Shvalagin Vitaliy, Tarakina Nadezda, Badamdorj Bolortuya, Lahrsen Inga-Marie, Bargiacchi Eleonora, Bardow Andre, Deng Ziqi, Wang Wenchao, Phillips David Lee, Guo Zhengxiao, Zhang Guigang, Tang Junwang, Savateev Oleksandr
Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, Potsdam 14476, Germany.
Energy & Process Systems Engineering, Department of Mechanical and Process Engineering, ETH Zurich, Tannenstrasse 3, Zurich 8092, Switzerland.
ACS Catal. 2024 Sep 23;14(19):14836-14854. doi: 10.1021/acscatal.4c04180. eCollection 2024 Oct 4.
In this work, protonated poly(heptazine imide) (H-PHI) was obtained by adding acid to the suspension of potassium PHI (K-PHI) in ethanol. It was established that the obtained H-PHI demonstrates very high photocatalytic activity in the reaction of hydrogen formation from ethanol in the presence of Pt nanoparticles under visible light irradiation in comparison with K-PHI. This enhancement can be attributed to improved efficiency of photogenerated charge transfer to the photocatalyst's surface, where redox processes occur. Various factors influencing the system's activity were evaluated. Notably, it was discovered that the conditions of acid introduction into the system can significantly affect the size of Pt (cocatalyst metal) deposition on the H-PHI surface, thereby enhancing the photocatalytic system's stability in producing molecular hydrogen. It was established that the system can operate efficiently in the presence of air without additional components on the photocatalyst surface to block air access. Under optimal conditions, the apparent quantum yield of molecular hydrogen production at 410 nm is around 73%, the highest reported value for carbon nitride materials to date. The addition of acid not only increases the activity of the reduction part of the system but also leads to the formation of a value-added product from ethanol-1,1-diethoxyethane (acetal) with high selectivity.
在这项工作中，通过向乙醇中碘化钾聚（七嗪酰亚胺）（K-PHI）悬浮液中添加酸来获得质子化聚（七嗪酰亚胺）（H-PHI）。结果表明，与K-PHI相比，所获得的H-PHI在可见光照射下，在Pt纳米颗粒存在的情况下，在由乙醇制氢的反应中表现出非常高的光催化活性。这种增强可归因于光生电荷转移到发生氧化还原过程的光催化剂表面的效率提高。评估了影响该系统活性的各种因素。值得注意的是，发现将酸引入系统的条件可显著影响Pt（助催化剂金属）在H-PHI表面的沉积尺寸，从而提高光催化系统在产生分子氢方面的稳定性。已确定该系统在存在空气的情况下无需在光催化剂表面添加额外成分来阻止空气进入即可有效运行。在最佳条件下，410nm处分子氢产生的表观量子产率约为73%，这是迄今为止氮化碳材料报道的最高值。酸的添加不仅提高了系统还原部分的活性，还导致从乙醇中以高选择性形成增值产物1,1-二乙氧基乙烷（缩醛）。
