We reported one novel strategy via band engineering of the semiconductor support to optimize the metal-support interactions at a Mott-Schottky heterojunction interface and enhance the metal’s electrocatalytic hydrodechlorination (EHDC) performance. Taking palladium-polymer carbon nitride (Pd/PCN) as a model, the band tuning of PCN by heteroatomic phosphorus (P) doping substantially boosted the EHDC of 2,4-dichlorophenol (2,4-DCP, one typical chlorinated organic pollutants (COPs)) on Pd, and a peak specific activity of 0.172 min⁻¹ cm_Pd⁻² was achieved by Pd/P-PCN-0.25 (0.25 reflected the P content, and denoted the mass ratio of the P source to PCN precursor used in P-PCN synthesis), quadrupling 0.041 min⁻¹ cm_Pd⁻² of Pd/C and outperforming most of the reported catalysts. The mechanism study revealed the P doping in PCN enabled the positive shift of its Fermi level, which weakened the Pd-PCN interactions and alleviated the electron excess of Pd in Pd/PCN. The P-PCN in Pd/P-PCN-0.25 with the ideal band structure evoked a Pd electronic state that maximized EHDC efficiency. Further investigation into the intermediate products of EHDC on Pd/P-PCN and the biological safety of the 2,4-DCP-contaminated water after EHDC treatment demonstrated the EHDC over our catalyst was environmental-benignity for COPs abatement.

我们报告了一种通过半导体载体的能带工程来优化Mott-Schottky异质结界面处的金属-载体相互作用并增强金属的电催化加氢脱氯（EHDC）性能的新颖策略。以钯聚合物氮化碳（Pd / PCN）为模型，通过杂原子磷（P）掺杂对PCN进行能带调谐大大提高了2,4-二氯苯酚（2,4-DCP（一种典型的氯化有机污染物）的EHDC（ COPs））在Pd上，通过Pd / P-PCN-0.25（0.25反映了P含量，表示P源与PCN前体的质量比）实现了0.172 min ^-1 cm _Pd ^-2的峰比活。在P-PCN合成中），四倍0.041分钟^-1 cm _Pd ^-2Pd / C的含量超过了大多数报道的催化剂。机理研究表明，PCN中的P掺杂使其费米能级发生正向移动，从而削弱了Pd-PCN的相互作用并减轻了Pd / PCN中Pd的电子过量。具有理想带结构的Pd / P-PCN-0.25中的P-PCN引发了Pd电子状态，该状态使EHDC效率最大化。对EHDC在Pd / P-PCN上的中间产物进行进一步研究，以及EHDC处理后被2,4-DCP污染的水的生物安全性表明，在我们的催化剂上，EHDC具有减少COPs的环境效益。