第一作者：Taoxia Ma, Ruqi Li, Yu-Cheng Huang
通讯作者：延安大学-杨春明、付峰、王丹军
DOI：10.1021/acscatal.3c05416
光催化氮还原反应(pNRR)是一种理想的氨合成技术。虽然在温和条件下制备的pNRR催化剂得到了广泛的发展，但仍存在N2吸附/活化不足和NH3选择性低的局限性。本文采用静电自组装方法构建了具有界面化学键的MoS2/ In-Bi2MoO6异质结催化剂。由于在MoS2和In-Bi2MoO6界面形成Mo-S键，促进了光生电子/空穴对的有效空间分离和加速载流子转移动力学。晶体轨道哈密顿族(COHP)分析进一步证实，电子从MoS2转移到N2的反键轨道，激活了被吸附的N2，有利于氮-氨(N2-to-NH3)转化。3% MoS2/ In-Bi2MoO6的NH3/NH4+产率达到90 μmol·g-1·h-1，比纯Bi2MoO6有显著提高，而NO3-产率极低。引入MoS2作为助催化剂可有效抑制NH3/NH4+氧化为NO3-，实现选择性pNRR。这项工作为选择性光催化固氮奠定了基础，为NH3的清洁生产提供了有价值的见解。
Figure 2. (a)Nitrogen fixation performance of the MoS2/In-BMO heterojunction. (b) Ammonia production rate. (c) Photocatalytic yield of NH3/NH4+, NO3−, and N2H4 using In-BMO as photocatalyst. (d) NO3− yield on BMO, 5% In-BMO, and 3% MoS2/In-BMO using NH4Cl as feedstock.(e) 1H NMR spectra after photocatalytic nitrogen fixation for ammonia using 14N2 or 15N2 feeding gas. (f) Long-time test of 3% MoS2/In-BMO for NH3/NH4+ yield. (g) Bi L3-edge, (h) Mo, and (i) In K-edge XANES spectra of 3% MoS2/In-BMO. (j) Bi L3-edge, (k) Mo, and (l) In K-edge EXAFS spectra shown in the k3 weighted R-space of 3% MoS2/In-BMO.
Figure 3. (a) Photocurrent responses, (b) Nyquist plots, (c) steady-state PL profiles, and (d) time-resolved PL spectra of BMO, MoS2, 5% In-BMO, and 3% MoS2/In-BMO.
Figure 4. Calculated average potential profile along the z-direction of (a) MoS2 and (b) In-BMO. (c) Model of Mo−S chemical-bonded MoS2/In-BMO heterostructure. (d) Electrostatic potential. (e) Charge density distribution. (f) S-scheme photogenerated carrier transfer pathway mechanism.
Figure 5. In situ XPS spectra of (a) Bi 4f and S 2p, (b) Mo 3d and S 2p, (c) In 3d, and (d) O 1s electrons of 3% MoS2/In-BMO.
Figure 6. (a) Schematic of NN bond adsorption/activation process. (b) Formation of interfical chemical-bond at MoS2 and In-BMO interface. (c) Partial DOS of Mo and S atoms. (d) Schematic representation of the synergistic electron interaction among Mo, and S in MoS2/In-BMO. (e) Charge density difference at the interface of the MoS2/In-BMO heterostructure. The yellow and blue regions represent net electron accumulation and depletion, respectively. (f) S-scheme carrier transfer pathway in MoS2/In-BMO heterojunction. (g) COHP of NN bond on MoS2/In-BMO heterostructures. (h) N2-TPD of MoS2/In-BMO heterostructures.
Interfacial Chemical-Bonded MoS2 /In−Bi2MoO6 Heterostructure for Enhanced Photocatalytic Nitrogen-to-Ammonia Co -nversion
来源 | 光催化顶刊动态
编辑 | 高 甜
初审 | 黎柯柯
审核 | 梁怡雪
责任编辑 | 胡忠艳
主编 | 王 平
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