Constructing Functional Radiation-Resistant Thorium Clusters for Catalytic Redox Reactions.

When catalytic reactions are interfered with by radiation sources, thorium clusters are promising as potential catalysts due to their superior radiation resistance. However, there is currently very little research on the design synthesis and catalytic application of radiation-stable thorium clusters. In this work, we have elaborately engineered and fabricated three high-nuclear thorium cluster catalysts denoted as Th12L3-MA12, Th12L3-MA6-BF6, and Th12L3-Fcc12, which did not undergo any significant alterations in their molecular structures and compositions after irradiation with 690 kGy γ-rays. We systematically investigated the photocatalytic/thermocatalytic properties of these radiation-resistant thorium clusters for the first time and found that γ-rays could not alter their catalytic activities. In addition, it was found that ligand engineering could modulate the catalytic activity of thorium clusters, thus expanding the range of catalytic applications of thorium clusters, including reduction reactions (nitroarene reduction) and some oxidation reactions (N-heterocyclic oxidative dehydrogenation and diphenylmethane oxidation). Meanwhile, all of these organic transformation reactions achieved a >80% conversion and nearly 100% product selectivity. Radiation experiments combined with DFT calculations showed that the synergistic catalysis of thorium-oxo core and ligands led to the generation of specific active species (H+, O2•-, or tBuO/tBuOO•) and activation of substrate molecules, thus achieving superior catalytic performance. This work is not only the first to develop radiation-resistant thorium cluster catalysts to perform efficient redox reactions but also provides design ideas for the construction of high-nuclearity thorium clusters under mild conditions.

Synthesis of Isotypic Giant Polymolybdate Cages for Efficient Photocatalytic C-C Coupling Reactions.

The construction of isotypic high-nuclearity inorganic cages with identical pristine parent structure and increasing nuclearity is highly important for molecular growth and structure-property relationship study, yet it still remains a great challenge. Here, we provide an in situ growth approach for successfully synthesizing a series of new giant hollow polymolybdate dodecahedral cages, Mo250, Mo260-I, and Mo260-E, whose structures are growth based on giant polymolybdate cage Mo240. Remarkably, they show two pathways of nuclear growth based on Mo240, that is, the growth of 10 and 20 Mo centers on the inner and outer surfaces to afford Mo250 and Mo260-I, respectively, and the growth of 10 Mo centers both on the inner and outer surfaces to give Mo260-E. To the best of our knowledge, this is the first study to display the internal and external nuclear growth of a giant hollow polyoxometalate cage. More importantly, regular variations in structure and nuclearity confer these polymolybdate cages with different optical properties, oxidative activities, and hydrogen atom transfer effect, thus allowing them to exhibit moderate to excellent photocatalytic performance in oxidative cross-coupling reactions between different unactivated alkanes and N-heteroarenes. In particular, Mo240 and Mo260-E with better comprehensive abilities can offer the desired coupling product with yield up to 92% within 1 h.

Solid-Liquid-Gas Three-Phase Indirect Electrolysis Enabled by Affinity Auxiliary Imparted Covalent Organic Frameworks.

The design of efficient heterogenous redox mediators with favorable affinity to substrate and electrolyte are much desired yet still challenging for the development of indirect electrolysis system. Herein, for the first time, we have developed a solid-liquid-gas three-phase indirect electrolysis system based on a covalent organic framework (Dha-COF-Cu) as heterogenous redox mediator for S-S coupling reaction. Dha-COF-Cu with the integration of high porosity, nanorod morphology, abundant hydroxyl groups and active Cu sites is much beneficial for the adsorption/activation of thiols, uniform dispersion and high wettability in electrolyte, and efficient interfacial electron transfer. Notably, Dha-COF-Cu as solid-phase redox mediator exhibits excellent electrocatalytic efficiency for the formation of value-added liquid-phase S-S bond product (yields up to 99%) coupling with the generation of gas-phase product of H2 (~1.40 mmol g-1 h-1), resulting in a powerful three-phase indirect electrolysis system. This is the first work about COFs that can be applied in three-phase indirect electrolysis system, which might promote the development of porous crystalline materials in this field.

Calix[4]arene-Functionalized Titanium-Oxo Compounds for Perceiving Differences in Catalytic Reactivity Between Mono- and Multimetallic Sites.

While the difference in catalytic reactivity between mono- and multimetallic sites is often attributed to more than just the number of active sites, still few catalyst model systems have been developed to explore more underlying causal factors. In this work, we have elaborately designed and constructed three stable calix[4]arene (C4A)-functionalized titanium-oxo compounds, Ti-C4A, Ti4-C4A, and Ti16-C4A, with well-defined crystal structures, increasing nuclearity, and tunable light absorption capacity and energy levels. Among them, Ti-C4A and Ti16-C4A can be taken as model catalysts to compare the differences in reactivity between mono- and multimetallic sites. Taking CO2 photoreduction as the basic catalytic reaction, both compounds can achieve CO2-to-HCOO- conversion with high selectivity (close to 100%). Moreover, the catalytic activity of multimetallic Ti16-C4A is up to 2265.5 µmol g-1 h-1, which is at least 12 times higher than that of monometallic Ti-C4A (180.0 µmol g-1 h-1), and is the best-performing crystalline cluster-based photocatalyst known to date. Catalytic characterization combined with density functional theory calculations shows that in addition to the advantage of having more metal active sites (for adsorption and activation of more CO2 molecules), Ti16-C4A can effectively reduce the activation energy required for the CO2 reduction reaction by completing the multiple electron-proton transfer process rapidly with synergistic metal-ligand catalysis, thus exhibiting superior catalytic performance to that of monometallic Ti-C4A. This work provides a crystalline catalyst model system to explore the potential factors underlying the difference in catalytic reactivity between mono- and multimetallic sites.

Interpenetrating 3D Covalent Organic Framework for Selective Stilbene Photoisomerization and Photocyclization.

The selective photoisomerization or photocyclization of stilbene to achieve value upgrade is of great significance in industry applications, yet it remains a challenge to accomplish both of them through a one-pot photocatalysis strategy under mild conditions. Here, a sevenfold interpenetrating 3D covalent organic framework (TPDT-COF) has been synthesized through covalent coupling between N,N,N,N-tetrakis(4-aminophenyl)-1,4-benzenediamine (light absorption and free radical generation) and 5,5'-(2,1,3-benzothiadiazole-4,7-diyl)bis[2-thiophenecarboxaldehyde] (catalytic center). The thus-obtained sevenfold interpenetrating structure presents a functional pore channel with a tunable photocatalytic ability and specific pore confinement effect that can be applied for selective stilbene photoisomerization and photocyclization. Noteworthily, it enables photogeneration of cis-stilbene or phenanthrene with >99% selectivity by simply changing the gas atmosphere under mild conditions (Ar, SeleCis. > 99%, SelePhen. < 1% and O2, SeleCis. < 1%, and SelePhen. > 99%). Theoretical calculations prove that different gas atmospheres possess varying influences on the energy barriers of reaction intermediates, and the pore confinement effect plays a synergistically catalytic role, thus inducing different product generation. This study might facilitate the exploration of porous crystalline materials in selective photoisomerization and photocyclization.

Achieving High-Efficient Photoelectrocatalytic Degradation of 4-Chlorophenol via Functional Reformation of Titanium-Oxo Clusters.

Rational design of crystalline catalysts with superior light absorption and charge transfer for efficient photoelectrocatalytic (PEC) reaction coupled with energy recovery remains a great challenge. In this work, we elaborately construct three stable titanium-oxo clusters (TOCs, Ti10Ac6, Ti10Fc8, and Ti12Fc2Ac4) modified with a monofunctionalized ligand (9-anthracenecarboxylic acid (Ac) or ferrocenecarboxylic acid (Fc)) and bifunctionalized ligands (Ac and Fc). They have tunable light-harvesting and charge transfer capacities and thus can serve as outstanding crystalline catalysts to achieve efficient PEC overall reaction, that is, the integration of anodic organic pollutant 4-chlorophenol (4-CP) degradation and cathodic wastewater-to-H2 conversion. These TOCs can all exhibit very high PEC activity and degradation efficiency of 4-CP. Especially, Ti12Fc2Ac4 decorated with bifunctionalized ligands exhibits better PEC degradation efficiency (over 99%) and H2 generation than Ti10Ac6 and Ti10Fc8 modified with a monofunctionalized ligand. The study of the 4-CP degradation pathway and mechanism revealed that such better PEC performance of Ti12Fc2Ac4 is probably due to its stronger interactions with the 4-CP molecule and better •OH radical production. This work not only presents the effective combination of organic pollutant degradation and simultaneously H2 evolution reaction using crystalline coordination clusters as both anodic and cathodic catalyst but also develops a new PEC application for crystalline coordination compounds.

Preventing Disused Bone Loss through Inhibition of Advanced Glycation End Products.

Bone loss occurs in astronauts during long-term space flight, but the mechanisms are still unclear. We previously showed that advanced glycation end products (AGEs) were involved in microgravity-induced osteoporosis. Here, we investigated the improvement effects of blocking AGEs formation on microgravity-induced bone loss by using the AGEs formation inhibitor, irbesartan. To achieve this objective, we used a tail-suspended (TS) rat model to simulate microgravity and treated the TS rats with 50 mg/kg/day irbesartan, as well as the fluorochrome biomarkers injected into rats to label dynamic bone formation. To assess the accumulation of AGEs, pentosidine (PEN), non-enzymatic cross-links (NE-xLR), and fluorescent AGEs (fAGEs) were identified in the bone; 8-hydroxydeoxyguanosine (8-OHdG) was analyzed for the reactive oxygen species (ROS) level in the bone. Meanwhile, bone mechanical properties, bone microstructure, and dynamic bone histomorphometry were tested for bone quality assessment, and Osterix and TRAP were immunofluorescences stained for the activities of osteoblastic and osteoclastic cells. Results showed AGEs increased significantly and 8-OHdG expression in bone showed an upward trend in TS rat hindlimbs. The bone quality (bone microstructure and mechanical properties) and bone formation process (dynamic bone formation and osteoblastic cells activities) were inhibited after tail-suspension, and showed a correlation with AGEs, suggesting the elevated AGEs contributed to the disused bone loss. After being treated with irbesartan, the increased AGEs and 8-OHdG expression were significantly inhibited, suggesting irbesartan may reduce ROS to inhibit dicarbonyl compounds, thus suppressing AGEs production after tail-suspension. The inhibition of AGEs can partially alter the bone remodeling process and improve bone quality. Both AGEs accumulation and bone alterations almost occurred in trabecular bone but not in cortical bone, suggesting AGEs effects on bone remodeling under microgravity are dependent on the biological milieu.

Oxidation-Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2 O2.

The full reaction photosynthesis of H2 O2 that can combine water-oxidation and oxygen-reduction without sacrificial agents is highly demanded to maximize the light-utilization and overcome the complex reaction-process of anthraquinone-oxidation. Here, a kind of oxidation-reduction molecular junction covalent-organic-framework (TTF-BT-COF) has been synthesized through the covalent-coupling of tetrathiafulvalene (photo-oxidation site) and benzothiazole (photo-reduction site), which presents visible-light-adsorption region, effective electron-hole separation-efficiency and photo-redox sites that enables full reaction generation of H2 O2 . Specifically, a record-high yield (TTF-BT-COF, ≈276 000 µM h-1 g-1 ) for H2 O2 photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation-reduction molecular junction COFs for full reaction photosynthesis of H2 O2 , which might extend the scope of COFs in H2 O2 production.

Regulation of Redox Molecular Junctions in Covalent Organic Frameworks for H2 O2 Photosynthesis Coupled with Biomass Valorization.

H2 O2 photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize the production of value-added products. Here, a series of COFs (i.e. Cu3 -BT-COF, Cu3 -pT-COF and TFP-BT-COF) with regulated redox molecular junctions have been prepared to study H2 O2 photosynthesis coupled with furfuryl alcohol (FFA) photo-oxidation to furoic acid (FA). The FA generation efficiency of Cu3 -BT-COF was found to be 575 mM g-1 (conversion ≈100 % and selectivity >99 %) and the H2 O2 production rate can reach up to 187 000 µM g-1 , which is much higher than Cu3 -pT-COF, TFP-BT-COF and its monomers. As shown by theoretical calculations, the covalent coupling of the Cu cluster and the thiazole group can promote charge transfer, substrate activation and FFA dehydrogenation, thus boosting both the kinetics of H2 O2 production and FFA photo-oxidation to increase the efficiency. This is the first report about COFs for H2 O2 photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous-crystalline catalysts in this field.

Achieving High Photo/Thermocatalytic Product Selectivity and Conversion via Thorium Clusters with Switchable Functional Ligands.

Structural exploration and functional application of thorium clusters are still very rare on account of their difficult synthesis caused by the susceptible hydrolysis of thorium element. In this work, we elaborately designed and constructed four stable thorium clusters modified with different functionalized capping ligands, Th6-MA, Th6-BEN, Th6-C8A, and Th6-Fcc, which possessed nearly the same hexanuclear thorium-oxo core but different capabilities in light absorption and charge separation. Consequently, for the first time, these new thorium clusters were treated as model catalysts to systematically investigate the light-induced oxidative coupling reaction of benzylamine and thermodriven oxidation of aniline, achieving >90% product selectivity and approximately 100% conversion, respectively. Concurrently, we found that thorium clusters modified by switchable functional ligands can effectively modulate the selectivity and conversion of catalytic reaction products. Moreover, catalytic characterization and density functional theory calculations consistently indicated that these thorium clusters can activate O2/H2O2 to generate active intermediates O2·-/HOO· and then improved the conversion of amines efficiently. Significantly, this work represents the first report of stable thorium clusters applied to photo/thermotriggered catalytic reactions and puts forward a new design avenue for the construction of more efficient thorium cluster catalysts.

Keeping Superprotonic Conductivity over a Wide Temperature Region via Sulfate Hopping Sites-Decorated Zirconium-Oxo Clusters.

Metal-oxo clusters have emerged as advanced proton conductors with well-defined and tunable structures. Nevertheless, the exploitation of metal-oxo clusters with high and stable proton conductivity over a relatively wide temperature range still remains a great challenge. Herein, three sulfate groups decorated zirconium-oxo clusters (Zr6 , Zr18 , and Zr70 ) as proton conductors are reported, which exhibit ultrahigh bulk proton conductivities of 1.71 × 10-1 , 2.01 × 10-2 , and 3.73 × 10-2  S cm-1 under 70 °C and 98% relative humidity (RH), respectively. Remarkably, Zr6 and Zr70 with multiple sulfate groups as proton hopping sites show ultralow activation energies of 0.22 and 0.18 eV, respectively, and stable bulk conductivities of >10-2  S cm-1 between 30 and 70 °C at 98% RH. Moreover, a time-dependent proton conductivity test reveals that the best performing Zr6 can maintain high proton conductivity up to 15 h with negligible loss at 70 °C and 98% RH, representing one of the best crystalline cluster-based proton conducting materials.

Redox-Active Crystalline Coordination Catalyst for Hybrid Electrocatalytic Methanol Oxidation and CO2 Reduction.

Hybrid CO2 electroreduction (HCER) is recognized as an important strategy to improve the total value of redox products and energy conversion efficiency. In this work, a coordination catalyst model system (Ni8 -TET with active oxidation sites, Ni-TPP with active reduction sites and PCN-601 with redox-active sites) for HCER was established for the first time. Especially, PCN-601 can complete both anodic methanol oxidation and cathodic CO2 reduction with FEHCOOH and FECO over 90 %. The performance can be further improved with light irradiation (FE nearly 100 %). DFT calculations reveal that the transfer of electrons from NiII 8 clusters to metalloporphyrins under electric fields results in the raised oxidizability of Ni8 clusters and the raised reducibility of metalloporphyrin, which then improves the electrocatalytic performance. This work serves as a well-defined model system and puts forward a new design idea for establishing efficient catalysts for hybrid CO2 electroreduction.

Covalent-Bonding Oxidation Group and Titanium Cluster to Synthesize a Porous Crystalline Catalyst for Selective Photo-Oxidation Biomass Valorization.

The selective photo-oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is important due to its substitute-role in polyester-fabrication. Here, a titanium-cluster based metal-covalent organic framework nanosheet has been synthesized through the covalent-coupling between Ti6 -NH2 and benzotrithiophene tricarbaldehyde (BTT). The integration of them endows the nanosheet with a visible-light-adsorption region, effective electron-hole separation-efficiency and suitable photo-oxidation ability. Specifically, its photo-selectivity for HMF-to-FDCA can be >95 % with ≈100 % conversion, which is more than 2, 5, and 10 times higher than MOF-901 (43 %), Ti6 -NH2 (19 %) and under-darkness (9 %), respectively. Notably, an O2 -based mechanism is proposed and the vital roles of Ti6 -NH2 and BTT are verified by DFT calculations. This work might facilitate the exploration of porous-crystalline-catalysts for selective biomass-valorization.

Light, Heat and Electricity Integrated Energy Conversion System: Photothermal-Assisted Co-Electrolysis of CO2 and Methanol.

Strategy that can design powerful photothermal-catalysts to achieve photothermal-effect assisted coupling-catalysis is much desired for the improvement of energy conversion efficiency and redox product value in CO2 electroreduction system. Herein, a kind of bifunctional viologen-containing covalent organic framework (Ni-2CBpy2+ -COF) has been prepared and successfully applied in photothermal-assisted co-electrolysis of CO2 and methanol. Specifically, the FECO (cathode) and FEHCOOH (anode) for Ni-2CBpy2+ -COF can reach up to ≈100 % at 1.9 V with ≈31.5 % saved overall electricity-consumption when the anodic oxygen evolution reaction (OER) is replaced by methanol oxidation. The superior performance could be attributed to the cyclic diquats in Ni-2CBpy2+ -COF that enhance the photothermal effect (ΔT=49.1 °C) to accelerate faster charge transfer between catalyst and immediate species as well as higher selectivity towards desired products as revealed by DFT calculations and characterizations.

Effects of advanced glycation end products on osteocytes mechanosensitivity.

Osteocytes are extremely sensitive to mechanical loading and govern bone remodeling process. Advanced glycation end products (AGEs) have the capacity to induce osteocyte apoptosis. In order to investigate the effects of AGEs on the mechanosensitivity of osteocytes, the osteocytic-like cells (MLO-Y4) were treated with low (50 µg/ml) and high (400 µg/ml) concentrations of AGEs for 1day and exposed to 15 dyne/cm2 of fluid shear stress. Then the F-actin cytoskeleton, prostaglandin E2(PGE2), Nitric oxide (NO), the Wnt/ß-catenin signaling pathway activity mRNA expressions were detected for osteocytes mechanical response changes; osteocalcin (OCN) and receptor activator of nuclear factor-kappa B ligand (RANKL)/osteoprotegerin (OPG) were detected for the regulation on bone remodeling function of osteocytes. The results showed that AGEs accumulation inhibited the sense of osteocytes to external mechincal loading, promoted shear-induced NO and PGE2 release, suppressed the mechanosensitivity of Wnt/ß-catenin signaling pathway, and furthermore promoted OCN and RANKL/OPG mRNA expressions. These indicated AGEs had an adverse impact on the mechanosensitivity of osteocytes, and led to a negative effect on their regulation of bone remodeling process under mechanical stimulation. This work provides a new perspective to interpret the alteration mechanism of osteocytes mechanosensitivity and provides a novel clue for exploring the mechanism of osteoporosis.

Simultaneous determination of primary particle size distribution and thermal accommodation coefficient of soot aggregates using low-fluence LII.

For the ill-posed inverse problem of LII-based nanoparticle size measurement, recovered primary particle size distribution (PPSD) is sensitive to the uncertainty of LII model parameters. In the absence of reliable prior knowledge, the thermal accommodation coefficient (TAC) and fractal-dependent shielding factor are often required to be inferred simultaneously with the PPSD. In the simplified LII model for low fluence regime, TAC and fractal-dependent shielding factor are combined to define a new fractal-dependent TAC. The present study theoretically verified the feasibility of inferring PPSD and fractal-dependent TAC from the normalized LII signals. Moreover, the inversion is independent of prior knowledge of most full LII model parameters, which is attributed to low laser fluence, normalized signal, and fractal-dependent TAC.

Periodic trapezoidal VO2-Ge multilayer absorber for dynamic radiative cooling.

Nowadays, the requirement for achieving dynamic radiative cooling is more and more intense, so a cooling system is proposed and developed to meet the demand in this paper. This cooling system is composed of a filter and a periodic trapezoidal VO2-Ge multilayer absorber (VGMA). The filter on the top enables the VGMA to reflect most of the solar irradiation at daytime and the absorptance or emittance of the VGMA is very different in the spectrum band of 8-13 µm for insulating and metallic VO2 due to the phase transition characteristic of VO2. With this cooling system, close-to-zero absorptance in the range of 0.3-2.5 µm and high (low) absorptance from 8 to 13 µm are achieved for metallic (insulating) VO2. Based on changing the temperature and absorptivity or emissivity simultaneously, radiative heat can be transferred dynamically to the outer space. When VO2 is in the insulating phase, the absorption mechanism of the absorber is magnetic resonance and surface plasmon polariton resonance, and broadband high absorptivity is achieved by exciting slowlight waveguide mode at broadband wavelengths when VO2 is in metallic phase. The spectral absorptance characteristics of the absorber in the two phase states are investigated as a function of the layer number and the incident angle of the electromagnetic waves. The results show that the absorber designed is insensitive to the incident angle. Moreover, the net cooling power of the VGMA of metallic VO2 is instantly 4 times more than that of insulating VO2 once the phase change temperature is reached. This work will be beneficial to the advancement of dynamic radiative cooling.

Comparison of the Ablation and Hyperechoic Zones in Different Tissues Using Microwave and Radio Frequency Ablation.

OBJECTIVES: The aim of this study was to compare the differences between the ablation region and hyperechoic zones in microwave and radio frequency ablation of different tissues. METHODS: Microwave and radio frequency ablation were performed on fresh porcine muscle and liver with different power levels for 90 seconds. These 2 ablation methods were then performed on rabbit liver in vivo using 20 W for 60 seconds. The volumes of the ablation and hyperechoic zones were compared following different ablation methods. RESULTS: The ablation zones were significantly greater than the hyperechoic zones (P < .05) with the same power and duration when using 2 ablation methods. The differences of the ablation and hyperechoic zones between muscle and liver tissues were significantly different (P < .05). The difference values of the ablation and hyperechoic zones were also significantly different (P < .05) using 2 ablation methods. CONCLUSIONS: The hyperechoic zone may have underestimated the extent of ablation using a specified ablation time. In the same tissue, the hyperechoic zone could more accurately estimate the ablation zones using microwave ablation.

Application of the sequential quadratic programming algorithm for reconstructing the distribution of optical parameters based on the time-domain radiative transfer equation.

Sequential quadratic programming (SQP) is used as an optimization algorithm to reconstruct the optical parameters based on the time-domain radiative transfer equation (TD-RTE). Numerous time-resolved measurement signals are obtained using the TD-RTE as forward model. For a high computational efficiency, the gradient of objective function is calculated using an adjoint equation technique. SQP algorithm is employed to solve the inverse problem and the regularization term based on the generalized Gaussian Markov random field (GGMRF) model is used to overcome the ill-posed problem. Simulated results show that the proposed reconstruction scheme performs efficiently and accurately.

Sulfur atom-directed metal-ligand synergistic catalysis in zirconium/hafnium-oxo clusters for highly efficient amine oxidation.

The performance applications (e.g., photocatalysis) of zirconium (Zr) and hafnium (Hf) based complexes are greatly hindered by the limited development of their structures and the relatively inert metal reactivity. In this work, we constructed two ultrastable Zr/Hf-based clusters (Zr9-TC4A and Hf9-TC4A) using hydrophobic 4-tert-butylthiacalix[4]arene (H4TC4A) ligands, in which unsaturated coordinated sulfur (S) atoms on the TC4A4- ligand can generate strong metal-ligand synergy with nearby active metal Zr/Hf sites. As a result, these two functionalized H4TC4A ligands modified Zr/Hf-oxo clusters, as catalysts for the amine oxidation reaction, exhibited excellent catalytic activity, achieving very high substrate conversion (>99%) and product selectivity (>90%). Combining comparative experiments and theoretical calculations, we found that these Zr/Hf-based cluster catalysts accomplish efficient amine oxidation reactions through synergistic effect between metals and ligands: (i) The photocatalytic benzylamine (BA) oxidation reaction was achieved by the synergistic effect of the dual active sites, in which, the naked S sites on the TC4A4- ligand oxidize the BA by photogenerated hole and oxygen molecules are reduced by photogenerated electrons on the metal active sites; (ii) in the aniline oxidation reaction, aniline was adsorbed by the bare S sites on ligands to be closer to metal active sites and then oxidized by the oxygen-containing radicals activated by the metal sites, thus completing the catalytic reaction under the synergistic catalytic effect of the proximity metal-ligand. In this work, the Zr/Hf-based complexes applied in the oxidation of organic amines have been realized using active S atom-directed metal-ligand synergistic catalysis and have demonstrated very high reactivity.