Advanced Hierarchically 2D and 3D Nanostructured Materials for Electrochemical Clean Energy Conversion
The effective utilization of clean energy and finding alternatives to fossil resources are highly important to ensure the sustainability of human society and are always among the major goals of both chemistry and material science research. Advanced electrochemical devices, such as fuel cells, water electrolysers and metal-air batteries, represent the most promising strategies for clean-energy utilization. In an electrochemical device, the redox reactions are spatially separated by a membrane, allowing direct extraction/transfer of electrons at an electrode-electrolyte interface, which leads to higher intrinsic energy conversion efficiencies, milder process conditions, easy product separation and excellent design features for coupling to renewable energy infrastructure. The performance of such electrochemical processes is fundamentally determined by the physicochemical properties of the electrochemical interfaces, encompassing both the electrocatalyst and the structure of the adjacent electrochemical double layer. Specifically, electrocatalysts play key roles in electrochemical reactions and often limit the performance of entire systems due to their insufficient activity, low durability or high cost. Ideally, the rate, efficiency, and selectivity of the above electrochemical reactions can be substantially improved by developing high-performance electrocatalyst. One of the central tasks for chemists and material scientists is to design and fabricate the high-efficient efficiency but low-cost electrocatalysts systems. The current promising electrochemical reactions mainly focus on the realization of the reversible conversion between chemical and electricity energy, e.g., the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen oxidation reaction (HOR), and hydrogen evolution reaction (HER). Coupling of the above electrochemical reactions provide a solid foundation for various essential electrochemical devices, such as direct hydrogen fuel cells (HOR + ORR); electrolysers (OER + HER); rechargeable zinc (Zn)-air battery (ORR + OER). Therefore, this thesis aims to design and synthesize high-performance electrocatalysts for HER, ORR and OER based on earth-abundant materials with proper hierarchical 2D or 3D nanostructures. Combined with the advanced characterization techniques and density functional theory (DFT) calculations, the relationship between the electrochemical activity and active sites of these earth-abundant electrocatalysts were detailedly explored and confirmed. Furthermore, to emphasize the hierarchical 2D or 3D nanostructures, the actual performance of these electrocatalysts was all evaluated in practical devices including Zn-air battery and proton exchange membrane fuel cell (PEMFC), specifically as follows: (1) The vast majority of the reported HER electrocatalysts performs poorly under alkaline conditions due to the sluggish water dissociation kinetics. In the first work, a hybridization catalyst construction concept is presented to dramatically enhance the alkaline HER activities of catalysts based on 2D transition metal dichalcogenides (TMDs) (MoS2 and WS2). A series of ultrathin 2D-hybrids are synthesized via facile controllable growth of 3d metal (Ni, Co, Fe, Mn) hydroxides on the monolayer 2D-TMD nanosheets. The resultant Ni(OH)2 and Co(OH)2 hybridized ultrathin MoS2 and WS2 nanosheet catalysts exhibit significantly enhanced alkaline HER activity and stability compared to their bare counterparts. The combined theoretical and experimental studies confirm that the formation of the heterostructured boundaries by suitable hybridization of the TMD and 3d metal hydroxides is responsible for the improved alkaline HER activities because of the enhanced water dissociation step and lowers the corresponding kinetic energy barrier by the hybridized 3d metal hydroxides. (2) Nitrogen-coordinated iron atoms on carbon matrix (Fe-N-C) materials are the most active Pt-group-metal-free ORR catalysts but still suffering their low stability and relatively lower activity compared to platinum-based materials. In the second work, Fe and Ni dual sites atomically dispersed in hierarchically ordered macroporous carbon support (Fe-Ni/N-HOMC) was designed and successfully prepared. Isolated atomic Fe- N4 and Ni-N4 active sites were confirmed via various characterizations. The ORR activity and stability of Fe-Ni/N-HOMC in both acid and alkaline electrolyte were much higher than commercial Pt/C and the mono-Fe doping counterpart, which was among the state-of-the-art ORR electrocatalysts. In addition, this 3D ordered interconnected macroporous structure with abundant mesopores and micropores could greatly increase the accessible ORR active site and also enhance the mass transport during the ORR process. When employed as cathodes for PEMFC, we found the excellent ORR activity of Fe-Ni/N-HOMC was completely translated to the cathode in the fuel cell. (3) High-performance bifunctional electrocatalysts with ORR and OER activity is the key to developing efficient rechargeable Zn-air batteries. In the third work, a high-performance bifunctional electrocatalysts for both OER and ORR were synthesized via further hybridizing as-prepared Fe-Ni/N-HOMC with NiFe layer double hydroxides (LDHs). Layered double hydroxides (LDHs) have been reported to be promising OER electrocatalysts with ultrahigh OER performances. The as-synthesized new composites exhibited almost the same ORR activity as Fe-Ni/N-HOMC, revealing that hybridization of NiFe-LDHs would not deteriorate the initial ORR activity. Moreover, the remarkable enhancement of OER activity was observed after the hybridization, which was attributed to the strong coupling of uniformly dispersed small NiFe-LDH nanoparticles with the carbon substrate. The prototype Zn-air battery was assembled using these new composites, which displayed the ultralow voltage gap and long-term stability. (4) Compared with Fe-N-C or Co-N-C based ORR electrocatalysts, the Cu-nitrogen-carbon composites were attracted little attention. However, the natural multicopper oxidases (MCOs) enzymes, such as laccase, can serve as efficient ORR catalyst with almost no overpotential. Inspired by their tris-copper centers in MCO, one novel Cu-nitrogen-carbon composite (Cu SAs/N-CS) with atomic Cu coordination sites were synthesized via the pyrolysis of the Cu-involved metal-organic-framework. The copper contents in Cu SAs/N-CS reaches as high as 3.17 wt.%, and the average distances of adjacent copper sites was around only 3.1 Å. Due to the synergetic effect of abundant single atomic copper active sites with closer distance and ultrathin carbon nanosheet structure, Cu SAs/N-CS exhibited superior ORR activity exceeding commercial Pt/C catalyst, methanol tolerance, and long-term stability in both alkaline and neutral electrolyte. In summary, four kinds of new composites were successfully designed and prepared as high-performance electrocatalysts for HER, ORR and OER. Multi-dimensional heterostructures, atomic metal coordination sites and 3D hierarchically porous structure were designed and observed, which contributed greatly to improve activities of these composites. This thesis suggests several new viewpoints in the design of electrocatalysts based on earth-abundant materials: (i) offering new strategies for the preparation of novel 2D and 3D heterostructures as electrocatalysts; (ii) expanding methods for the synthesis of atomic metal coordination sites and evaluating their activities for ORR; (iii) evaluating the practical performances of achieved electrocatalysts in proton exchange membrane fuel cell and Zn-air battery; (iv) attempting to explain reaction mechanisms of some electrocatalysts by DFT calculation.
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