Angew. Chem. | 生物质到甲酸的高效催化转化耦合低能耗电解水制氢

Figure 1 (a) Schematic diagram of conventional PEM water electrolysis; (b) Industrial methods for the synthesis of FA; (c) Schematic illustration of the co-production system of FA and hydrogen.

Figure 2 (a) The effects of POM species on the conversion of glucose and the yield of FA. Reaction conditions: voltage: 1.0 V (vs. Ag/AgCl), the concentration of various POMs: 0.3 M, the concentration of glucose: 0.1 M, temperature: 90 °C, reaction time: 8 h; (b) The effects of temperature on the conversion of glucose and the yield of FA. Reaction conditions: voltage: 1.0 V (vs. Ag/AgCl), the concentration of H₆[PMo₉V₃O₄₀]: 0.3 M, the concentration of glucose: 0.1 M, reaction time: 8 h; (c) Effects of different voltage on the conversion of glucose and yield of FA. Reaction conditions: the concentration of H₆[PMo₉V₃O₄₀]: 0.3 M, the concentration of glucose: 0.1 M, temperature: 90 °C, reaction time:8 h; (d) The glucose conversion and FA yield of H₆[PMo₉V₃O₄₀] recycled for five times; (e) The conversion and FA yield of different substrates. Reaction conditions: voltage: 1.0 V (vs. Ag/AgCl), the concentration of H6[PV3Mo9O40]: 0.3 M, the concentration of various substrates: 0.1 M, temperature: 90 °C, reaction time: 8 h; (f) Comparison of this work with the reported on the yield of FA, reaction temperature and pressure. Error bars represent the s.d. of at least three independent measurements.

Figure 3. Schematic diagram of the redox cycle in the anode chamber.

Figure 4 (a) The LSV curves of anode in the mixture of 3 M glucose and 0.3 M H₆[PMo₉V₃O₄₀] electrolyte after 3 h pre-reaction and 1 M H₃PO₄ electrolyte at 90 °C; (b) The power consumption analysis of this system. (c) Comparison of this work with the voltage required for electrocatalytic biomass conversion coupled with hydrogen production systems reported in the literature [22]; (d) Measured H₂ quantity compared with theoretically calculated H₂ quantity assuming a 100% Faradaic efficiency for the H₂ evolution. Theoretical H₂ = (total charge during potentiostatic electrolysis) × 2/ F, where F is the Faraday constant (96485 C mol⁻¹); (e) Economic efficiency analysis of conventional hydrogen production and the present work. The economic benefits of the whole system were calculated according to the price of hydrogen 2.5 $/kg, oxygen 0.108 $/kg, and FA 0.975 $/kg. Taking the power consumption of 1000 kWh as an example, the traditional electrolysis water hydrogen production device can produce about 21.2 kg H₂, which is worth 53.0 $, and the anode can produce about 169 kg O₂, which is worth 18.3$. The total economic value is 71.3 $. If we input a voltage of 1.22 V, we will get 30.7 kg of H₂, worth 76.7 $. In the anode electrolyte, approximately 321.0 kg of primary FA will be produced. Assuming that FA is obtained by distillation, it will consume approximately 45 kWh of electricity (0.11 $/kWh). Its value is about 308.0 $. The total value will reach 384.7 $, which will be 5.4 times the economic benefit of traditional electrolysis of water for hydrogen production.