Kumaravel Sakthivel, Erusappan Elangovan, Vignesh Shanmugam, Chicardi E, Periyasami Govindasami, Devarayapalli Kamakshaiah Charyulu, Kim Bolam, Oh Tae Hwan, Lee Dae Sung
Department of Environmental Engineering, Kyungpook National University, 80 Daehak-ro, Buk-gu, Daegu, 41566, Republic of Korea.
Saveetha School of Engineering, Saveetha Institute of Medical and Technical Sciences (SIMATS), Chennai, Tamil Nadu, 602105, India.
Environ Res. 2025 Mar 1;268:120793. doi: 10.1016/j.envres.2025.120793. Epub 2025 Jan 9.
In this study, graphitic carbon nitride (CN) and tungsten trioxide (WO) were successfully incorporated into bromine (Br)-doped graphitic carbon nitride (BCN) using an in-situ hydrothermal method. The photocatalytic efficiency of the resulting WO/Br-doped CN (WBCN) composites for the removal of tetracycline (TC) antibiotics under sunlight irradiation was evaluated. The mass ratio of WO to Br-doped CN (BCN) significantly influenced TC adsorption and photocatalytic degradation, with an optimal ratio of 9:1. The synthesized catalyst exhibited exceptional performance, achieving 98% TC detoxification under sunlight, attributed to enhanced light absorption, efficient charge separation, and reduced electron-hole (e/h) recombination facilitated by BCN doping. Trapping experiments and ESR analysis identified O and OH as the primary reactive species in TC decomposition, with h radicals playing a secondary role. Reusability tests further confirmed the high stability of the photocatalyst. The Z-scheme charge transfer mechanism was elucidated, highlighting the crucial role of Br doping in enhancing synergistic interactions between WO and CN. Additionally, the nickel foam (NF) electrode supported by the WBCN-2 composite demonstrated remarkable electrocatalytic activity for hydrogen evolution, achieving a minimum overpotential of 99 mV and a Tafel slope of 108 mV/dec at a current density of 10 mA/cm. The WBCN-2@NF composite catalyst also achieved excellent performance, with a low cell voltage of 1.77 V at 10 mA/cm. Chronopotentiometry (CP) tests revealed remarkable long-term stability, with minimal current loss over 15 h of continuous operation. Overall, the WBCN composite exhibits excellent photocatalytic and electrocatalytic performance, making it a promising candidate for practical environmental remediation and sustainable energy production.
在本研究中，采用原位水热法成功地将石墨相氮化碳（CN）和三氧化钨（WO₃）掺入溴（Br）掺杂的石墨相氮化碳（BCN）中。评估了所得WO₃/Br掺杂CN（WBCN）复合材料在阳光照射下对四环素（TC）抗生素的光催化去除效率。WO₃与Br掺杂CN（BCN）的质量比显著影响TC的吸附和光催化降解，最佳比例为9:1。合成的催化剂表现出优异的性能，在阳光下实现了98%的TC解毒，这归因于BCN掺杂促进了光吸收增强、电荷有效分离以及电子-空穴（e/h）复合减少。捕获实验和电子顺磁共振（ESR）分析确定O₂⁻和·OH是TC分解中的主要活性物种，h⁺自由基起次要作用。可重复使用性测试进一步证实了光催化剂的高稳定性。阐明了Z型电荷转移机制，突出了Br掺杂在增强WO₃和CN之间协同相互作用中的关键作用。此外，由WBCN-2复合材料支撑的泡沫镍（NF）电极对析氢表现出显著的电催化活性，在电流密度为10 mA/cm²时实现了99 mV的最小过电位和108 mV/dec的塔菲尔斜率。WBCN-2@NF复合催化剂也表现出优异的性能，在10 mA/cm²时电池电压低至1.77 V。计时电位法（CP）测试显示出显著的长期稳定性，在连续运行15小时内电流损失最小。总体而言，WBCN复合材料表现出优异的光催化和电催化性能，使其成为实际环境修复和可持续能源生产的有前途的候选材料。
