Biochar (BCH) is a carbon-based bio-material produced from thermochemical conversion of biomass. Several activation or functionalization methods are usually used to improve physicochemical and functional properties of BCHs. In the context of green and sustainable future development, activated and functionalized biochars with abundant surface functional groups and large surface area can act as effective catalysts or catalyst supports for chemical transformation of a range of bioproducts in biorefineries. Above the well-known BCH applications, their use as adsorbents to remove pollutants are the mostly discussed, although their potential as catalysts or catalyst supports for advanced (electro)catalytic processes has not been comprehensively explored. In this review, the production/activation/functionalization of metal-supported biochar (M-BCH) are scrutinized, giving special emphasis to the metal-functionalized biochar-based (electro)catalysts as promising catalysts for bioenergy and bioproducts production. Their performance in the fields of biorefinery processes, and energy storage and conversion as electrode materials for oxygen and hydrogen evolutions, oxygen reduction, and supercapacitors, are also reviewed and discussed.

To address aggravating environmental and energy problems, active, efficient, low-cost, and robust electrocatalysts (ECs) are actively pursued as substitutes for the current noble metal ECs. Therefore, in this study, we report the preparation of graphene flakes (GF) doped with S and N using 2-5-dimercapto-1,3,4-thiadiazole (S₃N₂) as precursor followed by the immobilization of cobalt spinel oxide (Co₃O₄) or manganese spinel oxide (Mn₃O₄) nanoparticles through a one-step co-precipitation procedure (Co/S₃N₂–GF and Mn/S₃N₂–GF). Characterization by different physicochemical techniques (Fourier Transform Infrared (FTIR), Raman spectroscopy, Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD)) of both composites shows the preservation of the metal oxide spinel structure and further confirms the successful preparation of the envisaged electrocatalysts. Co/S₃N₂–GF composite exhibits the best ORR performance with an onset potential of 0.91 V vs. RHE, a diffusion-limiting current density of −4.50 mA cm⁻² and selectivity for the direct four-electron pathway, matching the results obtained for commercial Pt/C. Moreover, both Co/S₃N₂–GF and Mn/S₃N₂–GF showed excellent tolerance to methanol poisoning and good stability.

The development of sustainable and high-performance oxygen reduction reaction (ORR) electrocatalysts is fundamental to fuel cell implementation. Non-precious transition metal oxides present interesting electrocatalytic behavior, and their incorporation into N-doped carbon supports leads to excellent ORR performance. Herein, we prepared a shrimp shell-derived biochar (CC), which was doped with nitrogen via a ball milling approach (N-CC), and then used as support for Co₃O₄ nanoparticles growth (N-CC@Co₃O₄). Co₃O₄ loading was optimized using three different amounts of cobalt precursor: 1.56, 2.33 and 3.11 mmol in N-CC@Co₃O₄_1, N-CC@Co₃O₄_2 and N-CC@Co₃O₄_3, respectively. Interestingly, all prepared electrocatalysts, including the initial biochar CC, presented electrocatalytic activity towards ORR. Both N-doping and the introduction of Co₃O₄ NPs had a significant positive effect on ORR performance. Meanwhile, the three composites showed distinct ORR behavior, demonstrating that it is possible to tune their electrocatalytic performance by changing the Co₃O₄ loading. Overall, N-CC@Co₃O₄_2 achieved the most promising ORR results, displaying an E_onset of 0.84 V vs. RHE, j_L of −3.45 mA cm⁻² and excellent selectivity for the 4-electron reduction (n = 3.50), besides good long-term stability. These results were explained by a combination of high content of pyridinic-N and graphitic-N, high ratio of pyridinic-N/graphitic-N, and optimized Co₃O₄ loading interacting synergistically with the porous N-CC support.