Successful Decontamination of 99TcO4− in Groundwater at Legacy Nuclear Sites by a Cationic Metal‐Organic Framework with Hydrophobic Pockets

⁹⁹Tc contamination at legacy nuclear sites is a serious and unsolved environmental issue. The selective remediation of ⁹⁹TcO₄^? in the presence of a large excess of NO₃^? and SO₄^2? from natural waste systems represents a significant scientific and technical challenge, since anions with a higher charge density are often preferentially sorbed by traditional anion‐exchange materials. We present a solution to this challenge based on a stable cationic metal‐organic framework, SCU‐102 (Ni₂(tipm)₃(NO₃)₄), which exhibits fast sorption kinetics, a large capacity (291 mg g^?1), a high distribution coefficient, and, most importantly, a record‐high TcO₄^? uptake selectivity. This material can almost quantitatively remove TcO₄^? in the presence of a large excess of NO₃^? and SO₄^2?. Decontamination experiments confirm that SCU‐102 represents the optimal Tc scavenger with the highest reported clean‐up efficiency, while first‐principle simulations reveal that the origin of the selectivity is the recognition of TcO₄^? by the hydrophobic pockets of the structure.     

Intrinsic Broadband White‐Light Emission from Ultrastable,Cationic Lead Halide Layered Materials

We report a family of cationic lead halide layered materials, formulated as [Pb₂X₂]²⁺[⁻O₂C(CH)₂CO₂⁻] (X=F, Cl, Br), exhibiting pronounced broadband white‐light emission in bulk form. These well‐defined PbX‐based structures achieve an external quantum efficiency as high as 11.8 %, which is comparable to the highest reported value (ca.9 %) for broadband phosphors based on layered organolead halide perovskites. More importantly, our cationic materials are ultrastable lead halide materials, which overcome the air/moisture‐sensitivity problems of lead perovskites. In contrast to the perovskites and other bulk emitters, the white‐light emission intensity of our materials remains undiminished after continuous UV irradiation for 30 days under atmospheric conditions (ca.60 % relative humidity). Our mechanistic studies confirm that the broadband emission is ascribed to short‐range electron‐phonon coupling in the strongly deformable lattice and generated self‐trapped carriers.     

Semiconductive Copper(I)–Organic Frameworks for Efficient Light‐Driven Hydrogen Generation Without Additional Photosensitizers and Cocatalysts

As the first example of a photocatalytic system for splitting water without additional cocatalysts and photosensitizers, the comparatively cost‐effective Cu₂I₂‐based MOF, Cu‐I‐bpy (bpy=4,4′‐bipyridine) exhibited highly efficient photocatalytic hydrogen production (7.09 mmol g⁻¹ h⁻¹). Density functional theory (DFT) calculations established the electronic structures of Cu‐I‐bpy with a narrow band gap of 2.05 eV, indicating its semiconductive behavior, which is consistent with the experimental value of 2.00 eV. The proposed mechanism demonstrates that Cu₂I₂ clusters of Cu‐I‐bpy serve as photoelectron generators to accelerate the copper(I) hydride interaction, providing redox reaction sites for hydrogen evolution. The highly stable cocatalyst‐free and self‐sensitized Cu‐I‐bpy provides new insights into the future design of cost‐effective d¹⁰‐based MOFs for highly efficient and long‐term solar fuels production.     

Cooperative Multifunctional Catalysts for Nitrone Synthesis: Platinum Nanoclusters in Amine‐Functionalized Metal–Organic Frameworks

Nitrones are key intermediates in organic synthesis and the pharmaceutical industry. The heterogeneous synthesis of nitrones with multifunctional catalysts is extremely attractive but rarely explored. Herein, we report ultrasmall platinum nanoclusters (PtNCs) encapsulated in amine‐functionalized Zr metal–organic framework (MOF), UiO‐66‐NH₂ (Pt@UiO‐66‐NH₂) as a multifunctional catalyst in the one‐pot tandem synthesis of nitrones. By virtue of the cooperative interplay among the selective hydrogenation activity provided by the ultrasmall PtNCs and Lewis acidity/basicity/nanoconfinement endowed by UiO‐66‐NH₂, Pt@UiO‐66‐NH₂ exhibits remarkable activity and selectivity, in comparison to Pt/carbon, Pt@UiO‐66, and Pd@UiO‐66‐NH₂. Pt@UiO‐66‐NH₂ also outperforms Pt nanoparticles supported on the external surface of the same MOF (Pt/UiO‐66‐NH₂). To our knowledge, this work demonstrates the first examples of one‐pot synthesis of nitrones using recyclable multifunctional heterogeneous catalysts.     

Effective and Selective Catalysts for Cinnamaldehyde Hydrogenation: Hydrophobic Hybrids of Metal–Organic Frameworks,Metal Nanoparticles,and Micro‐ and Mesoporous Polymers

Metal–organic frameworks (MOFs) as selectivity regulators for catalytic reactions have attracted much attention, especially MOFs and metal nanoparticle (NP) shelled structures, e.g., MOFs@NPs@MOFs. Nevertheless, making hydrophilic MOF shells for gathering hydrophobic reactants is challenging. Described here is a new and viable approach employing conjugated micro‐ and mesoporous polymers with iron(III) porphyrin (FeP‐CMPs) as a new shell to fabricate MIL‐101@Pt@FeP‐CMP. It is not only hydrophobic and porous for enriching reactants, but also possesses iron sites to activate C=O bonds, thereby regulating the selectivity for cinnamyl alcohol in the hydrogenation of cinnamaldehyde. Interestingly, MIL‐101@Pt@FeP‐CMP^sponge can achieve a high turnover frequency ( 1516.1 h⁻¹), with 97.3 % selectivity for cinnamyl alcohol at 97.6 % conversion.     

Carbon‐Incorporated Nickel–Cobalt Mixed Metal Phosphide Nanoboxes with Enhanced Electrocatalytic Activity for Oxygen Evolution

Hollow nanostructures have attracted increasing research interest in electrochemical energy storage and conversion owing to their unique structural features. However, the synthesis of hollow nanostructured metal phosphides, especially nonspherical hollow nanostructures, is rarely reported. Herein, we develop a metal–organic framework (MOF)‐based strategy to synthesize carbon incorporated Ni–Co mixed metal phosphide nanoboxes (denoted as NiCoP/C). The oxygen evolution reaction (OER) is selected as a demonstration to investigate the electrochemical performance of the NiCoP/C nanoboxes. For comparison, Ni–Co layered double hydroxide (Ni–Co LDH) and Ni–Co mixed metal phosphide (denoted as NiCoP) nanoboxes have also been synthesized. Benefiting from their structural and compositional merits, the as‐synthesized NiCoP/C nanoboxes exhibit excellent electrocatalytic activity and long‐term stability for OER.     

A Versatile Metalloporphyrinic Framework Platform for Highly Efficient Bioinspired,Photo‐ and Asymmetric Catalysis

Even though numerous bioinspired catalysts have been developed, there remain huge gaps between the artificial and natural catalysts, because it is very difficult to imitate simultaneously the complicated constituents, structures, and synergistic effect of enzymes. We report herein a versatile metalloporphyrinic framework platform, which exhibits high efficiency in bioinspired catalysis, photocatalysis, and asymmetric catalysis. The catalytic properties are highly dependent on the tunable constituents and their cooperation, and are significantly superior to the corresponding molecular catalyst systems which lack the synergistic effects. Since there are numerous functional moieties that can readily be incorporated into the metalloporphyrinic framework platform, a myriad of applications can be simply realized by embedding different functional moieties.     

Anion Exchange Renders Hydrophobic Capsules and Cargoes Water‐Soluble

Control over the solubility properties of container molecules is a central challenge in host–guest chemistry. Herein we present a simple anion‐exchange protocol that allows the dissolution in water of various hydrophobic metal–organic container molecules prepared by iron(II)‐templated subcomponent self‐assembly. Our process involved the exchange of less hydrophilic trifluoromethanesulfonate anions for hydrophilic sulfate; the resulting water‐soluble cages could be rendered water‐insoluble through reverse anion exchange. Notably, this strategy allowed cargoes within capsules, including polycyclic aromatic compounds and complex organic drugs, to be brought into water. Hydrophobic effects appeared to enhance binding, as many of these cargoes were not bound in non‐aqueous media. Studies of the scope of this method revealed that cages containing tetratopic and tritopic ligands were more stable in water, whereas cages with ditopic ligands disassembled.     

A Convenient and Versatile Amino‐Acid‐Boosted Biomimetic Strategy for the Nondestructive Encapsulation of Biomacromolecules within Metal–Organic Frameworks

Herein, an amino‐acid‐boosted biomimetic strategy is reported that enabled the rapid encapsulation, or co‐encapsulation, of a broad range of proteins into microporous metal–organic frameworks (MOFs), with an ultrahigh loading efficiency. It relies on the accelerated formation of prenucleation clusters around proteins via a metallothionein‐like self‐assembly. The encapsulated proteins maintained their native conformations, and the structural confinement within porous MOFs endowed enzymes with excellent bioactivity, even in harsh conditions (e.g. in the presence of proteolytic or chemical agents or at high temperature). Furthermore, owing to the merits of nondestructive and protein surface charge‐independent encapsulation, the feasibility of this biomimetic strategy for biostorage, enzyme cascades, and biosensing was also verified. It is believed that this convenient and versatile encapsulation strategy has great promise in the important fields of biomedicine, catalysis, and biosensing.     

Non‐3d Metal Modulation of a Cobalt Imidazolate Framework for Excellent Electrocatalytic Oxygen Evolution in Neutral Media

Cobalt imidazolate frameworks are classical electrocatalysts for the oxygen evolution reaction (OER) but suffer from the relatively low activity. Here, a non‐3d metal modulation strategy is presented for enhancing the OER activity of cobalt imidazolate frameworks. Two isomorphous frameworks [Co₄(MO₄)(eim)₆] (M=Mo or W, Heim=2‐ethylimidazole) having Co(eim)₃(MO₄) units and high water stabilities were designed and synthesized. In different neutral media, the Mo‐modulated framework coated on a glassy carbon electrode shows the best OER performances (1 mA cm^?2 at an overpotential of 210 mV in CO₂‐saturated 0.5 m KHCO₃ electrolyte and 2/10/22 mA cm^?2 at overpotential of 388/490/570 mV in phosphate buffer solution) among non‐precious metal catalysts and even outperforms RuO₂. Spectroscopic measurements and computational simulations revealed that the non‐3d metals modulate the electronic structure of Co for optimum reactant/product adsorption and tailor the energy of rate‐determining step to a more moderate value.     

Control of Metal–Organic Framework Crystallization by Metastable Intermediate Pre‐equilibrium Species

There is an increasing amount of interest in metal–organic frameworks (MOFs) for a variety of applications, from gas sensing and separations to electronics and catalysis. However, the mechanisms by which they crystallize remain poorly understood. Herein, an important new insight into MOF formation is reported. It is shown that, prior to network assembly, crystallization intermediates in the canonical ZIF‐8 system exist in a dynamic pre‐equilibrium, which depends on the reactant concentrations and the progress of reaction. Concentration can, therefore, be used as a synthetic handle to directly control particle size, with potential implications for industrial scale‐up and gas sorption applications. These findings enable the rationalization of apparent contradictions between previous studies of ZIF‐8 and opens up new opportunities for the control of crystallization in network solids more generally.     

Sorting of C4 Olefins with Interpenetrated Hybrid Ultramicroporous Materials by Combining Molecular Recognition and Size‐Sieving

C₄ olefin separations present one of the great challenges in hydrocarbon purifications owing to their similar structures, thus a single separation mechanism often met with limited success. Herein we report a series of anion‐pillared interpenetrated copper coordination for which the cavity and functional site disposition can be varied in 0.2 Å scale increments by altering the anion pillars and organic linkers (GeFSIX‐2‐Cu‐i (ZU‐32), NbFSIX‐2‐Cu‐i (ZU‐52), GeFSIX‐14‐Cu‐i (ZU‐33)), which enable selective recognition of different C₄ olefins. In these materials the rotation of the organic linkers is controlled to create a contracted flexible pore window that enables the size‐exclusion of specific C₄ olefins, while still adsorbing significant amounts of 1,3‐butadiene (C₄H₆) or 1‐butene (n‐C₄H₈). Combining the molecular recognition and size‐sieving effect, these materials unexpectedly realized the sieving of C₄H₆/n‐C₄H₈, C₄H₆/iso‐C₄H₈, and n‐C₄H₈/iso‐C₄H₈ with high capacity.