Engineering single-atomic ruthenium catalytic sites on defective nickel-iron layered double hydroxide for overall water splitting

Abstract

Rational design of single atom catalyst is critical for efficient sustainable energy conversion. However, the atomic-level control of active sites is essential for electrocatalytic materials in alkaline electrolyte. Moreover, well-defined surface structures lead to in-depth understanding of catalytic mechanisms. Herein, we report a single-atomic-site ruthenium stabilized on defective nickel-iron layered double hydroxide nanosheets (Ru1/D-NiFe LDH). Under precise regulation of local coordination environments of catalytically active sites and the existence of the defects, Ru1/D-NiFe LDH delivers an ultralow overpotential of 18 mV at 10 mA cm−2 for hydrogen evolution reaction, surpassing the commercial Pt/C catalyst. Density functional theory calculations reveal that Ru1/D-NiFe LDH optimizes the adsorption energies of intermediates for hydrogen evolution reaction and promotes the O–O coupling at a Ru–O active site for oxygen evolution reaction. The Ru1/D-NiFe LDH as an ideal model reveals superior water splitting performance with potential for the development of promising water-alkali electrocatalysts.

Competitive Coordination‐Oriented Monodispersed Ruthenium Sites in Conductive MOF/LDH Hetero‐Nanotree Catalysts for Efficient Overall Water Splitting in Alkaline Media

“…[ 40 ] Moreover, the weak peak of the RuOM (M = Co or Ni) contribution (2.84 Å) in the higher shell was mainly derived from the CoNiRu‐LDH nanotrunk. [ 41 ] The coordination number (CN) of RuN(O) was estimated to be 4.0, confirming that numerous unsaturated RuN(O) 4 sites were successfully immobilized in the CoNiRu‐NT structure (Figure 3e; and Figures S30 and S31 and Table S3, Supporting Information). Furthermore, the metal‐N and metal‐O bonds showed a slight difference in the XAS spectra.…”

“…Interestingly, CoNiRu‐NT exhibited an impressive mass activity of 998 A g metal −1 , which is much larger than that of CoNiRu‐LDH (11 A g metal −1 ), CoNiRu‐NT1 (494 A g metal −1 ), and CoNiRu‐NT3 (743 A g metal −1 ) and ≈3.3 times higher than that of Pt/C (307 A g metal −1 ). [ 41 ] The specific activity, normalized by BET surface areas [ 50 ] of CoNiRu‐NT (0.018 mA cm −2 ) was ≈4.5‐, 1.8‐, and 2.3‐ times higher than those of CoNiRu‐LDH, CoNiRu‐NT1, and CoNiRu‐NT3, respectively, further revealing its superior HER activity.…”

Research Progress and Application of Single-Atom Catalysts: A Review

“…As a simple and efficient method for hydrogen production and oxygen production, electrocatalytic water-splitting is widely used in industrial production [81]. The use of catalyst electrocatalytic water-splitting is an effective way to prepare hydrogen fuel [82], which can realize the conversion and use of high-efficiency renewable energy [83]. The catalytic efficiency of the catalyst is of great significance in the study of electrocatalytic water-splitting.…”

Exceptional Catalytic Activity of Oxygen Evolution Reaction via Two-Dimensional Graphene Multilayer Confined Metal-Organic Frameworks

“…It con rms again the lower overpotential from the experiment for NiFe-BTC//G (106 mV) rather than that on Ni-BTC//G (212 mV) Fe-BTC//G (226 mV) (see detailed data in Supplementary Figs. [27][28][29][30][31], and Supplementary Table 3).…”

“…Using this approach, the overpotential of NiFe-BTC surprisingly drops from 399 mV (vs. RHE) to 106 mV (i.e., NiFe-BTC//G) at current density of 10 mA cm − 2 in 1.0 M KOH, which is superior to state-of-the-art reported MOFs catalysts, and even outcompete noble metal-based catalysts. [28][29][30][31][32] Moreover, the NiFe-BTC//G electrodes are stable and retain the performance for more than 150 h without obvious activity decay. The mechanistic details and active sites of the NiFe-BTC//G are proposed by a combination of X-ray absorption (XAS) experiments and density-functional theory (DFT) calculations.…”