Pseudomorphic Transformation of Interpenetrated Prussian Blue Analogs into Defective Nickel Iron Selenides for Enhanced Electrochemical and Photo‐Electrochemical Water Splitting

Abstract

A significant methodology gap remains in the construction of advanced electrocatalysts, which has collaborative defective functionalities and structural coherence that maximizes electrochemical redox activity, electrical conductivity, and mass transport characteristics. Here, a coordinative self‐templated pseudomorphic transformation of an interpenetrated metal organic compound network is conceptualized into a defect‐rich porous framework that delivers highly reactive and durable photo(electro)chemical energy conversion functionalities. The coordinative‐template approach enables previously inaccessible synthesis routes to rationally accomplish an interconnected porous conductive network at the microscopic level, while exposing copious unsaturated reactive sites at the atomic level without electronic or structural integrity trade‐offs. Consequently, porous framework, interconnected motifs, and engineered defects endow remarkable electrocatalytic hydrogen evolution reaction and oxygen evolution reaction activity due to intrinsically improved turnover frequency, electrochemical surface area, and charge transfer. Moreover, when the hybrid is coupled with a silicon photocathode for solar‐driven water splitting, it enables photon assisted redox reactions, improved charge separation, and enhanced carrier transport via the built‐in heterojunction and additive co‐catalyst functionality, leading to a promising photo(electro)chemical hydrogen generation performance. This work signifies a viable and generic approach to prepare other functional interconnected metal organic coordinated compounds, which can be exploited for diverse energy storage, conversion, or environmental applications.

Stimulated Electrocatalytic Hydrogen Evolution Activity of MOF‐Derived MoS2 Basal Domains via Charge Injection through Surface Functionalization and Heteroatom Doping

“…Sci. [36] The Nyquist plots clearly reveal that MoS-CoS-Zn possesses a substantially smaller charge transfer resistance relative to CoS, MoS, and MoS-CoS. MoS-CoS-Zn possesses the highest 2C dl of 41.7 mF cm −2 , surpassing that of CoS (13.4 mF cm −2 ), MoS (16.5 mF cm −2 ), and MoS-CoS (19.8 mF cm −2 ), thus indicating rich active surface sites in MoS-CoS-Zn.…”

Oriented Transformation of Co‐LDH into 2D/3D ZIF‐67 to Achieve Co–N–C Hybrids for Efficient Overall Water Splitting

“…On the other hand, it should be remarked that the implementation of MOFs‐derived catalysts usually involved with Nafion polymer as the binder to cast the active materials onto glassy carbon electrode, in which the binder not only blocked the active sites, but also increased the interfacial resistance and the dwell volume, lowering the utilization of the active sites and lessening the mass transfer ability . To address these issues, assembling and space‐confining MOFs‐derived nanohybdrids on the current collector as a self‐supporting electrode is an effective strategy . For example, Cai et al reported the oriented growth of ZIF‐67 nanowall arrays on nickel foam through the coordination reaction between sacrificial metal oxide (CoO) nanowires arrays and 2‐methylimidazole (2‐MeIM) at room temperature and derived self‐supporting electrode for water splitting .…”

Highly dispersed ultrafine Ni particles embedded into MOF-74 arrays by partial carbonization for highly efficient hydrogen evolution

“…Up to now, the search for non-precious electrocatalysts with high performance for realizing highly efficient HER is still a challenging issue. [6][7][8][9][10][11][12][13] Numerous studies have demonstrated that a large number of HER catalysts, such as metal-organic frameworks (MOFs), [14][15][16][17] transition-metal carbides, [18][19][20] chalcogenides, [21][22][23][24][25] phosphides and nitrides, [26][27][28][29][30] are explored as highly efficient electrocatalysts in basic electrolytes. Especially in recent years, MOFs have attracted more and more interest.…”