南京工業大學王軍團隊報道了電合成高濃度中性過氧化氫的羧基化六方氮化硼/石墨烯構型。相關研究成果于2023年12月29日發表在《德國應用化學》。

　　通過雙電子（2e-）氧（O2）還原反應（ORR）電合成過氧化氫（H2O2）在取代傳統能源密集型蒽醌工藝方面具有巨大潛力，但低成本、高活性和選擇性催化劑的設計對于在工業相關電流密度下長期生產H2O2具有很大的挑戰性，尤其是在中性電解質下。

　　為了解決這個問題，研究人員通過B，N共摻雜與表面氧基團功能化的耦合，在商業活性炭上構建了羧化六方氮化硼/石墨烯（h-BN/G）異質結。最優催化劑具有高的2e-ORR選擇性（>95%）、產率（高達13.4 mol g-1 h-1）和法拉第效率（FE，>95%）。在100mA cm-2的高電流密度下長期產生H2O2導致累積濃度高達2.1 wt.%。

　　原位拉曼光譜和理論計算的結合表明，羧化的h-BN/G構型促進了O2的吸附和關鍵中間體（OOH*和HOOH*）的穩定，能夠使低能量勢壘用于活性位點釋放HOOH*的速率決定步驟，從而提高2e-ORR性能。利用這種電化學合成的H2O2快速降解染料，進一步說明了其有前景的實際應用。

附：英文原文

Title: Carboxylated Hexagonal Boron Nitride/Graphene Configuration for Electrosynthesis of High-Concentration Neutral Hydrogen Peroxide

Author: Zhixin Song, Xiao Chi, Shu Dong, Biao Meng, Xiaojiang Yu, Xiaoling Liu, Yu Zhou, Jun Wang

Issue&Volume: 2023-12-29

Abstract: The electrosynthesis of hydrogen peroxide (H2O2) via two-electron (2e-) oxygen (O2) reduction reaction (ORR) has great potential to replace the traditional energy-intensive anthraquinone process, but the design of low-cost and highly active and selective catalysts is greatly challenging for the long-term H2O2 production under industrial relevant current density, especially under neutral electrolytes. To address this issue, this work constructed a carboxylated hexagonal boron nitride/graphene (h-BN/G) heterojunction on the commercial activated carbon through the coupling of B, N co-doping with surface oxygen groups functionalization. The champion catalyst exhibited a high 2e- ORR selectivity (>95%), production rate (up to 13.4 mol g-1 h-1), and Faradaic efficiency (FE, >95%). The long-term H2O2 production under the high current density of 100 mA cm-2 caused the cumulative concentration as high as 2.1 wt.%. The combination of in-situ Raman spectra and theoretical calculation indicated that the carboxylated h-BN/G configuration promotes the adsorption of O2 and the stabilization of the key intermediates (OOH* and HOOH*), allowing a low energy barrier for the rate-determining step of HOOH* release from the active site, and thus improving the 2e- ORR performance. The fast dye degradation by using this electrochemical synthesized H2O2 further illustrated the promising practical application.

DOI: 10.1002/anie.202317267

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202317267