Regulating the electronic structure of dual active site Co/MoOx-cCNT for catalyzing NaBH4 hydrolysis towards controllable high-capacity hydrogen production

IF 13.3 1区 工程技术 Q1 ENGINEERING, CHEMICAL
Wei Zhao, Zhao Zhang, Zhenji Li, Yongjia Zhang, Chao Wang, Lang Han, Jun Guo, Xiangming Hu, Chong Peng, Seeram Ramakrishna, Li Guo
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Abstract

Hydrolysis of solid NaBH4 is a prospective technique towards on-site hydrogen requirements. The hydrogen generation efficiency, controllability, and stability of hydrolysis process plays a fundamental role for its practical orientation. In this article, we report the manipulation of dual-active-site Co/MoOx-cCNT catalysts with regulated electronic structure and explore its potential for boosting large-scale H2 production through hydrolysis of solid NaBH4 for the first time. A combination of DFT calculations and systematic characterizations with kinetic isotopic analysis reveal that the outstanding catalytic performance is attributed to the dual-active-site of Co and MoOx, which enabled the co-activation of NaBH4 and H2O. The incorporation of cCNT provides a fast conduction channel, which accelerates the electron conduction at the microscopic level and enriches the electron density on the active site surface. The hydrogen generation rate of optimal Co/5MoOx-cCNT catalyst exhibits an exceptional high HGR value of 8795.4 ml min−1 gcat-1 with an activation energy as low as 11.7 kJ mol−1. Furthermore, the studied catalyst can endure a water-limited environment without catalytic decay and reduce the heat accumulation during hydrolysis, which is attributed to the presence of cCNT, significantly accelerating the mass and heat transfer between multiphase interface of reactants. In the following long-duration hydrogen production test, an average hydrogen supply rate of 5.7 SLPM over 213 min, which is the highest level achieved by a single reactor based on the available international literature. The system archives the GHSC and VHSC as high as 5.7 wt% and 70 g/L, respectively, meeting the US DOE targets for 2025. Our study provides a comprehensive exploration of the catalytic NaBH4 hydrolysis mechanism and its potential for practical application. The strategy demonstrated here could shed a new light on the mitigation of issues such as poor stability and controllability of hydrolysis in solid state, marking a substantial stride toward industrializing NaBH4 hydrolysis.
调控双活性位点Co/MoOx-cCNT的电子结构,催化NaBH4水解实现可控大容量制氢
固体NaBH4的水解是一种有前景的现场氢需求技术。水解过程的产氢效率、可控性和稳定性对其实用方向起着至关重要的作用。在本文中,我们报道了调控电子结构的双活性位点Co/MoOx-cCNT催化剂的操作,并首次探索了其通过水解固体NaBH4促进大规模制氢的潜力。DFT计算、系统表征和动力学同位素分析表明,Co和MoOx的双活性位点使得NaBH4和H2O能够共活化,从而获得了优异的催化性能。cCNT的掺入提供了一个快速的传导通道,加速了微观层面的电子传导,丰富了活性位点表面的电子密度。优化后的Co/5MoOx-cCNT催化剂产氢率达到8795.4 ml min−1 gcat-1gcat-1,活化能低至11.7 kJ mol−1。此外,由于cCNT的存在,所研究的催化剂可以耐受限水环境而不发生催化衰变,并且减少了水解过程中的热量积累,显著加快了反应物多相界面之间的质量和热量传递。在接下来的长时间制氢试验中,平均供氢速率为5.7 SLPM / 213 min,这是根据现有国际文献得出的单反应堆最高水平。该系统记录的GHSC和VHSC分别高达5.7 wt%和70 g/L,达到了美国能源部2025年的目标。本研究对催化NaBH4水解机理及其实际应用潜力进行了全面探索。本文所展示的策略可以为缓解固态水解稳定性和可控性差等问题提供新的思路,标志着NaBH4水解工业化迈出了实质性的一步。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemical Engineering Journal
Chemical Engineering Journal 工程技术-工程:化工
CiteScore
21.70
自引率
9.30%
发文量
6781
审稿时长
2.4 months
期刊介绍: The Chemical Engineering Journal is an international research journal that invites contributions of original and novel fundamental research. It aims to provide an international platform for presenting original fundamental research, interpretative reviews, and discussions on new developments in chemical engineering. The journal welcomes papers that describe novel theory and its practical application, as well as those that demonstrate the transfer of techniques from other disciplines. It also welcomes reports on carefully conducted experimental work that is soundly interpreted. The main focus of the journal is on original and rigorous research results that have broad significance. The Catalysis section within the Chemical Engineering Journal focuses specifically on Experimental and Theoretical studies in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. These studies have industrial impact on various sectors such as chemicals, energy, materials, foods, healthcare, and environmental protection.
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