Boosting supercapacitive performance of pristine covalent organic frameworks via phenolic hydroxyl groups: A two-in-one strategy.

Two-dimensional covalent organic frameworks (COFs) are ideal electrode materials for electrochemical energy storage devices due to their unique structures and properties, and the accessibility and utilization efficiency of the redox-active sites within COFs are critical determinants of their pseudocapacitive performance. Via introducing meticulously designed phenolic hydroxyl (Ar-OH) groups with hydrogen-bond forming ability onto the imine COF skeletons, DHBD-Sb-COF exhibited improved hydrophilicity and crystallinity than the parent BD-Sb-COF, the redox-active sites (SbPh3 moieties) in COF electrodes could thus be highly accessed by aqueous electrolyte with a high active-site utilization of 93%. DHBD-Sb-COF//AC provided an excellent supercapacitive performance with an energy density of 78 Wh Kg-1 at the power density of 2553 W Kg-1 and super cycling stability, exceeding most of the previously reported pristine COF electrode-based supercapacitors. The "two-in-one" strategy of introducing hydroxyl groups onto imine COF skeletons to enhance both hydrophilicity and crystallinity provides a new avenue to improve the electrochemical performance of COF-based electrodes for high-performance supercapacitors.

Promoting effect of Cu as electron transfer medium on NH3-SCO reaction in asymmetric Ag-Ov-Ti-Sm-Cu ring active site.

Selective catalytic oxidation of ammonia (NH3-SCO) has become an effective method to reduce ammonia (NH3) emissions, and is a key part to solve the problem of NH3 pollution. Nevertheless, the optimization of this technology's performance relies heavily on innovation and the development of catalyst design. In this study, a SmCuAgTiOx catalyst with an asymmetric Ag-Ov-Ti-Sm-Cu ring active site was prepared and applied to the NH3-SCO reaction. The low conversion of Cu-based catalysts in NH3 at low temperature and the inherent low N2 selectivity of Ag-based catalysts were solved. The successful creation of the asymmetric ring active site improved the catalyst's reduction performance. Additionally, Cu, acting as an electron transfer medium, plays a crucial role in enhancing electron transfer within the asymmetric ring active site, thus increasing the redox cycle of the catalyst during the reaction. In addition, some lattice oxygen is lost in the catalyst, resulting in the formation of a large number of oxygen vacancies. This process stimulates the adsorption and activation of surface-adsorbed oxygen, facilitating the conversion of NH3 to an amide (NH2) intermediate during the reaction and reducing non-selective oxidation. The N2 selectivity was improved without significantly affecting the performance of Ag-based catalyst. In-situ diffuse reflectance fourier transform infrared spectroscopy (In-situ DRIFTS) analysis reveals that the SmCuAgTiOx catalyst primarily follows an "internal" selective catalytic reduction (iSCR) mechanism in the NH3-SCO reaction, complemented by the imide mechanism. The asymmetric Ag-Ov-Ti-Sm-Cu ring active site developed in this study provides a new perspective for efficiently solving NH3 pollution in the future.

Post-modification of covalent organic framework functionalized aminated carbon nanotubes with active site (Fe) for the sensitive detection of luteolin.

In this research, the TT-COF(Fe)@NH2-CNTs was innovatively prepared through a post-modification synthetic process functionalized TT-COF@NH2-CNTs with active site (Fe), where TT-COF@NH2-CNTs was prepared via a one-pot strategy using 5,10,15,20-tetrakis (para-aminophenyl) porphyrin (TTAP), 2,3,6,7-tetra (4-formylphenyl) tetrathiafulvalene (TTF) and aminated carbon nanotubes (NH2-CNTs) as raw materials. The complex TT-COF(Fe)@NH2-CNTs material possessed porous structures, outstanding conductivity and rich catalytic sites. Thus, it can be adopted to construct electrochemical sensor with glassy carbon electrode (GCE). The TT-COF(Fe)@NH2-CNTs/GCE can selectively detect luteolin (Lu) with a wide linear plot ranging from 0.005 to 3 µM and a low limit of detection (LOD) of 1.45 nM (S/N = 3). The Lu residues in carrot samples were determined using TT-COF(Fe)@NH2-CNTs sensor and UV-visible (UV-Vis) approach. This TT-COF(Fe)@NH2-CNTs/GCE sensor paves the way for the quantification of Lu through a cost-efficient and sensitive electrochemical approach, which can make a significant step in the sensing field based on crystalline COFs.

Highly Efficient Electrocatalytic Nitrate Reduction to Ammonia: Group VIII-Based Catalysts.

The accumulation of nitrates in the environment causes serious health and environmental problems. The electrochemical nitrate reduction reaction (e-NO3RR) has received attention for its ability to convert nitrate to value-added ammonia with renewable energy. The key to effective catalytic efficiency is the choice of materials. Group VIII-based catalysts demonstrate great potential for application in e-NO3RR because of their high activity, low cost, and good electron transfer capability. This review summarizes the Group VIII catalysts, including monatomic, bimetallic, oxides, phosphides, and other composites. On this basis, strategies to enhance the intrinsic activity of the catalysts through coordination environment modulation, synergistic effects, defect engineering and hybridization are discussed. Meanwhile, the ammonia recovery process is summarized. Finally, the current research status in this field is prospected and summarized. This review aims to realize the large-scale application of nitrate electrocatalytic reduction in industrial wastewater.

Leishmania donovani adenylosuccinate synthetase requires IMP for dimerization and organization of the active site.

Adenylosuccinate synthetase (AdSS), which catalyses the GTP-dependent conversion of inosine monophosphate (IMP) and aspartic acid to succinyl-AMP, plays a major role in purine biosynthesis. In some bacterial AdSS, it is implicated that IMP binding is important to organize the active site, but in certain plant AdSS, GTP performs this role. Here, we report that in Leishmania donovani AdSS, IMP binding favoured dimerization, induced greater conformational change and improved the protein stability more than GTP binding. IMP binding, which resulted in a network of hydrogen bonds, stabilized the conformation of active site loops and brought the switch loop to a closed conformation, which then facilitated GTP binding. Our results provide a basis for designing better inhibitors of leishmanial AdSS.

Exploration of phytoconstituents of Medhya Rasayana herbs to identify potential inhibitors for cerebroside sulfotransferase through high-throughput screening.

Cerebroside sulfotransferase (CST) is a key enzyme in sulfatide biosynthesis and regulation of the myelin sheath in the nervous system. To counter sulfatide accumulation with the deficiency of aryl sulfatase A, CST is considered a target protein in substrate reduction therapy in metachromatic leukodystrophy. In this study, 461 phytoconstituents from four herbs of Medhya Rasayana were screened using multi-pronged virtual screening methods including molecular docking, molecular dynamics (MD) simulation, and reverse pharmacophore analysis. The initial screening of the top 15 hits was based on the binding affinity of the compounds toward the CST substrate-binding site using the lowest free energy of a binding score cutoff of ≤ -7.5 kcal/mol, with the number of conformations in the largest cluster more than 75. The absorption, distribution, metabolism, and excretion (ADME) and toxicity-based pharmacokinetic analysis delivered the top four hits: 18alpha-glycyrrhetinic acid, lupeol, alpha carotene, and beta-carotene, with high blood-brain barrier permeability and negligible toxicity. Furthermore, a 100-ns simulation of protein-ligand complexes with a trajectory analysis of structural deviation, compactness, intramolecular interactions, principal component analysis, free energy landscape, and dynamic cross-correlation analysis showed the binding potential and positioning of the four hits in the binding pocket. Thus, an in-depth analysis of protein-ligand interactions from pre- and post-molecular dynamics simulation, along with reverse pharmacophore mapping, suggests that 18alpha-glycyrrhetinic acid is the most potent and specific CST inhibitor, while beta-carotene could be considered the second most potent compound for CST inhibition as it also exhibited overall stability throughout the simulation. Therefore, the computational drug screening approach applied in this study may contribute to the development of oral drugs as a therapeutic option for metachromatic leukodystrophy.

Atomically Dispersed High-Active Site Density Copper Electrocatalyst for the Reduction of Oxygen.

Enlarging the M-Nx active-site density is an effective route to enhance the ORR performance of M-N-C catalysts. In this work, a single-atom catalyst Cu-N@Cu-N-C with enlarged Cu-N4 active site density was prepared by the second doping and pyrolysis (SDP) of Cu-N-C derived from Cu-doped zeolite imidazole frameworks. The half-wave potentials of Cu-N@Cu-N-C were measured as 0.85 V in alkaline electrolyte and 0.75 V in acidic media, which was 50 mV and 60 mV higher than that of Cu-N-C, respectively. N2 adsorption-desorption isotherm curves and corresponding pore distribution analysis were used to verify the successful filling of additional Cu and N in micropores of Cu-N-C after SDP. The obvious increase in Cu contents for Cu-N@Cu-N-C (1.92 wt%) compared with Cu-N-C (0.88 wt%) tested by ICP demonstrated the successful doping of Cu into Cu-N-C. XAFS analysis confirmed the presence of Cu-N4 single-atom active centers in Cu-N@Cu-N-C. The N 1 s high-resolution XPS results proved a great increase in Cu-N4 contents from 13.15% for Cu-N-C to 18.36% for Cu-N@Cu-N-C. The enhanced ORR performance of Cu-N@Cu-N-C was attributed to the enlargement of Cu-N4 active site density, providing an effective route for the preparation of efficient and low-cost ORR catalysts.

Revealing the Intrinsic Correlation between Cu Scales and Free Radical Chain Reactions in the Regulation of Catalytic Behaviour.

Defining the copper-based catalysts that are responsible for the catalytic behaviour of oil-paper insulation systems and implementing effective regulation are of great significance. Accelerated ageing experiments were conducted to reveal variations in copper scales and deterioration in insulation properties. As ageing progressed, TEM images demonstrated that copper species were adsorbed and aggregated on the fibre surface in the form of nanoparticles (NPs). The scale of NPs exhibited a continuous increase, from 27.06 nm to 94.19 nm. Cu(I) and Cu(II) species were identified as the active sites for inducing intense free radical reactions, which significantly reduced the activation energy, making the insulating oil more susceptible to oxidation. The role of the antioxidant di-tert-butyl-p-cresol (DBPC) in extending the insulation life was regulated by determining the optimal addition time based on variations in the interfacial tension. After the second addition of DBPC, the ageing rates of the dissipation factor, acidity, micro-water and breakdown voltage in the Cu+DBPC group decreased by 28.8%, 43.2%, 52.9% and 46.7%, respectively, compared to the Cu group. This finding not only demonstrates the crucial role of DBPC in preventing the copper-based catalyst-induced oxidation of insulating oil, but also furnishes a vital foundation for enhancing the long-term stability of transformer insulation systems.

Enhancing catalytic efficiency of Bacillus subtilis laccase BsCotA through active site pocket design.

BsCotA laccase is a promising candidate for industrial application due to its excellent thermal stability. In this research, our objective was to enhance the catalytic efficiency of BsCotA by modifying the active site pocket. We utilized a strategy combining the diversity design of the active site pocket with molecular docking screening, which resulted in selecting five variants for characterization. All five variants proved functional, with four demonstrating improved turnover rates. The most effective variants exhibited a remarkable 7.7-fold increase in catalytic efficiency, evolved from 1.54 × 105 M-1 s-1 to 1.18 × 106 M-1 s-1, without any stability loss. To investigate the underlying molecular mechanisms, we conducted a comprehensive structural analysis of our variants. The analysis suggested that substituting Leu386 with aromatic residues could enhance BsCotA's ability to accommodate the 2,2'-azino-di-(3-ethylbenzothiazoline)-6-sulfonate (ABTS) substrate. However, the inclusion of charged residues, G323D and G417H, into the active site pocket reduced kcat. Ultimately, our research contributes to a deeper understanding of the role played by residues in the laccases' active site pocket, while successfully demonstrating a method to lift the catalytic efficiency of BsCotA. KEY POINTS: • Active site pocket design that enhanced BsCotA laccase efficiency • 7.7-fold improved in catalytic rate • All tested variants retain thermal stability.

Expanding the scope of resonance Raman spectroscopy in hydrogenase research: New observable states and reporter vibrations.

Oxygen-tolerant [NiFe] hydrogenases are valuable blueprints for the activation and evolution of molecular hydrogen under application-relevant conditions. Vibrational spectroscopic techniques play a key role in the investigation of these metalloenzymes. For instance, resonance Raman spectroscopy has been introduced as a site-selective approach for probing metal-ligand coordinates of the [NiFe] active site and FeS clusters. Despite its success, this approach is still challenged by a limited number of detectable active-site states - due to missing resonance enhancement or intrinsic light sensitivity - and difficulties in their assignment. Utilizing two oxygen-tolerant [NiFe] hydrogenases as model systems, we illustrate how these challenges can be met by extending excitation and detection wavelength regimes in resonance Raman spectroscopic studies. Specifically, we observe that this technique does not only probe low-frequency metal-ligand vibrations but also high-frequency intra-ligand modes of the diatomic CO/CN- ligands at the active site of [NiFe] hydrogenases. These reporter vibrations are routinely probed by infrared absorption spectroscopy, so that direct comparison of spectra from both techniques allows an unambiguous assignment of states detected by resonance Raman spectroscopy. Moreover, we find that a previously undetected state featuring a bridging hydroxo ligand between Ni and Fe can be probed using higher excitation wavelengths, as photoconversion occurring at lower wavelengths is avoided. In summary, this study expands the applicability of resonance Raman spectroscopy to hydrogenases and other complex metalloenzymes by introducing new strategies for probing and assigning redox-structural states of the active site.

Study on the Hydrophobic Modification Mechanism of Stearic Acid on the Surface of Coal Gasification Fly Ash.

In this study, the hydrophobic modification of coal gasification fly ash (FA) was investigated given the adverse effects of surface hydrophilic structures on the material field. The surface of FA was modified using stearic acid (SA), which successfully altered its hydrophilic structure. When the contact angle of S-FA increased from 23.4° to 127.2°, the activation index increased from 0 to 0.98, the oil absorption decreased from 0.564 g/g to 0.510 g/g, and the BET-specific surface area decreased from 13.973 m2/g to 3.218 m2/g. The failure temperature of SA on the surface of S-FA was 210 °C. The adsorption mechanism of FA was analyzed using density functional theory (DFT) and molecular dynamics (MD). The adsorption of water molecules by FA involved both chemical and physical adsorption, with active adsorption sites for Al, Fe, and Si. The adsorbed water molecules on the surface of FA formed hydrogen bonds with a bond length of 1.5-2.5 Å, leading to agglomeration. In addition, the long alkyl chain in SA mainly relied on the central carbon atom in the (-CH3) structure to obtain electrons in different directions from the H atoms in space, increasing the Coulomb repulsion with the O atoms in the water molecule and thereby achieving the hydrophobic effect. In the temperature range of 298 K to 358 K, the combination of FA and SA became stronger as the temperature increased.

Construction of molecular structure and active site analysis of Zichang coking coal: experimental and computational study.

In the study, the structural parameters of Zichang (ZC) coking coal from northern Shaanxi Province were examined. A theoretical calculation was employed to build a molecular structure model for ZC coal, as well as applying principles of quantum chemistry, the prediction of NMR spectrogram and density for the model was achieved, and the molecular chemical formula was C199H155O36N3. The molecular structure optimization and annealing kinetics calculations are based on molecular mechanics (MM) and molecular dynamics (MD). Subsequently, a representative simplified model was constructed using the aromatic structure as the fundamental unit. On this foundation, the electrostatic potential (ESP), atomic charge distribution, and energy level orbitals were analyzed for this simplified model. The outcomes of this research can serve as an essential guide for determining the reaction order of the active categories during the low-temperature oxidation process for ZC coking coal.

Structural Catalytic Core of the Members of the Superfamily of Acid Proteases.

The superfamily of acid proteases has two catalytic aspartates for proteolysis of their peptide substrates. Here, we show a minimal structural scaffold, the structural catalytic core (SCC), which is conserved within each family of acid proteases, but varies between families, and thus can serve as a structural marker of four individual protease families. The SCC is a dimer of several structural blocks, such as the DD-link, D-loop, and G-loop, around two catalytic aspartates in each protease subunit or an individual chain. A dimer made of two (D-loop + DD-link) structural elements makes a DD-zone, and the D-loop + G-loop combination makes a psi-loop. These structural markers are useful for protein comparison, structure identification, protein family separation, and protein engineering.

Genome-wide identification of HSP90 gene family in Rosa chinensis and its response to salt and drought stresses.

Heat shock protein 90 (HSP90) is important for many organisms, including plants. Based on the whole genome information, the gene number, gene structure, evolutionary relationship, protein structure, and active site of the HSP90 gene family in Rosa chinensis and Rubus idaeus were determined, and the expression of the HSP90 gene under salt, and drought stresses in two rose varieties Wangxifeng and Sweet Avalanche were analyzed. Six and eight HSP90 genes were identified from R. chinensis and Ru. idaeus, respectively. Phylogenetic analysis revealed that the analyzed genes were divided into two Groups and four subgroups (Classes 1a, 1b, 2a, and 2b). Although members within the same classes displayed highly similar gene structures, while the gene structures and conserved domains of Group 1 (Class 1a and 1b) and the Group 2 (Class 2a and 2b) are different. Tandem and segmental duplication genes were found in Ru. idaeus, but not in R. chinensis, perhaps explaining the difference in HSP90 gene quantity in the two analyzed species. Analysis of cis-acting elements revealed abundant abiotic stress, photolight-response, and hormone-response elements in R. chinensis HSP90s. qRT-PCR analysis suggested that RcHSP90-1-1, RcHSP90-5-1 and RcHSP90-6-1 in Sweet Avalanche and Wangxifeng varieties played important regulatory roles under salt and drought stress. The analysis of protein structure and active sites indicate that the potential different roles of RcHSP90-1-1, RcHSP90-5-1, and RcHSP90-6-1 in salt and drought stresses may come from the differences of corresponding protein structures and activation sites. These data will provide information for the breeding of rose varieties with high stress resistance. Supplementary Information: The online version contains supplementary material available at 10.1007/s13205-024-04052-0.

A suicidal and extensively disordered luciferase with a bright luminescence.

Gaussia luciferase (GLuc) is one of the most luminescent luciferases known and is widely used as a reporter in biochemistry and cell biology. During catalysis, GLuc undergoes inactivation by irreversible covalent modification. The mechanism by which GLuc generates luminescence and how it becomes inactivated are however not known. Here, we show that GLuc unlike other enzymes has an extensively disordered structure with a minimal hydrophobic core and no apparent binding pocket for the main substrate, coelenterazine. From an alanine scan, we identified two Arg residues required for light production. These residues separated with an average of about 22 Å and a major structural rearrangement is required if they are to interact with the substrate simultaneously. We furthermore show that in addition to coelenterazine, GLuc also can oxidize furimazine, however, in this case without production of light. Both substrates result in the formation of adducts with the enzyme, which eventually leads to enzyme inactivation. Our results demonstrate that a rigid protein structure and substrate-binding site are no prerequisites for high enzymatic activity and specificity. In addition to the increased understanding of enzymes in general, the findings will facilitate future improvement of GLuc as a reporter luciferase.

Insights into the Understanding of the Nickel-Based Pre-Catalyst Effect on Urea Oxidation Reaction Activity.

Nickel-based catalysts are regarded as the most excellent urea oxidation reaction (UOR) catalysts in alkaline media. Whatever kind of nickel-based catalysts is utilized to catalyze UOR, it is widely believed that the in situ-formed Ni3+ moieties are the true active sites and the as-utilized nickel-based catalysts just serve as pre-catalysts. Digging the pre-catalyst effect on the activity of Ni3+ moieties helps to better design nickel-based catalysts. Herein, five different anions of OH-, CO32-, SiO32-, MoO42-, and WO42- were used to bond with Ni2+ to fabricate the pre-catalysts ß-Ni(OH)2, Ni-CO3, Ni-SiO3, Ni-MoO4, and Ni-WO4. It is found that the true active sites of the five as-fabricated catalysts are the same in situ-formed Ni3+ moieties and the five as-fabricated catalysts demonstrate different UOR activity. Although the as-synthesized five catalysts just serve as the pre-catalysts, they determine the quantity of active sites and activity per active site, thus determining the catalytic activity of the catalysts. Among the five catalysts, the amorphous nickel tungstate exhibits the most superior activity per active site and can catalyze UOR to reach 158.10 mA·cm-2 at 1.6 V, exceeding the majority of catalysts. This work makes for a deeper understanding of the pre-catalyst effect on UOR activity and helps to better design nickel-based UOR catalysts.

Simultaneously improving the activity and thermostability of hyperthermophillic pullulanase by modifying the active-site tunnel and surface lysine.

Pullulanases are important starch-debranching enzymes that mainly hydrolyze the α-1,6-glycosidic linkages in pullulan, starch, and oligosaccharides. Nevertheless, their practical applications are constrained because of their poor activity and low thermostability. Moreover, the trade-off between activity and thermostability makes it challenging to simultaneously improve them. In this study, an engineered pullulanase was developed through reshaping the active-site tunnel and engineering the surface lysine residues using the pullulanase from Pyrococcus yayanosii CH1 (PulPY2). The specific activity of the engineered pullulanase was increased 3.1-fold, and thermostability was enhanced 1.8-fold. Moreover, the engineered pullulanase exhibited 11.4-fold improvement in catalytic efficiency (kcat/Km). Molecular dynamics simulations demonstrated an anti-correlated movement around the entrance of active-site tunnel and stronger interactions between the surface residues in the engineered pullulanase, which would be beneficial to the activity and thermostability improvement, respectively. The strategies used in this study and dynamic evidence for insight into enzyme performance improvement may provide guidance for the activity and thermostability engineering of other enzymes.

Selenium-induced anion vacancy and active site migration stimulating remarkable sulfide Na-Ion storage.

Heterojunctions and controllable anionic vacancies are perceived to be powerful means of ameliorating the performance of sodium-ion batteries assignable to their unique physical and chemical properties. However, the mechanism by which heterojunction and vacancy structures affect sodium-ion battery storage remains to be systemically explored. In this study, the Se doped CoS2@CoS1.035@Carbon (Se-CoS2@CoS1.035@C) heterostructure with anion vacancy was synthesized by a one-step calcination. These heterostructures with lower metal oxidation states and anionic vacancies exhibit exceptional Na+ storage performance (554.3 mA h g-1 after 1500 cycles at 5.0 A g-1). Both electrochemical tests and theoretical calculations demonstrate excellent pseudocapacitive behavior and enhanced Na+ adsorption during discharge because of anionic vacancies and Se doping. Additionally, introducing weaker Co-Se bonds and extending Co-S and Co-Se bonds reduce binding energies, which effectively accelerates the conversion reaction. Our findings provide a feasible way to rationally design and facilely prepare heterostructured anode materials with rich anionic vacancies for sodium-ion batteries.

A robust triphenylamine-based monolithic polymer network for selective sieving of CO2 and PM from flue gas.

The increasingly urgent issue of climate change is driving the development of carbon dioxide (CO2) capture and separation technologies in flue gas after combustion. The monolithic adsorbent stands out in practical adsorption applications for its simplified powder compaction process while maintaining the inherent balance between energy consumption for regeneration and selectivity for adsorption. However, optimizing the adsorption capacity and selectivity of CO2 separation materials remains a significant challenge. Herein, we synthesized monolithic polymer networks (N-CMPs) with triphenylamine adsorption sites, acid-base environment tolerance, and precise narrow microchannel pore systems for the selective sieving of CO2 and particulate matter (PM) in flue gas. The inherent continuous covalent bonding of N-CMPs, along with their highly delocalized π-π conjugated porous framework, ensures the stability of the monolithic polymer network's adsorption and separation capabilities under wet and acid-base conditions. Specifically, under the conditions of 1 bar at 273 K, the CO2 adsorption capacity of N-CMP-1 is 3.35 mmol/g. Attributed to the highly polar environment generated by triphenylamine and the inherent high micropore/mesopore ratio, N-CMPs exhibit an excellent ideal adsorbed solution theory (IAST) selectivity for CO2/N2 under simulated flue gas conditions (CO2/N2 = 15:85). Dynamic breakthrough experiments further visualize the high separation efficiency of N-CMPs in practical adsorption applications. Moreover, under acid-base conditions, N-CMPs achieve a capture efficiency exceeding 99.76 % for PM0.3, enabling the selective separation of CO2 and PM in flue gas. In fact, the combined capture of hazardous PM and CO2 from the exhaust gases produced by the combustion of fossil fuels will play a pivotal role in mitigating climate change and environmental issues until low-carbon and alternative energy technologies are widely adopted.

All-in-One: Plasmonic Janus Heterostructures for Efficient Cooperative Photoredox Catalysis.

Janus heterostructures consisting of multiple jointed components with distinct properties have gained growing interest in the photoredox catalytic field. Herein, we have developed a facile low-temperature method to gain anisotropic one-dimensional Au-tipped CdS (Au-CdS) nanorods (NRs), followed by assembling Ru molecular co-catalyst (RuN5) onto the surface of the NRs. The CdS NRs decorated with plasmonic Au nanoparticles and RuN5 complex harness the virtues of metal-semiconductor and inorganic-organic interface, giving directional charge transfer channels, spatially separated reaction sites, and enhanced local electric field distribution. As a result, the Au-CdS-RuN5 can act as an efficient dual-function photocatalyst for simultaneous H2 evolution and valorization of biomass-derived alcohols. Benefiting from the interfacial charge decoupling and selective chemical bond activation, the optimal all-in-one Au-CdS-RuN5 heterostructure shows greatly enhanced photoactivity and selectivity as compared to bare CdS NRs, along with a remarkable apparent quantum yield of 40.2 % at 400 nm. The structural evolution and working mechanism of the heterostructures are systematically analyzed based on experimental and computational results.