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As a critical radioactive anionic contaminant, traditional adsorbents primarily remove iodate (IO 3 - ) through ion exchange or hard acid-hard base interactions, but suffer from limited affinity and capacity. Herein, employing the synergistic effect of ion exchange and redox, we successfully synthesized a redox-active cationic polymer network (SCU-CPN-6, [C 9 H 10 O 2 N 5  ⋅ Cl] n ) by merging guanidino groups with ion-exchange capability and phenolic groups with redox ability via a Schiff base reaction. SCU-CPN-6 exhibits a groundbreaking adsorption capacity of 896 mg/g for IO 3 - . The inferior adsorption capacities of polymeric networks containing only redox (~0 mg/g) or ion exchange (232 mg/g) fragments underscore the synergistic "1+1>2" effect of the two mechanisms. Besides, SCU-CPN-6 shows excellent uptake selectivity for IO 3 - in the presence of high concentrations of SO 4 2- , Cl - , and NO 3 - . Meanwhile, a high distribution coefficient indicates its exemplary deep-removal performance for low IO 3 - concentration. The synergic strategy not only presents a breakthrough solution for the efficient removal of IO 3 - but also establishes a promising avenue for the design of advanced adsorbents for diverse applications., (© 2024 Wiley-VCH GmbH.)

Metal-organic framework (MOF) based heterostructures, which exhibit enhanced or unexpected functionality and properties due to synergistic effects, are typically synthesized using post-synthetic strategies. However, several reported post-synthetic strategies remain unsatisfactory, considering issues such as damage to the crystallinity of MOFs, presence of impure phases, and high time and energy consumption. In this work, we demonstrate for the first time a novel route for constructing MOF based heterostructures using radiation-induced post-synthesis, highlighting the merits of convenience, ambient conditions, large-scale production, and notable time and energy saving. Specifically, a new HKUST-1@Cu 2 O heterostructure was successfully synthesized by simply irradiating a methanol solution dispersed of HKUST-1 with gamma ray under ambient conditions. The copper source of Cu 2 O was directly derived from in situ radiation etching and reduction of the parent HKUST-1, without the use of any additional copper reagents. Significantly, the resulting HKUST-1@Cu 2 O heterostructure exhibits remarkable catalytic performance, with a catalytic rate constant nearly two orders of magnitude higher than that of the parent HKUST-1., (© 2024 Wiley-VCH GmbH.)

Activation of ubiquitous C(sp 3 )-H bonds is extremely attractive but remains a great challenge. Heterogeneous photocatalysis offers a promising and sustainable approach for C(sp 3 )-H activation and has been fast developing in the past decade. This Minireview focuses on mechanism and strategies for heterogeneous photocatalytic C(sp 3 )-H activation. After introducing mechanistic insights, heterogeneous photocatalytic strategies for C(sp 3 )-H activation including precise design of active sites, regulation of reactive radical species, improving charge separation and reactor innovations are discussed. In addition, recent advances in C(sp 3 )-H activation of hydrocarbons, alcohols, ethers, amines and amides by heterogeneous photocatalysis are summarized. Lastly, challenges and opportunities are outlined to encourage more efforts for the development of this exciting and promising field., (© 2024 Wiley-VCH GmbH.)

Carbonylation of ethanol with CO 2 as carbonyl source into value-added esters is of considerable significance and interest, while remains of great challenge due to the harsh conditions for activation of inert CO 2 in that the harsh conditions result in undesired activation of α-C-H and even cleavage of C-C bond in ethanol to deteriorate the specific activation of O-H bond. Herein, we propose a photo-thermal cooperative strategy for carbonylation of ethanol with CO 2 , in which CO 2 is activated to reactive CO via photo-catalysis with the assistance of *H from thermally-catalyzed dissociation of alcoholic O-H bond. To achieve this proposal, an interfacial site and oxygen vacancy both abundant SrTiCuO 3-x supported Cu 2 O (Cu 2 O-SrTiCuO 3-x ) has been designed. A production of up to 320 μmol g -1  h -1 for ethyl formate with a selectivity of 85.6 % to targeted alcoholic O-H activation has been afforded in photo-thermal assisted gas-solid process under 3.29 W cm -1 of UV/Vis light irradiation (144 °C) and 0.2 MPa CO 2 . In the photo-driven activation of CO 2 and following carbonylation, CO 2 activation energy decreases to 12.6 kJ mol -1 , and the cleavage of alcoholic α-C-H bond has been suppressed., (© 2023 Wiley-VCH GmbH.)

Halide perovskites (HPs) recently have emerged as one class of competitive scintillators for X-ray detection and imaging owing to its high quantum efficiency, short decay time, superior X-ray absorption capacity, low cost, and ease of crystal growth. The tunable structure and versatile chemical compositions of halide perovskites provide distinguishable advantages over traditional inorganic scintillators for optimizing scintillation performance. Since the first observation of the scintillation phenomenon in HPs, substantial efforts have been devoted to expanding the inventory of HP scintillators and regulating material properties. Understanding the relationship between the structure and scintillation properties of HP scintillators is essential for developing materials with improved X-ray detection and imaging capacities. This review summarizes strategies for improving the light yield of HP scintillators and provides a roadmap for improving the X-ray imaging performance. Additionally, methods for controlling the light propagation direction in HP scintillators are highlighted for improving X-ray imaging resolution. Finally, we highlight the current challenge in HP scintillators and provide a perspective on the future development of this emerging scintillator., (© 2023 Wiley-VCH GmbH.)

The development of high-performance X-ray detectors requires scintillators with fast decay time, high light yield, stability, and X-ray absorption capacity, which are difficult to achieve in a single material. Here, we present the first example of a lanthanide chalcogenide of LaCsSiS 4  : 1 % Ce 3+ that simultaneously integrates multiple desirable properties for an ideal scintillator. LaCsSiS 4  : 1 % Ce 3+ demonstrates a remarkably low detection limit of 43.13 nGy air  s -1 and a high photoluminescence quantum yield of 98.24 %, resulting in a high light yield of 50480±1441 photons/MeV. Notably, LaCsSiS 4  : 1 % Ce 3+ exhibits a fast decay time of only 29.35±0.16 ns, making it one of the fastest scintillators among all lanthanide-based inorganic scintillators. Furthermore, this material shows robust radiation and moisture resistance, endowing it with suitability for chemical processing under solution conditions. To demonstrate the X-ray imaging capacity of LaCsSiS 4  : 1 % Ce 3+ , we fabricated a flexible X-ray detector that achieved a high spatial resolution of 8.2 lp mm -1 . This work highlights the potential of lanthanide chalcogenide as a promising candidate for high-performance scintillators., (© 2023 Wiley-VCH GmbH.)

Periodically arranging coordination-distinct actinides into one crystalline architecture is intriguing but of great synthetic challenge. We report a rare example of a heterobimetallic actinide metal-organic framework (An-MOF) by a unique reaction-induced preorganization strategy. A thorium MOF (SCU-16) with the largest unit cell among all Th-MOFs was prepared as the precursor, then the uranyl was precisely embedded into the MOF precursor under oxidation condition. Single crystal of the resulting thorium-uranium MOF (SCU-16-U) shows that a uranyl-specific site was in situ induced by the formate-to-carbonate oxidation reaction. The heterobimetallic SCU-16-U exhibits multifunction catalysis properties derived from two distinct actinides. The strategy proposed here offers a new avenue to create mixed-actinide functional material with unique architecture and versatile functionality., (© 2023 Wiley-VCH GmbH.)

In-cell NMR spectroscopy is an effective tool for observing proteins at atomic resolution in their native cellular environment. However, its utility is limited by its low sensitivity and the extensive line broadening caused by nonspecific interactions in the cells, which is even more pronounced in human cells due to the difficulty of overexpressing or delivering high concentrations of isotopically labeled proteins. Here, we present a high-sensitivity tag (wPSP-6F) containing two trifluoromethyl groups that can efficiently label globular proteins with molecular weights in the 6-40 kDa range under mild conditions. This tag allowed us to detect globular proteins in human cells at concentrations as low as 1.0 μM, which would not have been achievable with 15 N or 3-fluorotyrosine labeling. Moreover, we detected conformational changes and interactions of proteins in the cellular environment. The new sensitive 19 F NMR tag may significantly expand the scope of protein NMR in human cells., (© 2023 Wiley-VCH GmbH.)

Metal organic frameworks (MOFs) are a distinct family of crystalline porous materials finding extensive applications. Their synthesis often requires elevated temperature and relatively long reaction time. We report here the first case of MOF synthesis activated by high-energy (1.5 MeV) electron beam radiation from a commercially available electron-accelerator. Using ZIF-8 as a representative for demonstration, this type of synthesis can be accomplished under ambient conditions within minutes, leading to energy consumption about two orders of magnitude lower than that of the solvothermal condition. Interestingly, by controlling the absorbed dose in the synthesis, the electron beam not only activates the formation reaction of ZIF-8, but also partially etches the material during the synthesis affording a hierarchical pore architecture and highly crystalline ZnO nanoparticles on the surface of ZIF-8. This gives rise to a new strategy to obtain MOF@metal oxide heterostructures, finding utilities in photocatalytic degradation of organic dyes., (© 2022 Wiley-VCH GmbH.)

Scintillators display radioluminescent properties when irradiated by high-energy photons and therefore play an essential role in radiation detection. The current inventory of scintillators is overwhelmingly represented by achiral structures, where the radioluminescence propagates isotropically after generation. Herein, we demonstrate that chiral perovskites of (R-3AP)PbBr 3 Cl⋅H 2 O (R-3APP) and (S-3AP)PbBr 3 Cl⋅H 2 O (S-3APP) emerge as a new type of scintillator displaying a distinct property of circularly polarized radioluminescence (CPRL). A high quantum yield of 27.6 %, high luminescence dissymmetric factors (g lum ) of 4×10 -2 , and high X-ray absorption coefficients were observed for these compounds. As proof of concept, we fabricated a polarized scintillator pair by assembling chiral scintillator crystals, which provides a new strategy to attenuate optical crosstalk between the scintillators by precisely controlling the radioluminescence propagation and improves the X-ray imaging quality at the boundary region., (© 2022 Wiley-VCH GmbH.)

Dry reforming of methane (DRM) has provided an effective avenue to convert two greenhouse gases, CH 4 and CO 2 , into syngas. Here, we design a DRM photocatalyst Rh/Ce x WO 3 that invokes both photothermal and photoelectric processes, which overcomes the thermodynamic limitation of DRM under conventional conditions. In contrast to plasmonic or UV-response photocatalysts, our photocatalyst produces a superior light-to-chemical energy efficiency (LTCEE) of 4.65 % with a moderate light intensity. We propose that a light-induced metal-to-metal charge transfer plays a crucial role in the DRM reaction, which induces a redox looping between Ce to W species to lower the activation energy. Quantum mechanical studies reveal that a high oxygen mobility of Ce x WO 3 , accompanied with the formation of oxo-bridge species, results in a substantial elimination of deposited C species during the reaction. Our catalyst design strategy could offer a promising energy-efficient industrial process for DRM., (© 2022 Wiley-VCH GmbH.)

Luminescent covalent organic frameworks (COFs) find promising applications in chemical sensing, photocatalysis, and optoelectronic devices, however, the majority of COFs are non or weakly emissive owing to the aggregation-caused quenching (ACQ) or the molecular thermal motion-based energy dissipation. Here, we report a previously unperceived approach to improve luminescence performance of COFs by introducing isotope effect, which is achieved through substitution of hydrogen from high-frequency oscillators X-H (X=O, N, C) by heavier isotope deuterium. Combining the "bottom-up" and in situ deuteration methods generates the first deuterated COF, which exhibits an impressively 19-fold enhancement in quantum yield over that of the non-deuterated counterpart. These results are interpreted by theoretical calculations as the consequence of slower C/N-D and OD⋅⋅⋅O vibrations that impede the nonradiative deactivation process. The proposed strategy is proved applicable to many other types of emissive COFs., (© 2021 Wiley-VCH GmbH.)

Zeolites are a well-known family of microporous aluminosilicate crystals with a wide range of applications. Their industrial synthetic method under hydrothermal condition requires elevated temperature and long crystallization time and is therefore quite energy-consuming. Herein, we utilize high-energy electron beam irradiation generated by an industrial accelerator as a distinct type of energy source to activate the formation reaction of Na-A zeolite. The initial efforts afford an attractive reaction process that can be achieved under ambient conditions and completed within minutes with almost quantitative yield, leading to notable energy saving of one order of magnitude compared to the hydrothermal reaction. More importantly, electron beam irradiation simultaneously exhibits an etching effect during the formation of zeolite generating a series of crystal defects and additional pore windows that can be controlled by irradiation dose. These observations give rise to significantly enhanced surface area and heavy metal removal capabilities in comparison with Na-A zeolite synthesized hydrothermally. Finally, we show that this method can be applied to many other types of zeolites., (© 2021 Wiley-VCH GmbH.)

We disclose the intrinsic semiconducting properties of one of the largest mixed-valent uranium clusters, [H 3 O + ][U V (U VI O 2 ) 8 (μ 3 -O) 6 (PhCOO) 2 (Py(CH 2 O) 2 ) 4 (DMF) 4 ] (Ph=phenyl, Py=pyridyl, DMF=N,N-dimethylformamide) (1). Single-crystal X-ray crystallography demonstrates that U V center is stabilized within a tetraoxo core surrounded by eight uranyl(VI) pentagonal bipyramidal centers. The oxidation states of uranium are substantiated by spectroscopic data and magnetic susceptibility measurement. Electronic spectroscopy and theory corroborate that U V species serve as electron donors and thus facilitate 1 being a n-type semiconductor. With the largest effective atomic number among all reported radiation-detection semiconductor materials, charge transport properties and photoconductivity were investigated under X-ray excitation for 1: a large on-off ratio of 500 and considerable charge mobility lifetime product of 2.3×10 -4  cm 2  V -1 , as well as a high detection sensitivity of 23.4 μC Gy air -1  cm -2 ., (© 2021 Wiley-VCH GmbH.)

Radio-photoluminescence (RPL) materials display a distinct radiation-induced permanent luminescence center, and therefore find application in the detection of ionizing radiation. The current inventory of RPL materials, which were discovered by serendipity, has been limited to a small number of metal-ion-doped inorganic materials. Here we document the RPL of a metal-organic framework (MOF) for the first time: X-ray induced free radicals are accumulated on the organic linker and are subsequently stabilized in the conjugated fragment in the structure, while the metal center acts as the X-ray attenuator. These radicals afford new emission features in both UV-excited and X-ray excited luminescence spectra, making it possible to establish linear relationships between the radiation dose and the normalized intensity of the new emission feature. The MOF-based RPL materials exhibit advantages in terms of the dose detection range, reusability, emission stability, and energy threshold. Based on a comprehensive electronic structure and energy diagram study, the rational design and a substantial expansion of candidate RPL materials can be anticipated., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Semiconductive metal-organic frameworks (MOFs) have emerged in applications such as chemical sensors, electrocatalysts, energy storage materials, and electronic devices. However, examples of semiconductive MOFs within flexible electronics have not been reported. We present flexible X-ray detectors prepared by thermoplastic dispersal of a semiconductive MOF (SCU-13) through a commercially available polymer, poly(vinylidene fluoride). The flexible detectors exhibit efficient X-ray-to-electric current conversion with enhanced charge-carrier mobility and low trap density compared to pelleted devices. A high X-ray detection sensitivity of 65.86 μCGy air -1  cm -2 was achieved, which outperforms other pelleted devices and commercial flexible X-ray detectors. We demonstrate that the MOF-based flexible detectors can be operated at multiple bending angles without a deterioration in detection performance. As a proof-of-concept, an X-ray phase contrast under bending conditions was constructed using a 5×5 pixelated MOF-based imager., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Mechanoluminescence (ML) and room-temperature photophosphorescence (RTP) were achieved in polymorphisms of a triphenylamine derivative with ortho-substitution. This molecular packing-dependent emission afforded crucial information to deeply understand the intrinsic mechanism of different emission forms and the possible packing-function relationship. With the incorporation of solid-state 13 C NMR spectra of single crystals, as well as the analysis of crystal structures, the preferred packing modes for ML and/or RTP were investigated in detail, which can guide the reasonable design of organic molecules with special light-emission properties., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

99 Tc contamination at legacy nuclear sites is a serious and unsolved environmental issue. The selective remediation of 99 TcO 4 - in the presence of a large excess of NO 3 - and SO 4 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 (Ni 2 (tipm) 3 (NO 3 ) 4 ), which exhibits fast sorption kinetics, a large capacity (291 mg g -1 ), a high distribution coefficient, and, most importantly, a record-high TcO 4 - uptake selectivity. This material can almost quantitatively remove TcO 4 - in the presence of a large excess of NO 3 - and SO 4 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 TcO 4 - by the hydrophobic pockets of the structure., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The combination of high atomic number and high oxidation state in U VI materials gives rise to both high X-ray attenuation efficiency and intense green luminescence originating from ligand-to-metal charge transfer. These two features suggest that U VI materials might act as superior X-ray scintillators, but this postulate has remained substantially untested. Now the first observation of intense X-ray scintillation in a uranyl-organic framework (SCU-9) that is observable by the naked eye is reported. Combining the advantage in minimizing the non-radiative relaxation during the X-ray excitation process over those of inorganic salts of uranium, SCU-9 exhibits a very efficient X-ray to green light luminescence conversion. The luminescence intensity shows an essentially linear correlation with the received X-ray intensity, and is comparable with that of commercially available CsI:Tl. SCU-9 possesses an improved X-ray attenuation efficiency (E>20 keV) as well as enhanced radiation resistance and decreased hygroscopy compared to CsI:Tl., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Actinide based metal-organic frameworks (MOFs) are unique not only because compared to the transition-metal and lanthanide systems they are substantially less explored, but also owing to the uniqueness of actinide ions in bonding and coordination. Now a 3D thorium-organic framework (SCU-11) contains a series of cages with an effective size of ca. 21×24 Å. Th 4+ in SCU-11 is 10-coordinate with a bicapped square prism coordination geometry, which has never been documented for any metal cation complexes. The bicapped position is occupied by two coordinated water molecules that can be removed to afford a very unique open Th 4+ site, confirmed by X-ray diffraction, color change, thermogravimetry, and spectroscopy. The degassed phase (SCU-11-A) exhibits a Brunauer-Emmett-Teller surface area of 1272 m 2  g -1 , one of the highest values among reported actinide materials, enabling it to sufficiently retain water vapor, Kr, and Xe with uptake capacities of 234 cm 3  g -1 , 0.77 mmol g -1 , 3.17 mmol g -1 , respectively, and a Xe/Kr selectivity of 5.7., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Precise detection of low-dose X- and γ-radiations remains a challenge and is particularly important for studying biological effects under low-dose ionizing radiation, safety control in medical radiation treatment, survey of environmental radiation background, and monitoring cosmic radiations. We report here a photoluminescent uranium organic framework, whose photoluminescence intensity can be accurately correlated with the exposure dose of X- or γ-radiations. This allows for precise and instant detection of ionizing radiations down to the level of 10 -4  Gy, representing a significant improvement on the detection limit of approximately two orders of magnitude, compared to other chemical dosimeters reported up to now. The electron paramagnetic resonance analysis suggests that with the exposure to radiations, the carbonyl double bonds break affording oxo-radicals that can be stabilized within the conjugated uranium oxalate-carboxylate sheet. This gives rise to a substantially enhanced equatorial bonding of the uranyl(VI) ions as elucidated by the single-crystal structure of the γ-ray irradiated material, and subsequently leads to a very effective photoluminescence quenching through phonon-assisted relaxation. The quenched sample can be easily recovered by heating, enabling recycled detection for multiple runs., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The kinetic resolution of 2-aryl-N-tosylaziridines and the asymmetric desymmetrization of meso-N-tosylaziridines by ring openings with various primary and secondary anilines, and aliphatic amines as nucleophile have been realized by using a single silver(I)/chiral diphosphine complex as catalyst for the first time. The simple starting materials, broad scope, and easy scalability render this protocol a practical way to chiral vicinal diamine derivatives., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ceria nanoparticles (nanoceria) are well known as a superoxide scavenger. However, inherent superoxide-scavenging ability has only been found in the nanoceria with sizes of less than 5 nm and with very limited shape diversity. Reported herein is a strategy to significantly improve the superoxide-scavenging activity of nanoceria sized at greater than 5 nm. The nanoceria with sizes of greater than 5 nm, with different shapes, and with a negligible Ce(3+)/Ce(4+) ratio can acquire remarkable superoxide-scavenging abilities through electron transfer. This method will make it possible to develop nanoceria-based superoxide-scavengers with long-acting activity and tailorable characteristics., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The combination of a new bifunctional phosphine and an acrylate generate a zwitterion in situ and it serves as an efficient catalyst for asymmetric reactions through a homogeneous ion-pairing mode. This new catalytic system has been successfully applied to Mannich-type reactions to give excellent results and it demonstrates a broad substrate scope. Such reactivity is not accessible with general organophosphine catalytic modes. Preliminary investigations into the mechanism are also presented., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Multifunctional glass windows that combine energy storage and electrochromism have been obtained by facile thermal evaporation and electrodeposition methods. For example, WO3 films that had been deposited on fluorine-doped tin oxide (FTO) glass exhibited a high specific capacitance of 639.8 F g(-1). Their color changed from transparent to deep blue with an abrupt decrease in optical transmittance from 91.3% to 15.1% at a wavelength of 633 nm when a voltage of -0.6 V (vs. Ag/AgCl) was applied, demonstrating its excellent energy-storage and electrochromism properties. As a second example, a polyaniline-based pseudocapacitive glass was also developed, and its color can change from green to blue. A large-scale pseudocapacitive WO3-based glass window (15×15 cm(2)) was fabricated as a prototype. Such smart pseudocapacitive glass windows show great potential in functioning as electrochromic windows and concurrently powering electronic devices, such as mobile phones or laptops., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)