Electrocatalytic CO₂ reduction (ECR) is regarded as an alternative strategy for tackling the energy demand problem as well as environmental issues such as global warming. The development of highly selective and stable, environmentally friendly, energy-efficient, and cost-natural advanced electrocatalysts is critical to facilitating this kinetically slow process. Herein, it has been aimed to form hierarchically ordered electrochemically active sites on three-dimensional graphene architecture as well as get benefit from the synergistic effect of co-doping of nitrogen and phosphorous, and thereby boosting the CO₂ conversion. Therefore, metal-free nitrogen and phosphorous co-doped three-dimensional graphene (N,P-3DGN) architecture has been fabricated via a facile, scalable one-step microwave-assisted hydrothermal production pathway. N,P-3DG possesses a higher electrochemical active area and electrical conductivity than N- or P-doped graphene structures, facilitating electron transfer from CO₂ to its radical anion or other key intermediates. Therefore, as-fabricated N,P-3DG structure with hierarchically ordered three-dimensional ion highways offered high faradaic efficiency of 93.7% for formate production at − 1.3 V (vs. Ag/AgCl) at a reasonable overpotential of 0.5 V. The onset potential of N,P-3DG has been found to be − 0.96 V (vs. Ag/AgCl), which is more positive than that of the three-dimensional graphene structure (3DG) (− 1.53 V). The N,S-3DG electrocatalyst successfully hindered the hydrogen evolution reaction and demonstrated stable electrocatalytic activity towards ECR. The results showed that the unique structure and synergistic effect of co-doping N,P atoms with C atoms pointed in the direction of conversion CO₂ to formate.

电催化 CO ₂还原 (ECR) 被视为解决能源需求问题以及全球变暖等环境问题的替代策略。开发高选择性、稳定、环保、节能且成本低廉的先进电催化剂对于促进这一动力学缓慢的过程至关重要。在此，其目的是在三维石墨烯结构上形成分级有序的电化学活性位点，并受益于氮和磷共掺杂的协同效应，从而提高 CO ₂转换。因此，无金属氮和磷共掺杂的三维石墨烯 (N,P-3DGN) 结构已通过一种简便、可扩展的一步微波辅助水热生产途径制造。N,P-3DG 比 N 或 P 掺杂的石墨烯结构具有更高的电化学活性面积和电导率，促进从 CO _{2 的}电子转移其自由基阴离子或其他关键中间体。因此，具有等级有序的三维离子高速公路的制造的 N,P-3DG 结构在 - 1.3 V（相对于 Ag/AgCl）和 0.5 V 的合理过电位下为甲酸盐生产提供了 93.7% 的高法拉第效率。已发现 N,P-3DG 的电位为 - 0.96 V（相对于 Ag/AgCl），这比三维石墨烯结构 (3DG) (- 1.53 V) 的电位更正。N,S-3DG 电催化剂成功地阻碍了析氢反应，并表现出对 ECR 的稳定电催化活性。结果表明，N、P原子与C原子共掺杂的独特结构和协同效应指向了CO ₂转化为甲酸盐的方向。