Al修饰C_2N对甲醛降解的吸附增强机理及潜在催化活性的密度泛函理论研究（英文）
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摘要
羰基化合物,特别是甲醛,是室内最常见的对人体有害的空气污染物之一.如何对甲醛进行有效的控制已成为当前研究热点.在本工作中,我们使用密度泛函理论化学计算方法研究了甲醛分子在C_2N和Al修饰C_2N上的吸附性能.结果表明,纯C_2N对甲醛分子的吸附能力较弱,吸附能仅为–0.583 eV,C_2N经Al原子修饰改性后,吸附能为–2.585 eV,超过了改性前的4倍,有效增强了体系对甲醛分子的吸附能力.为了研究甲醛分子在Al修饰C_2N上的吸附增强机理,我们对局部态密度(PDOS)、Mulliken电荷分布及电子密度分布进行了计算.结果表明,Al原子修饰改变了附近的电子分布,从而改变了修饰Al原子的化学和物理行为,使其起到了连接甲醛分子和C_2N层的桥梁作用,从而加强了吸附能力.此外,为了研究产生对甲醛活化有效的羟基自由基(·OH)和超氧(O_2~(·–))自由基的可能,我们还计算了C_2N结构对H_2O分子和O_2分子的吸附.结果表明,Al修饰的C_2N对H_2O分子和O_2分子同样有很强的吸附能力.对于H_2O分子,在纯C_2N结构中的吸附能为–0.743 eV,在Al原子修饰后的结构中,其吸附能高达–3.177 eV,并且此时H_2O分子能够自发解离成一个羟基和一个H原子,其中羟基与修饰的Al原子相连,这为羟基自由基的生成提供了良好的条件.而对于O_2分子,在纯C_2N结构中的吸附能仅为–0.206 eV,在Al原子修饰后其吸附能高达–2.767 eV,约为修饰前的13倍,这使得化学吸附的O_2分子也具有更高的获得额外电子和高电位被激活为超氧自由基的潜能,这也为超氧自由基的生成提供了良好基础.上述研究表明,Al修饰C_2N是一种有前途的材料,可用于甲醛分子的吸附及催化降解.
Carbonyl compounds,in particular formaldehyde(HCHO),are among the most common indoor air pollutants that have been found to be toxic to humans.Thus,in this study,density functional theory(DFT)calculations are performed to study the adsorption properties of HCHO on pristine and Al-decorated C_2N monolayer.The results indicate that Al-decorated C_2N has a strong adsorption ability for HCHO molecules with an adsorption energy of–2.585 eV.Moreover,partial density of states(PDOS),Mulliken atomic charges,and electron density distributions are calculated to investigate the adsorption enhancement mechanism.The results show that the Al atom serves as a bridge to connect the adsorbed molecules and the C_2N monolayer,thus strengthening the adsorption.Furthermore,we study the adsorption of H_2O and O_2 with the possible generation of hydroxyl(·OH)and superoxide(O_2~(·–))radicals,which are active for HCHO degradation;the results show that both molecules can also be strongly adsorbed on the Al-decorated C_2N surface.In particular,the dissociation of H_2O provides an excellent precondition for the generation of hydroxyl radicals.Our findings suggest that Al-decorated C_2N can be a promising material for the adsorption and subsequent catalytic degradation of HCHO molecules.
Carbonyl compounds,in particular formaldehyde(HCHO),are among the most common indoor air pollutants that have been found to be toxic to humans.Thus,in this study,density functional theory(DFT)calculations are performed to study the adsorption properties of HCHO on pristine and Al-decorated C_2N monolayer.The results indicate that Al-decorated C_2N has a strong adsorption ability for HCHO molecules with an adsorption energy of–2.585 eV.Moreover,partial density of states(PDOS),Mulliken atomic charges,and electron density distributions are calculated to investigate the adsorption enhancement mechanism.The results show that the Al atom serves as a bridge to connect the adsorbed molecules and the C_2N monolayer,thus strengthening the adsorption.Furthermore,we study the adsorption of H_2O and O_2 with the possible generation of hydroxyl(·OH)and superoxide(O_2~(·–))radicals,which are active for HCHO degradation;the results show that both molecules can also be strongly adsorbed on the Al-decorated C_2N surface.In particular,the dissociation of H_2O provides an excellent precondition for the generation of hydroxyl radicals.Our findings suggest that Al-decorated C_2N can be a promising material for the adsorption and subsequent catalytic degradation of HCHO molecules.
引文
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