双杂原子配位提高单原子锰位点的析氧活性

doi:10.1016/S1872-2067(23)64525-5

摘要/Abstract

摘要：

可再生能源的储存和转化可以增加能源利用的可及性, 是目前能源发展的主要方向. 析氧反应(OER)是电解水与可充电锌-空气电池的重要半反应, 然而其较高的反应势垒降低了能源利用效率. 因此, 开发高效和稳定的OER催化剂是提升能源利用的关键. 由于具有低成本和高原子利用率的优势, 非贵金属基单原子催化剂已被广泛应用于电催化析氧反应. 研究表明, 单原子催化剂的OER活性与其电子结构密切相关. 改变配位原子的种类和配位数可以调节单金属原子的d电子结构和自旋状态, 进一步优化反应中间体的吸附. 锰(Mn)是自然界光合作用系统的析氧中心, 近年来模拟Mn结构以最大程度激发催化活性受到了广泛的关注.

本文采用双杂原子配位方法来调节孤立锰位点的电子结构从而提升其OER性能. 以氧化石墨烯、氯化锰和硫粉为前驱体, 合成了双杂原子配位的单原子锰催化剂Mn-SG-500 (退火温度为500 °C), 其中单锰原子与两个硫原子和两个氧原子配位. 能谱分析(EDS)和X射线衍射(XRD)谱图中均未观察到锰基纳米粒子, 高角环形暗场-扫描透射电子显微镜(HAADF-STEM)图像显示均匀分散的亮点, 表明锰以单原子形式负载在石墨烯上. Mn的扩展X射线吸收精细结构(EXAFS)光谱结果表明, Mn-SG-500中的Mn表现出接近+2的化合价, 且不存在Mn-Mn键, 进一步说明Mn以单原子形式存在. 拟合结果显示, Mn-S键长为2.34 ± 0.07 Å, 配位数为1.7 ± 0.4; Mn-O键长为1.94 ± 0.05 Å, 配位数为1.8 ± 0.4. 电化学测试结果表明, 在碱性条件下, Mn-SG-500在电流密度为10 mA cm^-2时的过电位为332 mV, Tafel斜率为56 mV dec^-1. 与无硫掺杂样品Mn-G-500相比, 其过电位(η₁₀)降低了59 mV. 根据Arrhenius公式计算, S/O和Mn共配位降低了OER活化能. 此外, 在1.6 V (vs. RHE)电压下, Mn-SG-500连续运行25 h仍可保持电流密度在10 mA cm^-2以上. 差分脉冲伏安(DPV)结果表明, 在OER过程中, 锰的价态由+2变为+4, 说明四价锰是析氧反应的关键物种. 反应后的Mn 2p XPS谱图也证实了Mn(IV)的生成. 此外, 硫的加入使Mn⁴⁺到Mn²⁺的还原电位从1.39 V降至1.348 V, 提高了OER活性. 通过理论计算进一步揭示Mn-SG-500上OER催化活性中心为Mn-S₂O₂, 速率控步为*O氧化成*OOH, 其理论过电位为0.9 V, 远小于硫或氧单独配位的Mn-S₄和Mn-O₄.

综上所述, 催化剂Mn-SG-500的析氧活性提高是由于S和O的共配位引起了Mn电荷的重新分配和优化, 这对其它过渡金属基催化剂的进一步结构设计和性能优化具有参考意义, 也为相关催化领域的研究提供借鉴.

关键词: 双杂原子配体, 原位拉曼, 析氧反应, 单原子催化剂, 理论计算

Abstract:

The coordination of dual-heteroatom is an effective strategy to enhance the performance of oxygen evolution reaction (OER) of single-atom catalysts. Here, we synthesize Mn-SG-500 with isolated Mn sites coordinated with two sulfur and two oxygen atoms on graphene, and perform in-depth research on the structure-activity relationship for the OER. Under alkaline conditions, the Mn-SG-500 displays higher OER activity than commercial RuO₂. Combining in-situ structure analysis and theoretical calculations, we identify Mn-S₂O₂ as the catalytic active center, on which the oxidation of *O to *OOH is the rate-control step. The improved OER activity is attributed to the redistribution and optimization of Mn charges caused by the co-coordination of S and O. This work is helpful for further structure design and performance management of single-atom catalysts with dual-heteroatom doping.

Key words: Dual-heteroatom ligand, In-situ Raman, Oxygen evolution reaction, Single atom catalyst, Theoretical calculation

白雪, 韩璟怡, 陈思雨, 牛效迪, 管景奇. 双杂原子配位提高单原子锰位点的析氧活性[J]. 催化学报, 2023, 54: 212-219.

Xue Bai, Jingyi Han, Siyu Chen, Xiaodi Niu, Jingqi Guan. Improvement of oxygen evolution activity on isolated Mn sites by dual-heteroatom coordination[J]. Chinese Journal of Catalysis, 2023, 54: 212-219.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64525-5

https://www.cjcatal.com/CN/Y2023/V54/I11/212

图/表 5

Fig. 1. (a) Synthetic illustration of Mn-SG. (b) TEM image of Mn-SG-500. (c) HAADF-STEM image of Mn-SG-500. STEM image (d) and EDS elemental mappings (e) of Mn-SG-500.

Fig. 2. (a) XANES spectra at Mn K-edges of the Mn-SG-500 and referred samples. (b) FT-EXAFS spectra. (c) FT-EXAFS fitting spectrum. (d) Mn-S2O2 configuration.

Fig. 3. OER polarization curves (a) of G-500, SG-500, Mn-G-500, Mn-SG-500 and RuO2, and the corresponding Tafel slopes (b). (c) Activation energy of G-500, SG-500, Mn-G-500, and Mn-SG-500. (d) DPV curves of Mn-G-500 and Mn-SG-500. (e) Nyquist plots of the EIS test for the G-500, SG-500, Mn-G-500, and Mn-SG-500 (inset: the equivalent circuit used for fitting the Nyquist plots). (f) Chronoamperometry test for the Mn-SG-500.

Fig. 4. Ex-situ Mn 2p (a), S 2s (b), and O 1s (c) XPS spectra of fresh Mn-SG-500 and Mn-SG-500 after OER at overpotentials of 0.25, 0.35, 0.45 and 0.55 V, respectively.

Fig. 5. Population distributions for the DFT-calculated representative models: (a) Mn-S4G, (b) Mn-S3OG, (c) Mn-S2O2G para-position (d) Mn-S2O2G ortho-position, (e) Mn-SO3G, (f) Mn-S3G, (g) Mn-O3G and (h) Mn-O4G. (i) The optimized structures of three reaction intermediates of Mn-S2O2G and the reaction paths of free energy diagram for the OER on Mn-S4G, Mn-S3OG, Mn-S2O2G, Mn-SO3G, and Mn-S3G, Mn-O3G and Mn-O4G. (j) OER volcano plot of the overpotential η vs. the difference between the adsorption free energy of *O and *OOH for the seven models. (k) The projected DOS for the Mn-S2O2G. (l) The charge density differences of Mn in Mn-S2O2G. Yellow and blue areas represent charge density accumulation and depletion in the 3D map, respectively.

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