Engineering Multifunctional Collaborative Catalytic Interface Enabling Efficient Hydrogen Evolution in All pH Range and Seawater

Abstract

Developing electrocatalysts with high compatibility to the reaction systems with complicated chemical properties represents an important frontier of catalyst design. Herein, a strategy by engineering a multifunctional collaborative catalytic interface to propel the hydrogen evolution reaction (HER) in the full pH range and seawater is reported. Collaborative catalytic interfaces among MXene, bimetallic carbide, and hybridized carbon are demonstrated to afford overall enhancement in electrical conductivity, exposure of reactive sites, water dissociation kinetics, H+/water adsorption, and intermediate H binding capability, which satisfy highly variable chemical environment for HER under different pH conditions. Therefore, the HER performance of resultant electrocatalysts can compete with commercial Pt/C in 0.5 m H2SO4 or 1.0 m KOH but outperform it under pH 2.2–11.2. They also show exceptional performance for HER in natural seawater with stringent requirements in catalytic activity and stability, exhibiting the best combination of Pt‐like activity, long durability (225 h, 64 times that of Pt/C), and 98% Faradaic efficiency, comparable with commercial Pt/C and the best documented electrocatalysts by far. This work may shed fresh light into the design of effective electrocatalytic interface for regulating the energy chemistry over wide operation conditions, and also inspires the exploration of hydrogen energy utilization technologies and beyond.

Multilevel Hollow MXene Tailored Low‐Pt Catalyst for Efficient Hydrogen Evolution in Full‐pH Range and Seawater

“…[38][39][40][41][42][43] Electrolysis of neutral seawater to hydrogen attracted considerable attention because it is mild and eco-friendly to avoid the harsh conditions and contamination in traditional alkaline and PEM-based electrolyzers. [44] When integrating with the chlorine-alkali industry, the seawater electrolysis technology could bring more economic benefits in yielding hydrogen plus important industrial raw materials. [38] Motived by high activity of 2.4% Pt@mh-3D MXene, its HER performance is also evaluated in natural seawater (Bohai Sea, China).…”

“…Meanwhile, the electronegative surface of MXene with ultralow work function further provides more opportunities to attract H + while tailoring the electronic state of the catalyst. [33,34] All these merits enable the MXene to be a potentially ideal "multifunctional promoter" to cooperate well with Pt for yielding efficient and durable HER catalysts.…”

Etching‐Doping Sedimentation Equilibrium Strategy: Accelerating Kinetics on Hollow Rh‐Doped CoFe‐Layered Double Hydroxides for Water Splitting

“…As shown in Figure 3c and Table S2 in the Supporting Information, Rh-doped CoFe-ZLDH outperforms many other previously reported state-of-art HER electrocatalysts, such as Rh 2 P, [41] L-Ag, [42] single atomic Co supported on phosphorized carbon nitride nanosheets (Co 1 /PCN), [43] NiMoO x -Ni(OH) 2 /NF, [44] interface catalyst consisting of atomic cobalt array covalently bound to distorted 1T MoS 2 nanosheets (SA Co-D 1T MoS 2 ), [45] Pt clusters in hollow mesoporous carbon spheres (Pt 5 /HMCS), [46] Ni-Fe nanoparticle (Ni-Fe NF), [39] oxygen vacancy enrich CoFe 2 O 4 (r-CFO), [47] CoFeP TAPs/Ni, [48] nickel-molybdenum-nitride nanoplates on carbon fiber cloth (Ni-Mo-N/CFC), [40] Ru SA -N-S-Ti 3 C 2 T x , [9] W-CoP NAs-CC, [49] MoP@NCHs-900, [50] Co 9 S 8 @C, [51] and Co 0.31 Mo 1.69 C/MXene/NC. [52] The cyclic voltammetry (CV) method was utilized to calculate the electrochemical double-layer capacitance (C dl ) to reflect the electrochemical active area (ECSA). [53] As demonstrated in Figure 3d and Figure S15a in the Supporting Information, Rhdoped CoFe-ZLDH has the largest C dl of 33.8 mF cm −2 , which is much higher than that of Rh-doped CoFe-LDH (7.62 mF cm −2 ), CoFe-ZLDH (0.71 mF cm −2 ), CoFe-LDH (0.5 mF cm −2 ), and NF (0.44 mF cm −2 ), as calculated based on corresponding CV curves ( Figure S16, Supporting Information).…”

Recent Progress in MXene‐Based Materials: Potential High‐Performance Electrocatalysts

“…Compared with pure Mo 2 CT x MXene catalysts, MoS 2 @Mo 2 CT x nanohybrids showed significantly enhanced HER activity, with a low overpotential of 176 mV in alkaline media at a current density of 10 mA cm −2 and a very small transfer resistance of 26 Ω. DFT calculations indicated that the reduction of the hydrogen adsorption energy of the MoS 2 @Mo 2 CT x nanohybrids could be attributed to fast electron transport ensured by Mo 2 CT x with intrinsic conductivity and a large number of hydrogen adsorption sites provided by MoS 2 nanoflowers. In addition, Wu et al [53] demonstrated performing efficient HER in full pH range by precisely constructing multifunctional collaborative catalytic interface among bimetallic cobalt-molybdenum carbide, hybrid carbon, and MXene. The results indicated that the electrocatalytic performance of the synthesized electrocatalyst (Co x Mo 2−x C/MXene/NC) could compete with commercial Pt/C catalysts in 0.5 m H 2 SO 4 or 1.0 m KOH while outperforming it under pH 2.2-11.2.…”