Extra-High CO2 Adsorption and Controllable C2H2/CO2 Separation Regulated by the Interlayer Stacking in Pillar-Layered Metal-Organic Frameworks.

Pillar-layered metal-organic frameworks (PLMOFs) are promising gas adsorbents due to their high designability. In this work, high CO2 storage capacity as well as controllable C2H2/CO2 separation ability are acquired by rationally manipulating the interlayer stacking in pillar-layered MOF materials. The rational construction of pillar-layered MOFs started from the 2D Ni-BTC-pyridine layer, an isomorphic structure of pioneering MOF-1 reported in 1995. The replacement of terminal pyridine groups by bridging pyrazine linkers under optimized solvothermal conditions led to three 3D PLMOFs with different stacking types between adjacent Ni-BTC layers, named PLMOF 1 (ABAB stacking), PLMOF 2 (AABB stacking), and PLMOF 3 (AAAA stacking). Regulated by the layer arrangements, CO2 and C2H2 adsorption capacities (273 K and 1 bar) of PLMOFs 1-3 vary from 173.0/153.3, 185.0/162.4, to 203.5/159.5 cm3 g-1, respectively, which surpass the values of most MOF adsorbents. Dynamic breakthrough experiments further indicate that PLMOFs 1-3 have controllable C2H2/CO2 separation performance, which can successfully overcome the C2H2/CO2 separation challenge. Specially, PLMOFs 1-3 can remove trace CO2 (3%) from the C2H2/CO2 mixture and produce high-purity ethylene (99.9%) in one step with the C2H2 productivities of 1.68, 2.45, and 3.30 mmol g-1, respectively. GCMC simulations indicate that the superior CO2 adsorption and unique C2H2/CO2 separation performance are mainly ascribed to different degrees of CO2 agglomeration in the ultramicropores of these PLMOFs.

Spatially Confined π-Complexation within Pore-Space-Partitioned Metal-Organic Frameworks for Enhanced Light Hydrocarbon Separation and Purification.

Ultramicroporous metal-organic frameworks (MOFs) are demonstrated to be advantageous for the separation and purification of light hydrocarbons such as C2H2, C2H4, and CH4. The introduction of transition metal sites with strong π-complexation affinity into MOFs is more effective than other adsorption sites for the selective adsorption of π-electron-rich unsaturated hydrocarbon gases from their mixtures. However, lower coordination numbers make it challenging to produce robust MOFs directly utilizing metal ions with π-coordination activity, such as Cu+, Ag+, and Pd2+. Herein, a series of novel π-complexing MOFs (SNNU-33s) with a pore size of 4.6 Å are precisely constructed by cleverly introducing symmetrically matched C3-type [Cu(pyz)3] (pyz = pyrazine) coordinated fragments into 1D hexagonal channels of MIL-88 prototype frameworks. Benifit from the spatial confinement combined with π-complex-active Cu+ of [Cu(pyz)3], pore-space-partitioned SNNU-33 MOFs all present excellent C2H2/CH4, C2H4/CH4, and CO2/CH4 separation ability. Notably, the optimized SNNU-33b adsorbent demonstrates top-level IAST selectivity values for C2H2/CH4 (597.4) and C2H4/CH4 (69.8), as well as excellent breakthrough performance. Theoretical calculations further reveal that such benchmark light hydrocarbon separation and purification ability is mainly ascribed to the extra-strong binding affinity between Cu+ and π-electron donor molecules via a spatially confined π-complexation process.

Maximizing Electrostatic Interaction in Ultramicroporous Metal-Organic Frameworks for the One-Step Purification of Acetylene from Ternary Mixture.

Developing efficient adsorbents for acetylene purification from multicomponent mixtures is of critical significance in the chemical industry, but the trade-off between regenerability and selectivity significantly restricts practical industrial applications. Here, we report ultramicroporous metal-organic frameworks with acetylene-affinity channels to enhance electrostatic interaction between C2H2 and frameworks for the efficient one-step purification of C2H2 from C2H2/CO2/C2H4 mixtures, in which the electrostatic interaction led to high regenerability. The obtained SNNU-277 exhibits significantly higher adsorption capacity for C2H2 than that for both C2H4 and CO2 at 298 K and 0.1 bar, while an ultrahigh selectivity of C2H2/C2H4 (100.6 at 298 K) and C2H2/CO2 (32.8 at 298 K) were achieved at 1 bar. Breakthrough experiments validated that SNNU-277 can efficiently separate C2H2 from C2H2/C2H4/CO2 mixtures. CO2 and C2H4 broke through the adsorption column at 4 and 14.8 min g-1, whereas C2H2 was detected until 177.6 min g-1 at 298 K. Theoretical calculations suggest that the framework is electrostatically compatible with C2H2 and electrostatically repels C2H4 and CO2 in the mixed components. This work highlights the importance of rational pore engineering for maximizing the electrostatic effect with the preferentially absorbed guest molecule for efficient multicomponent separation.

High-Valence Metal Doping Induced Lattice Expansion for M-FeNi LDH toward Enhanced Urea Oxidation Electrocatalytic Activities.

The precise design of low-cost, efficient, and definite electrocatalysts is the key to sustainable renewable energy. The urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction for energy-saving hydrogen generation. In this study, by tuning the lattice expansion, a series of M-FeNi layered double hydroxides (M-FeNi LDHs, M: Mo, Mn, V) with excellent UOR performance are synthesized. The hydrolytic transformation of Fe-MIL-88A is assisted by urea, Ni2+ and high-valence metals, to form a hollow M-FeNi LDH. Owing to the large atomic radius of the high-valence metal, lattice expansion is induced, and the electronic structure of the FeNi-LDH is regulated. Doping with high-valence metal is more favorable for the formation of the high-valence active species, NiOOH, for the UOR. Moreover, the hollow spindle structure promoted mass transport. Thus, the optimal Mo-FeNi LDH showed outstanding UOR electrocatalytic activity, with 1.32 V at 10 mA cm-2 . Remarkably, the Pt/C||Mo-FeNi LDH catalyst required a cell voltage of 1.38 V at 10 mA·cm-2 in urea-assisted water electrolysis. This study suggests a new direction for constructing nanostructures and modulating electronic structures, which is expected to ultimately lead to the development of a class of auxiliary electrocatalysts.

Substituent Engineering in Pore-Space-Partitioned Metal-Organic Frameworks for CO2 Selective Adsorption and Fixation.

Comprehensive understanding of substituent groups located on the pore surface of metal-organic frameworks (which we call substituent engineering herein) can help to promote gas adsorption and catalytic performance through ligand functionalization. In this work, pore-space-partitioned metal-organic frameworks (PSP MOFs) were selected as a platform to evaluate the effect of organic functional groups on CO2 adsorption, separation, and catalytic conversion. Twelve partitioned acs metal-organic frameworks (pacs-MOFs, named SNNU-25-Rn here) containing different functional groups were synthesized, which can be classified into electron-donor groups (-OH, -NH2, -CH3, and -OCH3) and electron-acceptor groups (-NO2, -F, -Cl, and -Br). The experimental results showed that SNNU-25-Rn with electron donors usually perform better than those with electron acceptors for the comprehensive utilization of CO2. The CO2 uptake of the 12 SNNU-25-Rn MOFs ranged from 30.9 to 183.6 cm3 g-1 at 273 K and 1 bar, depending on the organic functional groups. In particular, SNNU-25-OH showed the highest CO2 adsorption, SNNU-25-CH3 had the highest IAST of CO2/CH4 (36.1), and SNNU-25-(OH)2 showed the best catalytic activity for the CO2 cycloaddition reaction. The -OH functionalized MOFs with excellent performance may be attributed to the Lewis acid-base and hydrogen-bonding interactions between -OH groups and the CO2 molecules. This work modulated the effect of the microenvironment of MOFs on CO2 adsorption, separation, and catalysis in terms of substituents, providing valuable information for the precise design of porous MOFs with a comprehensive utilization of CO2.

Development of a Mixed Multinuclear Cluster Strategy in Metal-Organic Frameworks for Methane Purification and Storage.

Metal-organic frameworks (MOFs) have attracted extensive attention in methane (CH4) purification and storage. Specially, multinuclear cluster-based MOFs usually have prominent performance because of large cluster size and abundant open metal sites. However, compared to diverse combinations of organic linkers, one MOF with two or more multinuclear clusters is difficult to achieve. In this paper, we demonstrate a mixed multinuclear cluster strategy, which successfully led to three new heterometallic MOFs (SNNU-328-330) with the same common H3TATB [2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine] tritopic linker and six types of multinuclear clusters ([YCd(COO)4(µ2-H2O)], [YCd2(COO)8], [In3(COO)6(µ3-OH)], [In3Eu2(COO)9(µ3-OH)3(µ4-O)], [Y9(COO)12(µ3-OH)14] and [Y2Cd8(COO)16(µ2-H2O)4(µ3-OH)8]). Three MOF adsorbents all show great potentials to remove the impurities (CO2 and C2-hydrocarbons) in natural gas and show prominent high-pressure methane storage capacity. Among them, the ideal adsorbed solution theory separation ratios of equimolar C2H2/CH4, C2H4/CH4, C2H6/CH4, and CO2/CH4 at 298 K for SNNU-328 reach to 29.7-16.0, 19.1-8.2, 33.2-10.3, and 74.3-8.5, which have surpassed many famous MOF adsorbents. Dynamic breakthrough experiments conducted at 273 and 298 K showed that SNNU-330 can separate CH4 from C2H2/CH4, C2H4/CH4, C2H6/CH4, and CO2/CH4 mixtures with the breakthrough interval times of about 48.2, 17.9, 37.2, and 17.1 min g-1 (273 K, 1 bar, v/v = 50/50, 2 mL min-1), respectively. Remarkably, SNNU-329 exhibits extremely high methane storage performance at 298 K with the total uptake and working capacity of 192 cm3 cm-3 (95 bar) and 171 cm3 cm-3 (65 bar) due to the synergistic effects of high surface area, suitable pore sizes, and multiple open metal sites.

Pore Environmental Modification by Alkoxy Groups in Pore-Space-Partitioned Metal-Organic Frameworks to Achieve Gas Uptake-Selectivity Balance.

Due to the trade-off barrier between high storage capacity and high selectivity, the controllable and systematic design of metal-organic frameworks (MOFs) aiming at performance optimization is still challenging. Herein, considering the effectiveness of alkoxy group functionalization and a pore-space partition strategy, a series of rigid Mg-pacs-MOFs (SNNU-10-n, n = 1-6) with flexible side chains are built for the first time, realizing systematic pore environmental modification. The steric hindrance effects, electron-donating ability, and the flexibility of alkoxy groups are considered as key factors, which lead to a regular change of gas adsorption capacity and selectivity. Notably, methoxy-modified SNNU-10-1 with moderately high storage capacities of C2H2 (139.4 cm3 g-1), C2H4 (100.4 cm3 g-1), CO2 (105.0 cm3 g-1), and high selectivity values for equimolar C2H2/CH4 (431.8), C2H4/CH4 (164.2), and CO2/CH4 (16.1) mixture separation at 273 K and 100 kPa achieves an ideal gas uptake-selectivity balance. Breakthrough experiments verified that it could effectively separate the above-mentioned mixtures under ambient conditions, and GCMC simulation provides a deep understanding of methoxy group functionalization. Undoubtedly, this work not only realizes controllable regulation of gas adsorption behavior but also proves the validity of improving selectivity by alkoxy groups in those platforms with high gas-uptake potential to overcome the trade-off barrier.

Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums.

The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF)6 ]{CoI [(µ3 -HAN)RE2 Cp*4 ]2 } (1-RE) and [K(Crypt)]2 {CoI [(µ3 -HAN)RE2 Cp*4 ]2 } (2-RE) containing hexaazatrinaphthylene radicals (HAN⋅3- ) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy. Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs.

Monodispersed Pt Sites Supported on NiFe-LDH from Synchronous Anchoring and Reduction for High Efficiency Overall Water Splitting.

Precise design of low-cost, efficient and definite electrocatalysts is the key to sustainable renewable energy. Herein, this work develops a targeted-anchored and subsequent spontaneous-redox strategy to synthesize nickel-iron layered double hydroxide (LDH) nanosheets anchored with monodispersed platinum (Pt) sites (Pt@LDH). Intermediate metal-organic frameworks (MOF)/LDH heterostructure not only provides numerous confine points to guarantee the stability of Pt sites, but also excites the spontaneous reduction for PtII . Electronic structure, charge transfer ability and reaction kinetics of Pt@LDH can be effectively facilitated by the monodispersed Pt moieties. As a result, the optimized Pt@LDH that with the 5% ultra-low content Pt exhibits the significant increment in electrochemical water splitting performance in alkaline media, which only afford low overpotentials of 58 mV at 10 mA cm-2 for hydrogen evolution reaction (HER) and 239 mV at 10 mA cm-2 for oxygen evolution reaction (OER), respectively. In a real device, Pt@LDH can drive an overall water-splitting at low cell voltage of 1.49 V at 10 mA cm-2 , which can be superior to most reported similar LDH-based catalysts. Moreover, the versatility of the method is extended to other MOF precursors and noble metals for the design of ultrathin LDH supported monodispersed noble metal electrocatalysts promoting research interest in material design.

De-Linker-Enabled Exceptional Volumetric Acetylene Storage Capacity and Benchmark C2 H2 /C2 H4 and C2 H2 /CO2 Separations in Metal-Organic Frameworks.

An ideal adsorbent for separation requires optimizing both storage capacity and selectivity, but maximizing both or achieving a desired balance remain challenging. Herein, a de-linker strategy is proposed to address this issue for metal-organic frameworks (MOFs). Broadly speaking, the de-linker idea targets a class of materials that may be viewed as being intermediate between zeolites and MOFs. Its feasibility is shown here by a series of ultra-microporous MOFs (SNNU-98-M, M=Mn, Co, Ni, Zn). SNNU-98 exhibit high volumetric C2 H2 uptake capacity under low and ambient pressures (175.3 cm3 cm-3 @ 0.1 bar, 222.9 cm3 cm-3 @ 1 bar, 298 K), as well as extraordinary selectivity (2405.7 for C2 H2 /C2 H4 , 22.7 for C2 H2 /CO2 ). Remarkably, SNNU-98-Mn can efficiently separate C2 H2 from C2 H2 /CO2 and C2 H2 /C2 H4 mixtures with a benchmark C2 H2 /C2 H4 (1/99) breakthrough time of 2325 min g-1 , and produce 99.9999 % C2 H4 with a productivity up to 64.6 mmol g-1 , surpassing values of reported MOF adsorbents.

Rational regulation of acetylene adsorption and separation for ultra-microporous copper-1,2,4-triazolate frameworks by halogen hydrogen bonds.

It is well known that the introduction of exposed fluorine (F) sites into metal-organic frameworks (MOFs) can effectively promote acetylene (C2H2) adsorption via C-H⋯F hydrogen bonds. However, such super strong hydrogen bonding interactions usually lead to very high acetylene adsorption enthalpy and thus require more energy during the adsorbent regeneration process. As the same group elements, chlorine (Cl), bromine (Br) and iodine (I) also can act as hydrogen bond acceptors but with relatively weak forces. So, it is speculated that the decoration of Cl, Br or I sites on the pore surface of MOF adsorbents may enhance acetylene adsorption but with lower energy consumption. Herein, ultra-microporous MOFs constructed by Cu4X4 (X = Cl, Br, I) motifs and 1,2,4-triazolate linkers, namely, [Cu8X4(TRZ)4]n (TRZ = 3,5-diethyl-1,2,4-triazole or detrz for SNNU-313-X, and 3,5-dipropyl-1,2,4-triazole or dptrz for SNNU-314-X), provide an ideal platform to investigate the effect of C-H⋯X (X = Cl, Br, I) hydrogen bonding on C2H2 adsorption and purification performance. Benefiting from the small pore size and pore environment, the C2H2 uptake and separation properties of this series of MOFs are systematically regulated. Detailed gas adsorption results show that with the same organic linker, the C2H2 uptake and separation (C2H2/C2H4 and C2H2/CO2) performance decrease clearly with the electronegativity of halogen ions (SNNU-313-Cl > SNNU-313-Br > SNNU-313-I). With the same halogen ion, the gas adsorption decreases with the bulk of decorated alkyl groups (SNNU-313-Cl > SNNU-314-Cl). Remarkably, SNNU-313/314 series MOF adsorbents exhibit moderate C2H2 uptake capacity and high separation ability, but the C2H2 adsorption enthalpies are much lower than those of MOF materials with exposed F sites. Dynamic fixed-bed column breakthrough experiments and Grand Canonical Monte Carlo (GCMC) simulations further indicate the critical effects of halogen hydrogen bonds on acetylene adsorption and separation. Overall, this work demonstrated an effective regulation of acetylene adsorption and separation by rational C-H⋯X hydrogen bonding, which may provide a new route for the exploration of energy-efficient acetylene adsorbent materials.

High-Performance Turn-On Fluorescent Metal-Organic Framework for Detecting Trace Water in Organic Solvents Based on the Excited-State Intramolecular Proton Transfer Mechanism.

Simple, fast, and sensitive detection of trace water in organic solvents is an urgent requirement for chemical industries. Herein, combining the unusual excited-state intramolecular proton transfer (ESIPT) mechanism with the effective strategy of pore space partition, for the first time, we construct a powerful fluorescent metal-organic framework (SNNU-301) probe with excellent water stability. The SNNU-301 probe shows a remarkable performance for turn-on ESIPT-based fluorescence response to water in nine common organic solvents, exhibiting wide linear ranges, low limit of detection values, and ultrafast response, especially in dimethyl sulfoxide (0-5.2%; 0.011%, v/v; 110 s). The typical ESIPT-sensitive linker 2,5-dihydroxyterephthalate (DHBDC) imparts it with discriminative detection properties via enol-keto tautomerism, and light-responsive triangular tri(pyridin-4-yl)-amine (TPA) realizes pore space partition. The theoretical calculation gives an in-depth explanation about the proton transfer mechanism. Comparative experiments and GCMC simulation provide evidence that the synergy of the ESIPT process and TPA of the framework further boosts its performance effectively. Definitely, this work not only offers a promising candidate with fast detection speed, high sensitivity, excellent universality, and visual observation for the determination of water in organic solvents but also provides valuable guidance for the design of high-performance fluorescent probes.

Precise Introduction of Single Vanadium Site into Indium-Organic Framework for CO2 Capture and Photocatalytic Fixation.

The capture and fixation of CO2 under mild conditions is a cost-effective route to reduce greenhouse gases, but it is challenging because of the low conversion and selectivity issues. Metal-organic frameworks (MOFs) are promising in the fields of adsorption and catalysis because of their structural tunability and variability. However, the precise structural design of MOFs is always pursued and elusive. In this work, a metal-mixed MOF (SNNU-97-InV) was designed by precisely introducing single vanadium site into the isostructural In-MOF (SNNU-97-In). The single V sites clearly change the interactions between the MOF framework and CO2 molecules, leading to a 71.3% improvement in the CO2 adsorption capacity. At the same time, the enhanced light absorption enables SNNU-97-InV to efficiently convert CO2 into cyclic carbonates (CCs) with epoxides under illumination. Controlled experiments showed that the promoted performance of SNNU-97-InV may be that the V═O site can more easily combine with CO2 and convert them into an intermediate state under illumination, and the possible mechanism was thus speculated.

Pore-Window Partitions in Metal-Organic Frameworks for Highly Efficient Reversed Ethylene/Ethane Separations.

The development of paraffin-selective adsorbents is desirable but extremely challenging because adsorbents usually prefer olefin over paraffin. Herein, a new pore-window-partition strategy is proposed for the rational design of highly efficient paraffin-preferred metal-organic framework (MOF) adsorbents. The power of this strategy is demonstrated by stepwise installations of linear bidentate N-donor linkers into a prototype MOF (SNNU-201) to produce a series of partitional MOF adsorbents (SNNU-202-204). With continuous pore-window partitions from SNNU-201 to SNNU-204, the isosteric heat of adsorption can be tuned from -34.4 to -19.4 kJ mol-1 for ethylene and from -25.5 to -20.7 kJ mol-1 for ethane. Accordingly, partitional MOFs exhibit much higher ethane adsorption capacities, especially for SNNU-204 (104.6 cm3 g-1), representing nearly 4 times as much ethane as the prototypical counterpart (SNNU-201; 27.5 cm3 g-1) under ambient conditions. The C2H6/C2H4 ideal adsorbed solution theory selectivity, dynamic breakthrough experiments, and theoretical simulations further indicate that pore-window partition is a promising and universal strategy for the exploration of highly efficient paraffin-selective MOF adsorbents.

Micropore Regulation in Ultrastable [Sc3O]-Organic Frameworks for Acetylene Storage and Purification.

High storage capacity, high separation selectivity, and high structure stability are essential for an idea gas adsorbent. However, it is not easy to achieve all three at the same time, even for the promising metal-organic framework (MOF) adsorbents. We demonstrate herein that robust [Sc3O]-organic frameworks could be regulated by a micropore combination strategy for high-performance acetylene adsorption. Under the same solvent system with formic acid as a modulator, similar tritopic ligands extend [Sc3O(COO)6] trigonal-prismatic clusters to generate SNNU-5-Sc and SNNU-150-Sc adsorbents. Notably, the two Sc-MOFs can keep their architectures over 24 h in water at different pH values (2-12) or at 90 °C. Modulated by the linker symmetry, the final stacking metal-organic polyhedral cages produce open window sizes of about 10 Å for SNNU-5-Sc and 5 Å + 7 Å for SNNU-150-Sc. Due to such micropore combinations, SNNU-5-Sc exhibits a top-level C2H2 uptake of 211.2 cm3 g-1 (1 atm and 273 K) and SNNU-150-Sc shows high C2H2/CH4, C2H2/C2H4, and C2H2/CO2 selectivities of 80.65, 4.03, and 8.19, respectively, under ambient conditions. Dynamic breakthrough curves obtained on a fixed-bed column and grand canonical Monte Carlo (GCMC) simulations further support their prominent acetylene storage and purification performance. High framework stability, storage capacity, and separation selectivity make SNNU-5-Sc and SNNU-150-Sc ideal acetylene adsorbents in practical applications.

Competitive Coordination-Oriented Monodispersed Ruthenium Sites in Conductive MOF/LDH Hetero-Nanotree Catalysts for Efficient Overall Water Splitting in Alkaline Media.

Rational exploration of efficient, inexpensive, and robust electrocatalysts is critical for the efficient water splitting. Conjugated conductive metal-organic frameworks (cMOFs) with multicomponent layered double hydroxides (LDHs) to construct bifunctional heterostructure catalysts are considered as an efficient but complicated strategy. Here, the fabrication of a cMOF/LDH hetero-nanotree array catalyst (CoNiRu-NT) coupled with monodispersed ruthenium (Ru) sites via a controllable grafted-growth strategy is reported. Rich-amino hexaiminotriphenylene linkers coordinate with the LDH nanotrunk to form cMOF nanobranches, providing numerous anchoring sites to precisely confine and stabilize RuN4 sites. Moreover, monodispersed and reduced Ru moieties facilitate H2 O adsorption and dissociation, and the heterointerface between the cMOF and the LDH further modifies the chemical and electronic structures. Optimized CoNiRu-NT displays a significant increase in electrochemical water-splitting properties in alkaline media, affording low overpotentials of 22 mV at 10 mA cm-2 and 255 mV at 20 mA cm-2 for the hydrogen evolution reaction and oxygen evolution reaction, respectively. In an actual electrochemical system, CoNiRu-NT drives an overall water splitting at a low cell voltage of 1.47 V to reach 10 mA cm-2 . This performance is comparable to that of pure noble-metal-based materials and superior to most reported MOF-based catalysts.

Recent advancement in Bi5O7I-based nanocomposites for high performance photocatalysts.

Bi5O7I belongs to the family of bismuth oxyhalides (BiOX, X = Cl, Br, I), having a unique layered structure with an internal electrostatic field that promotes the separation and transfer of photo-generated charge carriers. Interestingly, Bi5O7I exhibits higher thermal stability compared to its other BiOX member compounds and absorption spectrum extended to the visible region. Bi5O7I has demonstrated applications in diverse fields such as photocatalytic degradation of various organic pollutants, marine antifouling, etc. Unfortunately, owing to its wide band gap of ∼2.9 eV, its absorption lies mainly in the ultraviolet region, and a tiny portion of absorption lies in the visible region. Due to limited absorption, the photocatalytic performance of pure Bi5O7I is still facing challenges. In order to reduce the band gap and increase the light absorption capability of Bi5O7I, doping and formation of heterostructure strategies have been employed, which showed promising results in the photocatalytic performance. In addition, the plasmonic heterostructures of Bi5O7I were also developed to further boost the efficiency of Bi5O7I as a photocatalyst. Here, in this review article, we present such recent efforts made for the advanced development of Bi5O7I regarding its synthesis, properties and applications. The strategies for photocatalytic performance enhancement have been discussed in detail. Moreover, in the conclusion section, we have presented the current challenges and discussed possible prospective developments in this field.

Amide-Functionalized Metal-Organic Frameworks Coupled with Open Fe/Sc Sites for Efficient Acetylene Purification.

Acetylene (C2H2) purification is of great importance for many chemical synthesis and processes. Metal-organic frameworks (MOFs) are widely used for gas adsorption and separation due to their variable structure and porosity. However, the exploitation of ideal MOF adsorbents for C2H2 keeps a challenging task. Herein, a combination of open metal sites (OMSs) and Lewis basic sites (LBSs) in robust MOFs is demonstrated to effectively promote the C2H2 purification performance. Accordingly, SNNU-37(Fe/Sc), two isostructural MOFs constituted by [Fe3O(COO)6] or [Sc3O(COO)6] trinuclear clusters and amide-functionalized tricarboxylate linkers, were designed with extra-stable 3,6-connected new architectures. Derived from the coexistence of high-density OMSs and LBSs, the C2H2 adsorption amounts of SNNU-37(Fe/Sc) are much higher than those values for C2H4 and CO2. Theoretical IAST selectivity values of SNNU-37(Fe) are 2.4 for C2H2/C2H4 (50/50, v/v) and 9.9 for C2H2/CO2 (50/50, v/v) at 298 K and 1 bar, indicating an excellent C2H2 separation ability. Experimental breakthrough curves also revealed that SNNU-37(Fe) could effectively separate C2H2/C2H4 and C2H2/CO2 under ambient conditions. GCMC simulations further indicate that open Fe or Sc sites and amide groups mainly contribute to stronger adsorption sites for C2H2 molecules.

Enhancement of the fluorescence properties via introducing the tetraphenylethylene chromophores into a novel Mn-organic framework with a rare [Mn4(µ3-OH)2] cluster.

By employing a tetraphenylethylene (TPE)-based tetracarboxylate linker, tetrakis(4-carboxyphenyl)ethylene (H4TCPE), we herein constructed a novel luminescent Mn-MOF based on a rare [Mn4(µ3-OH)2] cluster (SQNU-55). Interestingly, the TPE-based SQNU-55 not only provides a good material for the blue LED device, but also has a better luminescent molecular thermometer for low-temperature detection.

Cobalt phosphide nanorings towards efficient electrocatalytic nitrate reduction to ammonia.

High-quality CoP nanorings (CoP NRs) are easily achieved using a phosphorating treatment of CoOOH nanorings, and reveal high activity towards the hydrogen evolution reaction and the nitrate electrocatalytic reduction reaction due to substantial coordinately unsaturated active sites, a high surface area, and available mass transfer pathways. Consequently, the CoP NRs can achieve a faradaic efficiency of 97.1% towards NO3--to-NH3 conversion and provide an NH3 yield of 30.1 mg h-1 mg-1cat at a -0.5 V potential.