Cu(I)-based catalysts have proven to play an important role in the formation of specific hydrocarbon products from electrochemical carbon dioxide reduction reaction (CO 2 RR). However, it is difficult to understand the effect of intrinsic cuprophilic interactions inside the Cu(I) catalysts on the electrocatalytic mechanism and performance. Herein, two stable copper(I)-based coordination polymer (NNU-32 and NNU-33(S)) catalysts are synthesized and integrated into a CO 2 flow cell electrolyzer, which exhibited very high selectivity for electrocatalytic CO 2 -to-CH 4 conversion due to clearly inherent intramolecular cuprophilic interactions. Substitution of hydroxyl radicals for sulfate radicals during the electrocatalytic process results in an in situ dynamic crystal structure transition from NNU-33(S) to NNU-33(H), which further strengthens the cuprophilic interactions inside the catalyst structure. Consequently, NNU-33(H) with enhanced cuprophilic interactions shows an outstanding product (CH 4 ) selectivity of 82% at −0.9 V (vs reversible hydrogen electrode, j = 391 mA cm −2 ), which represents the best crystalline catalyst for electrocatalytic CO 2 -to-CH 4 conversion to date. Moreover, the detailed DFT calculations also prove that the cuprophilic interactions can effectively facilitate the electroreduction of CO 2 to CH 4 by decreasing the Gibbs free energy change of potential determining step (*H 2 COOH → *OCH 2 ). Significantly, this work first explored the effect of intrinsic cuprophilic interactions of Cu(I)-based catalysts on the electrocatalytic performance of CO 2 RR and provides an important case study for designing more stable and efficient crystalline catalysts to reduce CO 2 to high-value carbon products.

Nano-immunotherapy has been recognized as a highly promising strategy for cancer treatment in recent decades, which combines nanotechnology and immunotherapy to combat against tumors. Hybrid nanomaterials consisting of at least two constituents with distinct compositions and properties, usually organic and inorganic, have been engineered with integrated functions and enormous potential in boosting cancer immunotherapy. This review provides a summary of hybrid nanomaterials reported for cancer immunotherapy, including nanoscale metal-organic frameworks, metal-phenolic networks, mesoporous organosilica nanoparticles, metallofullerene nanomaterials, polymer-lipid, and biomacromolecule-based hybrid nanomaterials. The combination of immunotherapy with chemotherapy, chemodynamic therapy, radiotherapy, radiodynamic therapy, photothermal therapy, photodynamic therapy, and sonodynamic therapy based on hybrid nanomaterials is also discussed. Finally, the current challenges and the prospects for designing hybrid nanomaterials and their application in cancer immunotherapy are outlined.

The development of hydrogen-bonded organic frameworks (HOFs) with predictable topologies and robust structures for targeted functionality was initially hindered by the relatively weak H-bonding interactions as many HOFs would collapse upon guest solvent removal. Recently, the design of tectons with large π-conjugated systems that form intermolecular shape-fitted π-π stacking interactions has proven to be an effective strategy to create chemically and thermally stable HOFs. More importantly, these HOFs with large π-conjugated tectons exhibit accelerated redox hopping processes due to more favorable through-space orbital overlap interactions. These intrinsic photoelectric properties render HOFs an appealing and unique class of photoactive and electroactive porous materials for catalysis, sensing, and biomedical applications. Based on shape-fitted π-π stacking strategy, various robust photoactive and electroactive HOFs have been built from tectons containing both photosensitive or redox-active organic cores and hydrogen bonding sites. This review summarizes the recent advancements, including synthetic methods and diverse applications, in the development of photo-and electro-active HOFs. Considering the numerous photo-and electro-active organic units available, as well as the virtually unlimited potential combinations of organic cores and hydrogen bonding sites, we anticipate that this review will inspire scientists in a range of disciplines, ranging from porous materials to organic photoelectric materials and catalysis scientists, to further explore functional photo-and electro-active HOF materials.

Comprehensive Summary Recently, artificial and semi‐artificial photosynthesis have attracted extensive attentions in addressing the crisis of energy from fossil fuels and reducing excessive CO2 emission. Metal‐organic frameworks (MOFs) have been considered as ideal platforms for constructing artificial photosynthesis systems due to their unique properties like large specific surface area, high porosity and diverse framework topology, and tunable functionalities. This review discussed the characteristics, superiorities and challenges of MOF‐based photocatalysts, and detailed summarization of several common design strategies for MOF‐based artificial systems, including i) enhancement of light absorption, ii) acceleration of the charge separation and transfer, and iii) introduction of additional active units. Particularly, we give examples showing the applications of MOF‐based photocatalysts, where the mechanisms of superior photocatalytic activity and selectivity are also analyzed, thereby providing theoretical guidance for rational design of MOF‐based photocatalysts. Finally, the challenges and future research directions of MOF‐based photocatalysts are prospected.