Abstract Crystal‐facet heterojunction engineering of mesoporous nanoreactors with highly redox‐active represents an efficacious strategy for the transformation of CO 2 into valuable C 2 products (e.g., C 2 H 4 ). Herein, hollow mesoporous cube‐like CuS nanoreactors (~860 nm) with controlled anisotropic crystal‐facets are prepared through an interfacial‐confined ion dynamic migration‐rearrangement strategy. The regulation of the S 2− ion concentration facilitates the modulation of the highly active (110) to (100) crystal‐facet ratios from 0.119 to 0.288, and induces the formation of anisotropic crystal‐facet heterojunctions. The controllable crystal‐facet heterojunctions trigger the directional charge carrier migration, and are accompanied with the formation of tandem S‐defect sites (Cu 0 ‐S 1 @S 3 ). Both of them promote the efficient electron‐hole pair dissociation and attain asymmetric C−C coupling. The hollow mesoporous CuS nanoreactors with optimized crystal‐facet ratio of 0.224 (HMe‐CuS‐3) deliver a high selectivity of 72.7 % for the photocatalytic reduction of CO 2 to acetylene (C 2 H 2 ). Further constructed Au‐(110) and Co 3 O 4 ‐(100) spatially separated cascade nanoreactors (SS‐Au@Co 3 O 4 ‐CuS) achieve CO 2 ‐C 2 H 4 photoreduction, in which the Co‐sites enhance H 2 O dissociation to provide protons and the protonation of *CO to *COH. The *COH is further captured by Au‐sites to accomplish the asymmetric *CO‐*COH coupling and subsequent protonation, ensuring a high C 2 H 4 generation rate of 4.11 μmol/g/h with a selectivity as high as 90.6 %.

Metal-organic framework (MOF) glasses are an emerging class of glasses which complement traditional inorganic, organic and metallic counterparts due to their hybrid nature. Although a few zeolitic imidazolate frameworks have been made into glasses, how to melt and quench the largest subclass of MOFs, metal carboxylate frameworks, into glasses remains challenging. Here, we develop a strategy by grafting the zwitterions on the carboxylate ligands and incorporating organic acids in the framework channels to enable the glass formation. The charge delocalization of zwitterion-acid subsystem and the densely filled channels facilitate the coordination bonding mismatch and thus reduce the melting temperature. Following melt-quenching realizes the glass formation of a family of carboxylate MOFs (UiO-67, UiO-68 and DUT-5), which are usually believed to be un-meltable. Our work opens up an avenue for melt-quenching porous molecular solids into glasses.

Main group metals are routinely considered as catalytically inactive. In this work, we for the first time prepared a p-block tin single atom catalyst (Sn SA –NC) with Sn–N 4 active site for effectively improving the lithium–sulfur battery performance.

Abstract The design of three‐dimensional covalent organic frameworks (3D COFs) using linear and trigonal linkers remains challenging due to the difficulty in achieving a specific non‐planar spatial arrangement with low‐connectivity building units. Here, we report the novel 3D COFs with linear and trigonal linkers, termed TMB‐COFs, exhibiting srs topology. The steric hindrance provides an additional force to alter the torsion angles of peripheral triangular units, guiding the linear unit to connect with the trigonal unit into 3D srs frameworks, rather than the more commonly observed two‐dimensional (2D) hcb structures. Furthermore, we comprehensively examined the hydrogen peroxide photocatalytic production capacity of the TMB‐COFs in comparison with analogous 2D COFs. The experimental results and DFT calculations demonstrate a significant enhancement in photocatalytic hydrogen peroxide production efficacy through framework regulation. This work emphasizes the steric configuration using low connectivity building units, offering a fresh perspective on the design and application of 3D COFs.

Abstract The development of low‐cost, high‐efficiency, and stable electrocatalysts for hydrogen evolution reaction (HER) under alkaline conditions is a key challenge in water electrolysis. Here, an interfacial engineering strategy that is capable of simultaneously regulating nanoscale structure, electronic structure, and interfacial structure of Mo 2 N quantum dots decorated on conductive N‐doped graphene via codoping single‐atom Al and O (denoted as AlO@Mo 2 N‐NrGO) is reported. The conversion of Anderson polyoxometalates anion cluster ([AlMo 6 O 24 H 6 ] 3− , denoted as AlMo6) to Mo 2 N quantum dots not only result in the generation of more exposed active sites but also in situ codoping atomically dispersed Al and O, that can fine‐tune the electronic structure of Mo 2 N. It is also identified that the surface reconstruction of AlOH hydrates in AlO@Mo 2 N quantum dots plays an essential role in enhancing hydrophilicity and lowering the energy barriers for water dissociation and hydrogen desorption, resulting in a remarkable alkaline HER performance, even better than the commercial 20% Pt/C. Moreover, the strong interfacial interaction (MoN bonds) between AlO@Mo 2 N and N‐doped graphene can significantly improve electron transfer efficiency and interfacial stability. As a result, outstanding stability over 300 h at a current density higher than 100 mA cm −2 is achieved, demonstrating great potential for the practical application of this catalyst.

Abstract The oriented assembly of heterostructures at the boundaries of nanosheets offers substantial advantages over surface‐based heterostructures, owing to their enhanced built‐in electric fields, more efficient charge transport pathways, and greater accessibility of active sites. However, the precise design of boundary‐engineered heterojunctions remains challenging due to the complex process and unclear growth mechanism. Herein, the development of a boundary‐engineered heterojunction is reported by loading Ce‐Ni(OH) 2 onto the edges of Co‐MOF nanosheets through a regulated electrodeposition process, driven by boundary effect induced by Ce single‐atom doping. A systematic investigation is conducted to explore the effects of boundary effect on the construction of boundary‐engineered heterojunctions. The Co‐MOF/Ce‐Ni(OH) 2 @CC exhibits superior oxygen evolution reaction (OER) activity, achieving an ultra‐low overpotential of 140 mV at 10 mA cm −2 in 1 M KOH. Enhanced by density functional theory (DFT) calculations and in situ Raman characterization, the Ce single‐atom acts as an electron reservoir for Ni sites via the Ce─O─Ni chain during OER, thereby facilitating electron transfer from Ni(OH) 2 to Co‐MOF. This promotes the formation of NiOOH and boosts the OER activity. Furthermore, the Kelvin probe force microscopy (KPFM) analysis reveals that the incorporation of Ce intensifies the local electric field at the nanosheet boundary, and facilitates the deposition of Ni(OH) 2 on the edges, thereby promoting the formation of boundary‐engineered heterojunctions.

Abstract Dynamically self‐adaptive optimizing the local microenvironment of Ru─O bonds to enhance the adsorption of the *H is crucial for the efficient catalytic process. However, the limited regulatory strategies are unable to spontaneously control the Ru─O reconstruction process, thereby preventing the competitive adsorption of key intermediates at the catalytic active sites. Herein, an electronic asymmetry engineering is proposed by Ru single atoms coordinate with P and O atoms to create a local asymmetric O─Ru─P moiety, achieving dynamic optimization of Ru─O bond under the potential driven state during the HER process. The resultant Ru SA ─CoP electrocatalyst exhibits remarkable overpotentials of 15, 38, and 36 mV at a current density of 10 mA cm −2 in alkaline, acidic, and neutral media. Advanced in‐situ characterization reveals that the asymmetric O─Ru─P sites can modulate electron redistribution under the potential‐driven conditions, which achieves dynamic optimization of Ru─O bonds and strengthens Ru─H bonding interactions. More importantly, when the voltage is removed, the Ru─O bond is clearly observed again, which reveals the dynamic adaptation of Ru─O coordination during the reaction process. This work reveals the influence of the dynamic coordination evolution and structural adaptability of electrocatalysts on catalytic performance, providing valuable ideas for the design and synthesis of efficient electrocatalysts.