Metal-organic frameworks (MOFs) have been recognized as compelling platforms for the development of miscellaneous applications because of their structural diversity and functional tunability. Here, we propose that the electrocatalytic properties could be well modified by incorporating missing linkers into the MOF. Theoretical calculations suggest the electronic structure of MOFs can be tuned by introducing missing linkers, which improves oxygen evolution reaction (OER) performance of the MOF. Inspired by these aspects, we introduced various missing linkers into a layered-pillared MOF Co2(OH)2(C8H4O4) (termed as CoBDC) to prepare missing-linker MOFs. Transmission electron microscope and synchrotron X-ray measurements confirmed that the missing linkers in the MOF could be introduced and well controlled by our strategy. The self-supported MOF nanoarrays with missing linkers of carboxyferrocene exhibit excellent OER performance with ultralow overpotential of 241 mV at 100 mA cm−2. This work opens a new prospect to develop efficient MOF-based electrocatalysts by introducing missing linkers.

Developing high-performance electrocatalysts toward hydrogen evolution reaction is important for clean and sustainable hydrogen energy, yet still challenging. Herein, we report a single-atom strategy to construct excellent metal-organic frameworks (MOFs) hydrogen evolution reaction electrocatalyst (NiRu0.13-BDC) by introducing atomically dispersed Ru. Significantly, the obtained NiRu0.13-BDC exhibits outstanding hydrogen evolution activity in all pH, especially with a low overpotential of 36 mV at a current density of 10 mA cm−2 in 1 M phosphate buffered saline solution, which is comparable to commercial Pt/C. X-ray absorption fine structures and the density functional theory calculations reveal that introducing Ru single-atom can modulate electronic structure of metal center in the MOF, leading to the optimization of binding strength for H2O and H*, and the enhancement of HER performance. This work establishes single-atom strategy as an efficient approach to modulate electronic structure of MOFs for catalyst design.

Interface engineering has been recognized as one of the most promising strategies for regulating the physical and chemical properties of materials. However, constructing well‐defined nanointerfaces with efficient oxygen evolution reaction (OER) still remains a challenge. Herein, cross columnar NiTe nanoarrays supported on nickel foam are prepared. Subsequently, NiTe/NiS nanointerfaces are constructed by an ion‐exchange process. Importantly, the electrocatalytic performance for the OER can be facilitated by coupling NiTe and NiS. As a result, NiTe/NiS shows excellent OER activity with an ultralow overpotential of only 257 mV at a current density of 100 mA cm−2, and a Tafel slope of 49 mV dec−1 in 1.0 m KOH. The calculated and experimental results reveal that the strong electron interaction on nanointerfaces induces electronic structure modulation, which optimizes the binding energy of *OOH intermediates, thus improving the OER performance.

Exploring effective electrocatalysts for oxygen evolution reaction (OER) is a crucial requirement of many energy storage and conversion systems, involving fuel cells, water splitting, and metal–air batteries. Herein, a heterogeneity metal‐organic framework (MOF) is prepared by the assembling of metals, terephthalic (A) and 2‐aminoterephthalic ligands (B), defined as A2.7B‐MOF‐FeCo1.6. More importantly, A2.7B‐MOF‐FeCo1.6 exhibits excellent OER activity with an ultralow overpotential of 288 mV at 10 mA cm−2 and a Tafel slope of 39 mV dec−1. The high electrocatalytic performance for OER is attributed to the optimized electronic structure of the intrinsic catalytic center in MOFs via the engineering of the metal node and linkers. The work offers not only a benchmark for pure MOFs in electrocatalysis but also a new efficient strategy to improve electrocatalytic performance by electronic structure engineering of catalytic active centers in MOFs.

The exploration of novel porous core–shell materials is of great significance because of their prospectively improved performance and extensive applications in separation, energy conversion, and catalysis. Here, mesoporous metal–organic frameworks (MOFs) NH 2 ‐MIL‐101(Fe) as a core generate a shell with mesoporous covalent organic frameworks (COFs) NUT‐COF‐1(NTU) by a covalent linking process, the composite NH 2 ‐MIL‐101(Fe)@NTU keeping retentive crystallinity with hierarchical porosity well. Importantly, the NH 2 ‐MIL‐101(Fe)@NTU composite shows significantly enhanced catalytic conversion and selectivity during styrene oxidation. It is mainly due to the hydrophilic MOF nanocrystals readily gathering the hydrophobic reactants styrene and boosting the radical mechanism path after combining the hydrophobic COFs shell. The synthetic strategy in this systematic study develops a new rational design for the synthesis of other core–shell MOF/COF‐based hybrid materials, which can expand the promising applications.