Ru sensitized MOF electronic structure for efficient water electrolysis
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摘要: 金属有机框架(MOF)材料因其强大的结构和功能可调性已成为极具潜力的电解水催化剂。然而，MOF催化剂由于自身较弱的电荷转移能力及有限的稳定性，其固有活性较低。因此，设计出兼具高活性与高稳定性的MOF催化剂仍是具有挑战性的难题。本文通过两步水热法成功合成了CoRu-BDC/NF(BDC：对苯二甲酸、NF:泡沫镍)，Ru的引入调节了负载在NF上Co-BDC的内在活性，赋予了CoRu-BDC/NF丰富的活性位点、较快的电荷传输能力，有利于电催化性能的提升。结果表明，CoRu-BDC/NF在酸性环境中电流密度达到10 mA·cm−2时，HER过电位为34 mV，Tafel斜率为33 mV·dec−1。值得注意的是，在碱性条件下，当电流密度为10 mA·cm−2，HER和OER所需的过电位也仅为32 mV和280 mV，Tafel斜率分别为39 mV·dec−1 、49 mV·dec−1，均表现出优异的电催化性能。Ru的引入导致Co的电子结构和配位环境发生变化，使原始Co-MOF的表面积增加，为电化学反应提供了更好的电子转移平台，加快了电子在电极和电解液界面间的传递，进一步提升了电催化性能。Abstract: Metal-organic framework (MOF) materials have become potential catalysts for water electrolysis due to their strong structural and functional adjustability. However, the intrinsic activity of MOF catalyst is low due to its weak charge transfer ability and limited stability. Therefore, it is still a challenging problem to design MOF catalysts with high activity and high stability. In this paper, CoRu-BDC/NF(BDC: terylene acid, NF: nickel foam) was successfully synthesized by two-step hydrothermal method. The introduction of Ru regulated the intrinsic activity of Co-BDC loaded on NF, endowed CoRu-BDC/NF with abundant active sites and fast charge transport capacity, which was conducive to the improvement of electrocatalytic performance. The results show that when the current density of CoRu-BDC/NF reaches 10 mA·cm−2 in acidic environment, HER overpotential is 34 mV and Tafel slope is 33 mV·dec−1. It is worth noting that under alkaline conditions, when the current density is 10 mA·cm−2, the required overpotential of HER and OER is only 32 mV and 280 mV, and the slope of Tafel is 39 mV·dec−1 and 49 mV·dec−1, showing excellent electrocatalytic performance. The introduction of Ru leads to changes in the electronic structure and coordination environment of Co, increasing the surface area of the original Co-MOF, providing a better electron transfer platform for the electrochemical reaction, speeding up the transfer of electrons between the electrode and the electrolyte interface, and further improving the electrocatalytic performance.
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Key words:
- CoRu-BDC /
- Ru introduction /
- HER /
- OER /
- coordinated environment
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图 1 (a-d)分别CoRu-BDC/NF纳米复合材料的FE-SEM图像；(e-h,k)为CoRu-BDC的TEM图；(i-j)为CoRu-BDC的TEM-EDX图；(l)为CoRu-BDC电子衍射图
Figure 1. Fig 1(a-d) are the FE-SEM images of CoRu-BDC/NF nanocomposites, respectively. (e-h,k-i) indicates the TEM image of CoRu-BDC, (i-j) is the TEM-EDX image of CoRu-BDC
BDC—Terylene acid; NF—NAickel foam
图 2 Co-BDC和CoRu-BDC(a)XRD图；(b)拉曼图；(c)傅里叶变换红外光谱；(d) XPS全谱图；(e) Co 2p轨道的高分辨XPS图；(f) Ru 3d轨道的高分辨XPS图
Figure 2. Co-BDC and CoRu-BDC (a) XRD; (b) Raman map; (c) Fourier transform infrared spectrum; (d) XPS full spectrum; (e) high resolution XPS map of Co 2p orbit; (f) high resolution XPS map of Ru 3d orbit
图 3 NF、Co-BDC/NF、Ru-BDC/NF、CoRu-BDC/NF在0.5 mol/L H2SO4中的电化学HER测量：(a) 极化曲线；(b) Tafel斜率； (c) CoRU-BDC/NF不同扫速下的CV曲线； (d) 0.25 V (vs.RHE)处电流密度与扫速的差值； (e) 阻抗图；(f)HER过程中CoRu-BDC/NF的稳定性
Figure 3. Electrochemical HER measurements of NF, Co-BDC/NF, Ru-BDC/NF and CoRu-BDC/NF in 0.5 M H2SO4 . (a) Polarization curves, (b) Tafel plots,(c) CV curves at different sweeps of CoRu-BDC/NF speed, (d) Difference of current density at 0.25 V( vs.RHE) as a function of scan rate, (e) Nyquist plots, (f) Stability of the CoRu-BDC/NF during the HER process
j—Current density; E —Overpotentials; Z’ —Impedance the real part; Z’’ —Impedance virtual part
图 4 NF、Co-BDC/NF、Ru-BDC/NF和CoRu-BDC/NF：(a)在1 mol/L KOH中的电化学HER测试的极化曲线；(b)Tafel斜率；(c)测试前后XRD；(d)测试后的SEM图
Figure 4. NF, Co-BDC/NF, Ru-BDC/NF and CoRu-BDC/NF.(a) Polarization curves for the electrochemical HER tests in 1 M KOH,(b)Tafel plots,(c,d)XRD and SEM plots before and after testing
图 5 NF、Co-BDC/NF、Ru-BDC/NF和CoRu-BDC/NF：(a)在1 mol/L KOH中的电化学OER测试的极化曲线；(b) Tafel斜率； (c)阻抗图；(d) CoRU-BDC/NF不同扫速下的CV曲线； (e) 0.25 V (vs.RHE)处电流密度与扫速的差值；(f) CoRu-BDC/NF||CoRu-BDC/NF以5 mV·s−1在1 mol/L KOH整体水分的极化曲线。
Figure 5. NF, Co-BDC/NF, Ru-BDC/NF and CoRu-BDC/NF. (a) Polarization curves for the electrochemical OER tests in 1 M KOH, (b)Tafel plots, (c) Nyquist plots, (d) CV curves at different sweeps of CoRu-BDC/NF speed, (e) Difference of current density at 0.25 V (vs.RHE) as a function of scan rate, (e) Polarization curves for CoRu-BDC/NF||CoRu-BDC/NF couples toward overall water splitting recorded at a scan rate of 5 mV s −1 in 1 M KOH.
表 1 近期报道的相关材料全解水性能的比较
Table 1. Comparison of the recent reported overall water solution properties of related materials
Electrocatalyst Acid conditions
HER η10/mVAlkaline conditions
HER η10/mVAlkaline conditions
OER η10/mVOverall Water/V Reference CoRu-BDC/NF 34 32 280 1.47 This work Co-Co2C/CC / 96 261 1.63 [51] CoFeP-N / 64 219 1.56 [52] CoCu@NC / 199 301 1.87 [53] Co-CN@NiFe / 87 233 1.55 [54] Notes：η10—Overpotentials with a current density of 10 mA·cm−2 
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