Strongly coupled dual zerovalent nonmetal doped nickel phosphide Nanoparticles/N, B-graphene hybrid for pH-Universal hydrogen evolution catalysis
Introduction
The energy crisis and environment pollution call for clean and renewable energy to replace the current widely used fossil fuels [[1], [2], [3], [4]]. Hydrogen, as an alternative energy carrier, is becoming a key player in the future energy system attributed to its high energy density and environmentally friendly characteristics [5,6]. Electrochemical hydrogen evolution reaction is considered as an economically feasible approach in water electrolysis and drawn a significant amount of attention, but requires efficient electrocatalysts to reach high current density at a low overpotential [[7], [8], [9]]. Currently, noble metals, e.g., platinum (Pt), has been regarded as the prerequisite electrocatalysts, nevertheless, the high cost and rarity seriously impeded their widely practical application. Therefore, a variety of earth-abundant non-noble metal catalysts, containing transition metal compounds like sulfides, phosphides, carbides, nitrides, oxides and selenides had been proverbially developed to solve such problems [[10], [11], [12], [13], [14], [15], [16]]. However, their catalytic activity is yet unfulfilling in comparison with noble metals. Further, the majority of them perform their optimal activity only in acidic medium or basic electrolyte. An ideal electrocatalyst needs to fulfill the requests of the inevitable change of proton concentration during the hydrogen evolution reaction (HER) process in different pH environments, in order that the water dissociation process can be more energy efficient. Driven by these challenges, finding a low-cost, high-efficiency and long-stability catalyst with the ability to work well at different pH values is still an urgent task, but is of great significance.
Recently, metal doping engineering has been considered to be an effective mean to optimize the electronic structures of electrocatalysts for enhancing their catalytic activity [[17], [18], [19], [20]]. However, the introduction of exogenous metal elements may serve as active sites, which in turn affects the exploration of the catalytic mechanism. Meanwhile, the insertion of metal elements is unfavorable for maintaining the stable crystal structure. In this regard, a few recent studies are undertaken to regulate HER kinetics and enhance their electrocatalytic activities by incorporating nonmetal elements (O, S or N) in the transition metal-based HER electrocatalysts, such as O-doped Co2P [21], N doped CoS2 [22] and S doped CoP [23]. They have been demonstrated to be highly active electrocatalysts to catalyze HER. Nevertheless, the performance improvement of these non-metal doped electrocatalysts is still very limited, which may be due to the inadequate optimization of the adsorption energy for reaction intermediates. Besides, most of the non-metal heteroatoms exist as anions in the structure of electrocatalysts. The anions incorporation may not be beneficial to the host crystal lattice by changing the oxidation states of the host crystal or generate vacancies, thereby causing the structure of the electrocatalyst to be unstable during the catalytic process. Given the ability to retain charge balancing and structural stability of host materials, zero-valent non-metal incorporation, especially dual zero-valent heteroatoms incorporation is expected to be a new effective avenue to design active and stable electrocatalysts.
On the other hand, integrating catalyst particles with highly conductive carbon materials has been widely used to prevent the agglomeration of electrocatalysts, heighten charge transport ability and increase active site exposure and thus upgrade catalytic performance [[24], [25], [26], [27], [28], [29]]. However, the lack of strongly coupled bonds at the interface of the substrates and electrocatalysts, which functions as an electron transport channel, still seriously restricts their interfacial charge-transfer process. Nowadays, some electrocatalysts that strongly couple to carbon could be obtained from the post-treatment of metal-organic frameworks (MOF) [[30], [31], [32]]. However, MOFs are always built from metal ions and costly organic ligands which is uneconomical and not suitable for large-scale applications. Graphene, as a highly conductive two-dimensional material, can not only accelerate electron transfer, but also provide ideal support for the in-situ growth of nanoparticles without agglomeration [[33], [34], [35]]. In this aspect, the strongly coupled dual zero-valent nonmetal doped transition metal compounds/graphene hybrid materials is highly desirable for HER.
In this study, we report a strong couple of dual zero-valent nonmetal (N, B) doped Ni2P nanoparticles hybridized with N, B-graphene (denoted as N, B-Ni2P/G) as stable and outstanding pH-universal HER electrocatalysts. Attributed to the enhanced intrinsic catalytic activity and charge transport ability, the N, B-Ni2P/G exhibits the enhanced HER performance in universal pH conditions. Especially, for current density, the obtained material showed an enhancement of about 10.7 times than pure Ni2P in neutral solution. Density functional theory (DFT) calculations further prove that zero-valent N, B atoms incorporation can effectively optimize the adsorption energy of activated water and hydrogen adsorption free energy synchronously in Ni2P, resulting in favorable kinetics of the pH-universal HER. The presented work may open up new possibilities of designing highly efficient HER catalysts for boosting HER performance at all pHs.
Section snippets
Synthesis of Ni-Bi nanosheets/graphene layered heterostructures (Ni-Bi NS/G)
The Ni-Bi NS/G heterostructure was made by a room temperature chemical synthesis method via in situ self-assembly [36]. Typically, 1 mmol nickel nitrate hexahydrate (Ni(NO3)2·6H2O) and 5 mL GO (1.5 mg mL−1) was dispersed into 100 mL deionized water under ultrasonication for 15 min and stirred for another 40 min to complete dissolution. After full desorption between Ni2+ and GO, a 5 mL solution containing NaBH4 (0.5 mol/L) was added and in situ vertical growth of nickel boron oxide on graphene
Results and discussion
The N, B doped Ni2P nanoparticles strongly coupled to graphene (N, B-Ni2P/G) was realized via two steps: (i) synthesis of Ni-Bi nanosheets on graphene (Ni-Bi NS/G) via in situ self-assembly method (Figure S1, S2); (ii) conversion of the obtained Ni-Bi NS/G precursor to N, B-Ni2P/G by in situ phosphidation process in Ar/NH3 atmosphere, as illustrated in Scheme 1. The detailed structural features of the obtained sample were firstly investigated by X-ray diffraction (XRD). All the diffraction
Conclusion
In summary, the hybrid electrocatalyst of well-dispersed dual zerovalent nonmetal (N and B) doped Ni2P nanoparticles anchored on the N, B-graphene is reported, which achieves a large enhancement of the HER catalytic activity and stability in all pH condition. As evidenced by the XPS results, not like common anion doping, the nitrogen and boron are doped into the lattice of N, B-Ni2P nanoparticles in the form of zero valence. Moreover, density functional theory (DFT) calculations further confirm
CRediT authorship contribution statement
Yiqiang Sun: Methodology, Investigation, Writing - original draft. Kun Xu: Conceptualization, Writing - review & editing, Supervision. Zihan Zhao: Validation, Investigation. Xiuling Li: Formal analysis. Guozhu Chen: Formal analysis. Cuncheng Li: Writing - review & editing, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work is supported by the National Natural Science Foundation of China (Grant No. 51671094, 21803031), Shandong Provincial Natural Science Foundation (ZR2019BEM007), Shandong postdoctoral innova talents support plan and the supports from UJN, Natural Science Foundation of the Jiangsu Higher Education Institution of China (Grant No. 18KJB150022).
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2023, Advances in Colloid and Interface ScienceCitation Excerpt :It is established that a change in chemical characteristics and the formation of an intermediate tunnelling resistance are responsible for the significant increase in performance following the relaxation of the polymer-based substrate (Fig. 15i, j) [192]. Hetero-atom doping continually and effectively modifies the electronic properties and hydrogen evolution performance of an electrocatalyst without altering its chemical components [193–205]. Consequently, hetero-atom doping is an efficient and extensively employed method for optimizing HER function.