yu Shuhong. From 2012 to 2016, he has successively conducted postdoctoral research at the University of Delaware, Argonne National Laboratory and the Institute of Colloid and Interface of the Max Planck Association of Germany. Selected in the National High-Level Talent Program Youth Project (Excellent Final Assessment) and Elsevier's China Highly Cited Scholars List (Chemistry).
research direction is based on the controllable synthesis and optimization of inorganic nanomaterial structures to achieve efficient and cheap storage and conversion of sustainable electricity in clean hydrogen and high value-added fuel molecules.In the past five years, more than 30 corresponding author papers have been published, including such as Nat. Catal. (1), Nat. Commun. (7), Angew. Chem. (8), JACS (5), EES (3), and Adv. Mater. (2). He has won the Youth Teacher Career Award from the Overseas Alumni Foundation of China University of Science and Technology (2021), Energy & Fuels Rising Star (2021), China's New Science and Technology Figures (2020), RSC JMCA emerging investigator (2020), Hong Kong Qiushi Foundation's "Outstanding Young Scholar Award" (2018), Chinese Academy of Sciences Outstanding Doctoral Thesis (2014), Chinese Academy of Sciences Special Award (2012) and other awards. Currently serving as a director of the China Youth Science and Technology Workers Association (2020).
Lansi , professor, doctoral supervisor, vice president, national youth, national key R&D program young scientist, Jiangsu Province outstanding youth. He serves as a member of the Amorphous Alloy Branch of the Chinese Metal Society, a member of the Jiangsu Materials Society and Physics Society, a member of the MRS, TMS and Hong Kong Physics Association, a member of the China Spallation Neutron Source Science and Technology Committee and User Committee, an expert on the Japanese Neutron Source J-PARC letter evaluation, a member of the VEBLEO of the International Scientific Organization, and a young editor of international journals such as MRL, Rare Metals (Chinese and English), and Journal of Metals. He won the third prize of the top ten new scientific and technological figures in China in 2021 and the 2021 Jiangsu Higher Education Institutions Science and Technology Research Achievements.
Professor Lans has long been committed to research on the fields related to the structure and phase transformation mechanism of amorphous alloys, and has published papers in international authoritative journals such as Nature Materials, Nature Catalysis, Nature Communications, Acta Materialia, Physical Review Letters, Nano Letters, etc. Recently, the intermediate-order ordered structural primitives that can bridge amorphous and crystalline matter have been observed and deciphered by experimental means, and contributed to solving the problem of the nature of amorphous structure. Related work has been reported by the National Foundation of China's homepage news many times.
