Pd supported on Co@CN derived from ZIF-67 as catalyst for hydrogen generation from formic acid
Introduction
Hydrogen has attracted wide attention as a propitious energy in a number of fields. Formic acid (FA) is considered as a promising chemical hydrogen storage media due to the unique characteristics of nontoxicity, excellent stability, high hydrogen content (ca. 4.4 wt%). Numerous researches [1], [2] have been devoted to exploring catalysts for hydrogen generation form FA. Pd catalysts are used in decomposition of FA. Incorporation of non-precious metal into the Pd catalysts may not only tailor electronic properties and geometric structure of Pd nanoparticles (NPs) to enhance the catalytic activity and selectivity, but also reduce the consumption of the noble metals [3], [4]. Besides, doping N-containing functional groups into support materials modify Pd electron state [5] and facilitate the anchoring of Pd NPs to increase its dispersity [6].
Zeolitic imidazolate frameworks (ZIFs) composed of 2-methyl imidazolate (2-mIM) ligands coordinated with transition metal cations that results in a sodalite (SOD) topology. ZIFs have emerged as promising precursors for the production of transition-metal and N-doped porous carbon composite materials by pyrolysis [7]. Herein, for the first time, we report Pd NPs immobilized in porous carbon derived from ZIF-67 as efficient catalysts, which exhibit good activity for FA decomposition to hydrogen.
Section snippets
Experiment
ZIF-67 was synthesized at room temperature and carbonized at 900 °C in Ar flow for using as catalyst support (denoted as Co@CN, wherein CN means N-rich porous carbon). Co@CN was sonicated in deionized water and then the solution of H2PdCl4 were added in it by stirring at room temperature. NaBH4 was added for reduction after adjusting the pH value. The catalyst was obtained after centrifugal, washing and drying (denoted as Pd/Co@CN). For comparison, Pd/CN (treating Co@CN with HF to remove Co)
Results and discussion
The XRD pattern of the catalysts indexed to parental ZIFs (Fig. S2) disappear by the observation of new peaks (Fig. 1a), indicating the destruction of the initial structure. The peak was observed at 2θ = 26.0°, which can be assigned to the (0 0 2) planes of graphitic carbon (JCPDS: 41–1487). This was due to Co acted as a catalyst for growth of highly graphitic frameworks [8]. For Co@CN, the diffraction peaks at 2θ = 44.0° (JCPDS: 15–0806) derived from the (1 1 1) diffraction of Co. Compared
Conclusions
In summary, Pd NPs assembled on porous carbon which derived from ZIF-67, which provides a method to prepare well-dispersed Pd catalyst for the hydrogen generation from FA without undesired CO contamination. The Co and N species inherited from ZIF-67 improved the catalytic activity of Pd by regulating its electronic state and structure and promoting its dispersion. The excellent performance of catalyst (TOF of 1403 h−1) was highlighting the feasibility of renewable FA as a convenient in situ
CRediT authorship contribution statement
Mengqin Yao: Conceptualization, Methodology, Data curation, Writing - original draft. Yuling Ye: Visualization, Investigation. Honglin Chen: Writing - review & editing. Xiaoming Zhang: 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.
Acknowledgment
This work was supported by the National Key R&D Program of China [grant number 2018YFB0604902].
References (18)
- et al.
Appl. Catal. B-Environ.
(2017) - et al.
Appl. Surf. Sci.
(2019) - et al.
Mater. Lett.
(2019) - et al.
Electrochim. Acta
(2016) - et al.
Catal. Sci. Technol.
(2016) - et al.
Acc. Chem. Res.
(2017) - et al.
Angew. Chem. Int. Ed. Engl.
(2016) - et al.
J. Mater. Chem. A
(2013) - et al.
Angew. Chem. Int. Ed. Engl.
(2015)
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2-Dimensional metal-organic framework derived N-doped carbon immobilized Pd nanoparticles for hydrogen release from formic acid
2023, International Journal of Hydrogen EnergyCitation Excerpt :From Fig. 5, the distinguishable peaks located at 2θ ≈ 25° for all samples are derived from the amorphous staking of graphitic carbon [49,50]. For Pd/NCZIF-L and Pd/AC catalysts, four obvious peaks can be detected at 40.2°, 46.7°, 68.2°, and 82.1°, which are due to the typical peaks of Pd [51,52]. No obvious peaks of Pd particles are detected in Pd/NCZIF-L (KCl), indicating Pd particles are well dispersed in the catalyst.
Insights into N dopants during dehydrogenation of formic acid over Pd/N-doped carbon catalysts
2022, Journal of the Energy InstituteCitation Excerpt :The composition of produced gas was monitored by using an Agilent 7820A GC. FA dehydrogenation experiment was done in a self-made reactor which was used in our previous studies [31,32]. Briefly, 3 ml of H2O was injected into a glass reactor containing 53 mg catalyst.