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Abstract Electrochemical valorization of biomass represents an emerging research frontier, capitalizing on renewable feedstocks to mitigate carbon emissions. Traditional electrochemical approaches often suffer from energy inefficiencies due to the requirement of a second electrochemical conversion at the counter electrode which might generate non‐value‐added byproducts. This review article presents the advancement of paired electrocatalysis as an alternative strategy, wherein both half‐reactions in an electrochemical cell are harnessed to concurrently produce value‐added chemicals from biomass‐derived feedstocks, potentially doubling the Faradaic efficiency of the whole process. The operational principles and advantages of different cell configurations, including 1‐compartment undivided cells, H‐type cells, and flow cells, in the context of paired electrolysis are introduced and compared, followed by the analysis of various catalytic strategies, from catalyst‐free systems to sophisticated homogeneous and heterogeneous electrocatalysts, tailored for optimized performance. Key substrates, such as CO₂, 5‐hydroxymethylfurfural (HMF), furfural, glycerol, and lignin are highlighted to demonstrate the versatility and efficacy of paired electrocatalysis. This work aims to provide a clear understanding of why and how both cathode and anode reactions can be effectively utilized in electrocatalytic biomass valorization leading to innovative industrial scalability. 

Abstract The broad employment of water electrolysis for hydrogen (H₂) production is restricted by its large voltage requirement and low energy conversion efficiency because of the sluggish oxygen evolution reaction (OER). Herein, we report a strategy to replace OER with a thermodynamically more favorable reaction, the partial oxidation of formaldehyde to formate under alkaline conditions, using a Cu₃Ag₇electrocatalyst. Such a strategy not only produces more valuable anodic product than O₂but also releases H₂at the anode with a small voltage input. Density functional theory studies indicate the H₂C(OH)O intermediate from formaldehyde hydration can be better stabilized on Cu₃Ag₇than on Cu or Ag, leading to a lower C-H cleavage barrier. A two-electrode electrolyzer employing an electrocatalyst of Cu₃Ag₇(+)||Ni₃N/Ni(–) can produce H₂at both anode and cathode simultaneously with an apparent 200% Faradaic efficiency, reaching a current density of 500 mA/cm²with a cell voltage of only 0.60 V. 

Employing water as a hydrogen source is an attractive and sustainable option in electricity-driven organic hydrogenation, which can overcome the drawbacks associated with traditional hydrogen sources like H₂. 

Electrochemical conversion of biomass-derived intermediate compounds to high-value products has emerged as a promising approach in the field of biorefinery. Biomass upgrading allows for the production of chemicals from non-fossil-based carbon sources and capitalization on electricity as a green energy input. Amino acids, as products of biomass upgrading, have received relatively little attention. Pharmaceutical and food industries will benefit from an alternative strategy for the production of amino acids that does not rely on inefficient fermentation processes. The use of renewable biomass resources as starting materials makes this proposed strategy more desirable. Herein, we report an electrochemical approach for the selective oxidation of biomass-derived α-hydroxyl acids to α-keto acids, followed by electrochemical reductive amination to yield amino acids as the final products. Such a strategy takes advantage of both reactions at the anode and cathode and produces amino acids under ambient conditions with high energy efficiency. A flow electrolyzer was also successfully employed for the conversion of α-hydroxyl acids to amino acids, highlighting its great potential for large-scale application.