In electrochemical hydrogen production, a major contribution to the energy demand is the anodic oxygen evolution reaction, although byproduct oxygen is often not utilized. This motivates the search for alternative anodic oxidation reactions. Glycerol has been proposed as a promising reagent for the anode since it is widely available, cheap, and green. However, it is still unclear if this would have energetic and economic benefits. To this end, we evaluated the anodic oxidation of glycerol to the 14 alternative products that have been mentioned in the literature. We screened these possible oxidation products based on two criteria: (i) a surrogate for the energy demand (reversible and thermoneutral voltages) and (ii) an economic value. To address the challenge of data availability, we took thermodynamic properties estimated by group contribution methods and machine learning. For the economic data, we use both laboratory price data from Sigma-Aldrich and industry price data from ChemAnalyst and Kahlstorf et al. We also compare the current and projected production rates of hydrogen and find that the current glycerol supply will not suffice to cover the hydrogen demand, yet still coupled glycerol oxidation and hydrogen evolution can serve as an alternative to convert glycerol waste streams from biodiesel plants to higher value while additionally producing hydrogen. All glycerol oxidation reactions considered have the potential to significantly reduce the energy demand for green hydrogen production. Some of them potentially add value through byproducts, although product prices are highly uncertain.

中文翻译：

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甘油氧化替代水电解中析氧的热力学和经济潜力

在电化学制氢中，对能量需求的主要贡献是阳极析氧反应，尽管副产物氧气通常不被利用。这促使人们寻找替代的阳极氧化反应。甘油被认为是一种有前途的阳极试剂，因为它广泛可用、廉价且绿色。然而，目前尚不清楚这是否会带来能源和经济效益。为此，我们对文献中提到的 14 种替代产品的甘油阳极氧化进行了评估。我们根据两个标准筛选这些可能的氧化产物：(i) 能源需求的替代品（可逆电压和热中性电压）和 (ii) 经济价值。为了解决数据可用性的挑战，我们采用了通过群体贡献方法和机器学习估计的热力学性质。对于经济数据，我们使用 Sigma-Aldrich 的实验室价格数据以及 ChemAnalyst 和 Kahlstorf 等人的行业价格数据。我们还比较了当前和预计的氢气生产率，发现当前的甘油供应不足以满足氢气需求，但仍然耦合的甘油氧化和析氢可以作为将生物柴油厂的甘油废物流转化为更高浓度的替代方案。价值，同时额外产生氢气。所有考虑的甘油氧化反应都有可能显着降低绿色氢气生产的能源需求。尽管产品价格高度不确定，但其中一些可能通过副产品增加价值。