Multi-site Co2P catalyst derived from soybean biomass for dehydrogenation of formic acid
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摘要: 本研究报道了一种通过大豆和钴盐热解制备的甲酸脱氢用Co2P催化剂，制备过程简单且环境友好。催化过程中，催化剂上的含K固体碱可作为路易斯酸性位点促进HCOO−中间体的吸附，而自掺杂的N可作为碱性位点促进H+的吸附。大豆生物质中的P可与钴盐结合并热解成Co2P，该位点可裂解HCOO−的H−C键。催化剂制备过程中当Co(NO3)2·6H2O/大豆的质量比为1∶15时，所得Co2P催化剂对甲酸脱氢反应的产气率可达237.47 mL/(g·h)，并展现出良好的稳定性。本研究结果可为甲酸选择性产氢用非贵金属非均相催化剂的开发提供一定的借鉴基础。Abstract: Formic acid (FA) is a sustainable liquid organic hydrogen carrier and the catalyst for hydrogen production from FA has received significant attention. However, the development of efficient non-noble metal catalysts still remains challenges. In this work, we provide a technologically rather simple and environmental-friendly strategy to synthesize Co2P catalyst for dehydrogenation of FA by pyrolyzing soybean powder and cobalt salt. The K-containing solid bases in catalyst could act as Lewis acid sites for the HCOO− intermediate adsorption while the self-doped N could act as Lewis base sites to enhance the H+ adsorption. The P contained in soybean could combine with Co to form Co2P for H−C bond cleavage of HCOO−. At a Co(NO3)2·6H2O/soybean mass ratio of 1∶15, the as prepared Co2P catalyst demonstrated a gas production rate of 237.47 mL/(g·h) and a good stability. This study provides a novel strategy to develop non-noble metal heterogeneous catalysts for FA dehydrogenation.
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Key words:
- formic acid /
- heterogeneous catalyst /
- biomass /
- dehydrogenation
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Figure 3 (a)−(b) SEM and (c) TEM images of soybean-derived C support; (d) EDS spectrum of (Co2P)1-SB15; (e)−(f) TEM images and (g) HAADF-STEM mappings of (Co2P)1-SB15.
Figure 6 Gas production rates of (a) (Co2P)1-SB10 synthesized at different pyrolysis temperatures and (b) (Co2P)x-SBy pyrolyzed at 750 °C, (c) volume of gas produced during five cycles and (d) accumulated gas volume in a 63 h-continuous test over (Co2P)1-SB15
(Reaction conditions: 20 mL of 10.39 mol/L FA, 98 °C)
Figure 7 (a) XRD patterns of (Co2P)1-SB15 after H2SO4 treatment: (b) Gas production rate comparison of (Co2P)1-SB15 catalyst before and after H2SO4 or KSCN treatment.
(Reaction conditions: 20 mL of 10.39 mol/L FA, 98 °C)
Table 1 Co and P contents of catalyst and corresponding FA solution in 10.39 mol/L FA, 98 °C
Sample Co P Unit (Co2P)1-SB15 1.04 0.77 % (Co2P)1-SB15-1 h 0.86 0.28 % (Co2P)1-SB15-63 h 0.81 0.27 % FA solution-63 h 95.3 139.3 mg/L 
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Table 2 K contents of (Co2P)1-SB15 collected after 1 h and 63 h reaction in 10.39 M FA, 98 °C
Sample K Unit (Co2P)1-SB15-1 h 0.59 wt.% (Co2P)1-SB15-63 h 0.13 wt.%
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