Adsorption Activity Research Articles

Design of Bi4O5Br2/g‐C3N4 heterojunction for efficient photocatalytic removal of persistent organic pollutants from water

AbstractDyes and antibiotics as typical persistent organic pollutants (POPs) are widely present in the environment, but can hardly be removed completely by traditional water treatment methods. Here, we designed Bi4O5Br2/g‐C3N4 composite nanosheets for efficient photocatalytic removal of POPs in water. The Bi4O5Br2/g‐C3N4 composite with a heterojunction structure exhibited high adsorption and photocatalytic activity for removal of tetracycline (TC) and ciprofloxacin (CIP) with excellent cyclic stability, owing to its large specific surface area as well as enhanced charge separation and visible light utilization. Our characterization revealed that h+ and ·OH are responsible for the photocatalytic degradation of TC and CIP. This work provides insights into the design of photocatalytic materials with synergy of adsorption and photocatalytic degradation, and offers a heterojunction construction strategy for addressing the increasingly severe environmental issues.

X-RAY PHOTOELECTRON SPECTROSCOPY STUDY OF THE REDUCTION AND ADSORPTION CAPACITY OF CARBON NANOMATERIALS BY THE RELEASE OF Mn(VII) IONS

The reductive and adsorption capacity of hierarchically structured carbon films synthesized from glucose on a molten aluminum catalyst under a layer of molten salts and thermally reduced graphene oxide upon their interaction with a sodium permanganate solution in a neutral medium at room temperature has been studied. The data obtained by X-ray photoelectron spectroscopy show that all manganese adsorbed on the surface of all carbon nanomaterials is in a reduced form – most of it is in the form of quadrivalent manganese ions, and about 20% is in the form of trivalent manganese ions, which makes the formed carbon-oxide composites promising materials as cathodes of chemical current sources. Thermally reduced graphene oxide demonstrated the lowest adsorption activity. Hierarchically structured carbon films make it possible to adsorb up to 100 wt % of the original manganese in neutral media, which is much higher than with all known commercial adsorbents.

Bimetallic Metal Organic Framework Composites for Carbondioxide Capture

Maintaining breathable air in human space flight missions is a challenge since there will be a gradual increase in the concentration of CO2 due to the exhalation of the spacecraft crew. Modern air revitalization technology for space missions uses temperature swing adsorption with zeolite-based materials as the adsorbent. However, the major drawbacks of zeolites are difficulty in regenerating used adsorbent and low selectivity towards CO2. Besides, frequent replacement of adsorption beds is necessary because of their low adsorption capacity towards CO2. This requires carrying a few spare beds in the spacecraft, which is not preferred because of the low-weight requirements for space missions. Hence, shifting to alternate materials with more selectivity and adsorption capacity toward CO2 becomes essential. Metal-organic frameworks (MOFs) are a class of crystalline materials found to be potential adsorbents for CO2 capture. Due to their ultra-high porosity, tunable pore characteristics, selective capture, and synergistic performance, they could replace the existing zeolite-based adsorbents. Further enhancement in the adsorption capacity could be achieved by introducing a secondary metal into the framework. This will bring heterogeneity in the structure, creation of defects, and open metal sites, thus enhancing the adsorption behavior. Incorporating a secondary metal into the framework and an additional filler material like activated carbon, making a BMOF composite, would lead to an exemplary improvement in the adsorption activity. The addition of filler material will lead to an increase in pore volume, which will enhance the adsorption capacity. In the current work, activated carbon was synthesized from sawdust via chemical activation method using KOH as the activating agent. It was carried out at low temperatures to boost the porous structure formation. Then the composite of Cu-Ni bimetallic MOF with activated carbon was prepared through one-pot solvothermal synthesis. The incorporation of activated carbon created an additional number of pores in the system leading to enhanced adsorption. N2 adsorption-desorption analysis was carried out to find the surface area. The results showed that the surface area of activated carbon and Cu-Ni-Activated carbon BMOF composite was found to be 576 m2/g and 1321 m2/g, respectively. The analysis also revealed the presence of microporous system in the material. Several characterization techniques, such as IR, SEM, XRD etc., were used to study morphology and characteristic features. The SEM shows that the incorporation of nickel and activated carbon have made a profound modification on the octahedral morphology of copper.CO2 adsorption studies were carried out at 1 bar, 25°C. The BMOF composite adsorbent was found to adsorb ~4.52 mmol/g of CO2 whereas the as-synthesized activated carbon and ZSM-5 were found to adsorb ~2.71 mmol/g and ~1.68 mmol/g respectively. To understand the level of microporosity in the supermicropores range, CO2 adsorption analysis at 1 bar and 0°C was carried out since N2 adsorption at -196°C have limitations due to kinetic diffusion related problems at low temperatures. It revealed a micropore volume (<1.066nm) of 0.252 cm3 /g and a pore size range of 4-10 angstroms, which is ideal for selective CO2 adsorption. Also, the BMOF composite was found to adsorb ~8.27 mmol/g at 0°C, which showed that adsorption capacity increases with a decrease in temperature. Hence, the BMOF composites could serve as a promising adsorbent for selective CO2 capture. Figure 1

Synthesis and characterization of an antibacterial nanocomposite derived from two metal-organic frameworks for dye adsorption and antibacterial activity applications

In recent years, humans have been forced to create effective water treatment methods because of the increasing water contamination caused by various industrial activities. This study focuses on synthesizing a nanocomposite consisting of two metal-organic frameworks based on ZIF-8 with effective antibacterial characteristics and water-stable, highly porous UiO-66-NH2. After characterizing the synthesized nanocomposite, its application as (i) an adsorbent for methylene blue (MB) removal from a polluted aqueous environment and (ii) an antibacterial agent; was considered. The impact of different factors on the uptake of MB, including dye concentration, adsorption temperature, and the initial pH of the solution, was studied. When the temperature was raised to 45 °C, the maximum adsorption capacity of UiO-66-NH2 @ZIF-8 for MB improved to 215.78 mg/g. Moreover, the pseudo-second-order model accurately described the experimental MB uptake results. According to the thermodynamic analysis, the spontaneous endothermic adsorption process of MB onto the synthesized UiO-66-NH2 @ZIF-8 was the consequence of an entropy impact instead of an enthalpy change. Additionally, the synthesized nanocomposite exhibited antibacterial efficacy against two different bacteria, gram-negative E. coli and gram-positive S. aureus, with a minimum inhibitory concentration (MIC) of 30 mg/L against both strains. The results indicated that the synthesized MOF@MOF nanocomposite is efficient in dye removal for water treatment and has excellent potential in disinfection applications.

The adsorption behavior of individual Cu(II), Zn(II), and Cd(II) ions over a CuO-modified ceramic membrane synthesized from fly ash

The ceramic membrane synthesized from fly ash as the base material with the addition of CuO was used as an adsorbent for Cu(II), Zn(II), and Cd(II) ions in an aqueous solution. The effect of CuO on the characteristics and adsorption activity of fly ash-based ceramic membrane has been studied over Cu(II), Zn(II) and Cd(II) ions with different pH of 2–8, contact time of 30–150 min, and initial concentration of metal ions of 0.1–0.7 mmol/L. The adsorption using the batch method was carried out on Cu(II), Zn(II), and Cd(II) ions individually. This study showed that the surface area and the total pore volume of the fly ash-based ceramic membrane with addition of CuO increased to about nearly eight folds and more than three folds, respectively, compared to the original fly ash-based ceramic membrane. However, the pore size of the fly ash-based ceramic membrane with addition of CuO decreased to more than a-half of the original pore size. The optimum adsorption activity of each Cu(II), Zn(II), and Cd(II) ion was achieved at a pH of 4, 6, and 5, respectively. The adsorption kinetics of Cu(II), Zn(II), and Cd(II) ions on the fly ash-based ceramic membrane with addition of CuO followed the second-order pseudo kinetics model. Moreover, the isotherm study on the adsorption of Cu(II), Zn(II), and Cd(II) ions on the fly ash-based ceramic membrane with addition of CuO followed the Langmuir isotherm model. The adsorption capacity of the fly ash-based ceramic membrane with addition of CuO for Cu(II), Zn(II) and Cd(II) ions was 205 mmol/g, 188 mmol/g, and 111 mmol/g, respectively. This study showed clearly that the fly ash-based ceramic membrane with addition of CuO was an effective adsorbent for the adsorption of Cu(II), Zn(II) and Cd(II) ions.

High-Entropy Oxides as Nanozymes for Non-Immunological Electrochemical Monitoring of Cortisol

High entropy oxides (HEOs) are a class of materials that have garnered significant attention in recent years due to their potential use as catalysts in energy-related applications[1]. These materials are derived from high entropy compounds, which consist of equimolar or near equimolar ratios of multiple primary elements and have configurational entropy in the formation of a single-phase structure. The cocktail effect of HEOs gives rise to various catalytically active sites due to the synergistic interaction of the different elements, and lattice distortion during the formation of a single-phase solid solution results in the generation of abundant oxygen vacancies, which enhances the adsorption activity of HEOs and improves their catalytic performance[2]. HEOs can also be cost-efficient by utilizing low-cost transition metal elements as their active centers. Despite their widespread use as catalysts, the application of HEOs in electrocatalysis for molecule monitoring and early diagnosis remains largely unexplored.Cortisol, a glucocorticoid hormone that regulates many aspects of metabolism, stress, and immune response, is closely related to various diseases and disorders[3]. Current methods for noninvasive monitoring of cortisol relies upon immunological assays and typically limited to labor-intensive and time-consuming laboratory techniques. As a consequence, detecting cortisol in a label-free manner that is low cost and offers significant sensor stability and high sensitivity is desirable for many emerging applications, particularly for on-body monitoring.Here, we present work that examines the catalytic activities of HEOs as nanozymes for the electrocatalysis of cortisol. The electrochemical cortisol sensor is based on a novel one-pot microwave-assisted reaction synthesized (Fe, Co, Mn, Ni, Cu) Ox. The catalytic mechanism of electrochemical sensors depends on the formation of various valence metal redox species pairs, where the higher valence state oxidizes cortisol species present on the electrode surface, accompanied by a reduced lower valence state. The one-pot microwave-assisted synthesized HEOs exhibited ultra-high catalytic activity towards cortisol species as measured by cyclic voltammetry and chronoamperometry. Experimental results show a superior sensing performance including a detection limit as low as 0.5 µM (s/N=3), a good linear detection range between 0.01 ~ 4.01 µM, and a sensitivity of 46.5 µA µM-1 cm-2.

Cobalt-loaded three-dimensional mesoporous carbon as sulfur host for lithium‑sulfur batteries

The practical application of lithium‑sulfur batteries has been limited due to the poor electrical conductivity of sulfur, the shuttling effect of polysulfide, and the slow redox kinetics of sulfur species. Designing a multifunctional sulfur host with good conductivity, strong adsorption, and high catalytic activity could effectively address these issues. In this work, the cobalt nanoparticles-loaded three-dimensional mesoporous carbon (Co-TDMC) composite was developed as the multifunctional host for lithium‑sulfur batteries. Due to its large specific surface area (2404.7 m2 g−1), abundant mesopores, and good-catalytic performance, the composite could effectively contain sulfur, adsorb polysulfide, and accelerates the conversion reaction of sulfur species. Therefore, when Co-TDMC was used as the sulfur carrier, the sulfur cathode had an excellent initial discharge capacity (1403 mAh g−1 at 0.1C) and a good rate performance (780.2 mAh g−1 at 1C)·In addition, it has excellent long-term cycling stability (a low decay rate of 0.06 % per cycle during 500 cycles at 1C). This work provides a feasible strategy for improving the cycle stability of lithium‑sulfur batteries.

Biogenesis Synthesis of ZnO NPs: Its adsorption and photocatalytic activity for removal of acid black 210 dye

Biogenesis Synthesis of ZnO NPs: Its adsorption and photocatalytic activity for removal of acid black 210 dye

Multi-phase CdS loaded on biochar for photocatalytic activation of peroxymonosulfate for thiamethoxam degradation: π-conjugation improves PMS adsorption

Mounting evidence highlights the negative impacts of thiamethoxam (THM) on non-target organisms and ecosystem. Herein, multi-phase cadmium sulfide loaded on biochar (CdS@BC) was used to photocatalytic activate peroxymonosulfate (PMS) to remove THM. The obtained CdS@BC significantly improved the photocatalytic performance of PMS on THM degradation with a superior rate constant of 0.165 min−1, 60 times more than that of BC. In addition, the catalyst displayed excellent stability and reusability. The mechanism of free radical formation by adsorption activation of PMS adsorbed on CdS@BC was characterized using active species detection and Density functional theory (DFT) calculations. According to the DFT study, the phase junction and π-conjugated structure contribute to the stable migration of π-electrons, thus effectively activating the PMS to produce active substances for the degradation of THM. The findings provide a theoretical basis for the design and synthesis of effective catalysts for AOPs to remove emerging organic contaminants from wastewater.

Chitosan Hydrogels for Water Purification Applications.

Chitosan-based hydrogels have gained significant attention for their potential applications in water treatment and purification due to their remarkable properties such as bioavailability, biocompatibility, biodegradability, environmental friendliness, high pollutants adsorption capacity, and water adsorption capacity. This article comprehensively reviews recent advances in chitosan-based hydrogel materials for water purification applications. The synthesis methods, structural properties, and water purification performance of chitosan-based hydrogels are critically analyzed. The incorporation of various nanomaterials into chitosan-based hydrogels, such as nanoparticles, graphene, and metal-organic frameworks, has been explored to enhance their performance. The mechanisms of water purification, including adsorption, filtration, and antimicrobial activity, are also discussed in detail. The potential of chitosan-based hydrogels for the removal of pollutants, such as heavy metals, organic contaminants, and microorganisms, from water sources is highlighted. Moreover, the challenges and future perspectives of chitosan-based hydrogels in water treatment and water purification applications are also illustrated. Overall, this article provides valuable insights into the current state of the art regarding chitosan-based hydrogels for water purification applications and highlights their potential for addressing global water pollution challenges.

Prediction of Adsorptive Activities of MOFs for Pollutants in Aqueous Phase Based on Machine Learning

Prediction of Adsorptive Activities of MOFs for Pollutants in Aqueous Phase Based on Machine Learning

In-situ retention of nitrogen, phosphorus in agricultural drainage and soil nutrients by biochar at different temperatures and the effects on soil microbial response

This study conducted a two-year experiment to investigate the impacts of biochar with various temperatures (350 °C, 500 °C, and 650 °C), on the reduction of pollutants in agricultural runoff and the enhancement of soil fertility. The results showed that the biochar significantly reduced the concentrations of total nitrogen and total phosphorus in farmland runoff. Moreover, higher-temperature biochar demonstrated greater efficacy in decreasing pollutants in farmland drainage. Treatment with RB650 resulted in a reduction of the total nitrogen and total phosphorus output load by 29.31–30.67 % and 21.92–25.21 %, respectively, compared to RB350. Furthermore, biochar exhibited substantial enhancements in soil fertility. This was supported by heightened soil organic matter content, increased availability of nutrients, and a noteworthy (P < 0.05) upsurge in pH, organic matter, total nitrogen, and total phosphorus content observed in the second year following the application of biochar. Biochar has the potential to enhance soil enzyme activity and affect microbial community composition, thereby facilitating nutrient cycling. The findings illustrated the regenerative and recyclable characteristics of biochar's adsorption activity throughout crop growth. This process enables sustained improvement in soil nutrient retention capacity and fertility. Thus, it emphasizes the potential of biochar as an in-situ model for nutrient retention and recycling, offering an effective approach to mitigate agricultural non-point source (NPS) pollution and enhance soil fertility.

Application of Metal-Organic Frameworks for Efficient Removal of Doxorubicin Hydrochloride: Removal Process Optimization and Biological Activity.

This study looked at the doxorubicin hydrochloride (DOX) anticancer drug's adsorption characteristics on a silver-based metal-organic framework (Ag-MOF). X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) were used for the characterization of Ag-MOF. The pore volume and surface area of Ag-MOF were determined through Brunauer-Emmett-Teller (BET) testing at 77 K to be 0.509 cm3/g and 676.059 m2/g, respectively. Adsorption at pH 6 was established to be the best for DOX compared to alkaline solution. Ag-MOF has a good capacity for eliminating DOX (1.85 mmol/g), according to adsorption experiments. From the adsorption results, we can find that Langmuir is the most fitted adsorption isotherm model and the pseudo-second order model best fitted the adsorption kinetics. The energy of activation for adsorption, which was determined to be 15.23 kJ/mol, also supported a chemisorption process. The mechanism of adsorption was evaluated, and details of all possible interactions between DOX and Ag-MOF were illustrated. On the other hand, while examining the impact of temperature, we identified the thermodynamic constraints as ΔG°, ΔH°, and ΔS° and confirmed that the reaction was an endothermic one and spontaneous. Even after numerous reuse cycles, the efficiency remained constant. The synthetic adsorbent was remarkably recyclable at a rate of more than 91.6%. By using the MTT assay, the cytotoxicity of the tested Ag-MOF and DOX@Ag-MOF against human breast cancer cells (MCF-7) was evaluated in vitro. The in vitro antimicrobial activity of Ag-MOF and DOX@Ag-MOF was also tested.

Removal of oxytetracycline from water by S-doped MIL-53(Fe): Synergistic effect of surface adsorption and persulfate activation

In this study, a novel catalyst based on MIL-53(Fe) was synthesized and modified through sublimed sulfur (S-MIL-53(Fe)) to induce a synergistic effect of surface adsorption and persulfate activation. The S-doped modification not only increased the surface area but also accelerated the electron transfer process of the iron cycle. The performance of the newly synthesized S-MIL-53(Fe) adsorptive catalyst was evaluated by chemical adsorption and peroxydisulfate (PDS) activated removal of an emerging pollutants, oxytetracycline (OTC). The S-MIL-53(Fe) adsorptive catalyst was able to adsorb 61.7% of OTC after 120 min, and the removal efficiency reached 84.8% within 5 min after PDS dosing. The boosting effect of sulfur on the system was confirmed by characterization analysis and experimental testing. Even after 7 cycles, the removal efficiency of S-MIL-53(Fe) (69.0%) for OTC remained superior to that of pure MIL-53(Fe) (25.1%). Additionally, the adsorption kinetics and adsorption isotherm model of the material were investigated. The possible OTC degrading process was proposed based on radical quenching and electron paramagnetic resonance (EPR). This study provides a feasible way to fabricate an S-doped MIL-53(Fe) adsorptive catalyst for the remediation of antibiotics-containing wastewater.

Fast g-C3N4 sonocoated activated carbon for enhanced solar photocatalytic oxidation of organic pollutants through Adsorb & Shuttle process

To solve low mass transfer in photocatalytic technology for water treatment, the combination of photoactive nanoparticles with highly adsorptive materials has been regarded as a successful approach. The optimization of photoactive particle coating in terms of dispersion on the surface of adsorbing support is the main key to reach a maximum synergism for pollutants removal. This study discusses the coating of as-prepared biomass based activated carbon by g-C3N4 using three routes, namely ball milling (AC-CN@BM), physical stirring (AC-CN@Phy) and ultrasonic assisted coating (AC-CN@US). The coating mechanisms by different processes were discussed using different characterization techniques. Ball milling based coating provides good g-C3N4 dispersion on the surface of AC, however, a partial degradation of g-C3N4 structure and a lower surface area were confirmed by FTIR, XRD and BET analysis. Physically designed sample shows a significant agglomeration of particles on the surface of AC. However, ultrasonic coating provides excellent distribution of g-C3N4 and high surface of the composite. In terms of photoactivity, AC-CN@BM exhibits the lowest adsorption and photocatalytic activity under solar light for the removal of ciprofloxacin. AC-CN@Phy showed medium performance, but less physical stability of g-C3N4 particles on AC, leading to their partial release. AC-CN@US showed the highest efficiency and stability after using; suggesting the good combination between g-C3N4 and AC, which in turn maximizes the removal of ciprofloxacin via Adsorb & shuttle process. The overall costs of composite, including the starting elements and the coating ultrasonic process are relatively low and green as compared to commonly reported routes.

The initial application of conch-shell hydroxyapatite and HACC as functional filler in PMMA bone cement

In this study, we acquired conch-shell Hydroxyapatite (cHA)with a mean size of 99.41 nm using a microwave-assisted method, and hydroxypropyl trimethyl ammonium chloride chitosan (HACC) with a molecular weight of 41 kDa was synthesized from deacetylated chitosan. These two additives were added to plain PMMA bone cement, improving its biological activity. It was shown that the addition of cHA and HACC balanced the mechanical performance and porosity of the implant, improving its biocompatibility with mouse pre-osteoblasts (MC3T3-E1). A composite cement with 30 wt% cHA and 0.5 wt% HACC significantly enhanced mineralization efficiency, protein adsorption, and alkaline phosphatase (ALP) activity.

UV-induced graft polymerization of polyamide-6 for electroless copper deposition

A simple and chromium-free method for the metallization on engineering plastic polyamide-6 (PA6) by UV irradiation is proposed in this article. The surface graft polymers with specific adsorption activity are developed through one-step UV exposure operation, which captures Pd2+ in the activation process. The chemisorption of Pd2+ is further reduced into catalytic Pd0 to enable the substrate with catalytic nucleus for conventional copper electroless deposition (ELD). The grafting layer and the deposited copper coating are characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, contact angle measurements, scanning electron microscopy, and X-ray diffraction. The results indicate that successful grafting occurs on PA6 after UV excitation. In addition, the as-deposited copper layer shows excellent conductive performance and high adhesion with the PA6 substrate. It’s expected that this emerging and feasible approach would have broad prospects for the metallization of plastic and offer significant value in the plating industry.

Synthesis of Porous Activated Carbon Doped with Tetramethylammonium Hydroxide: Evaluation of Excellent Gasoline Vapor Adsorption Performance and Activation Mechanism.

The rapid urbanization and industrialization in China have led to an urgent dilemma for controlling urban air pollution, including the intensified emission of gasoline vapor into the atmosphere. Herein, we selected highland barley straw as a raw material and KOH and tetramethylammonium hydroxide (TMAOH) as activators to synthesize nitrogen-doped layered porous carbon (K-thAC) by a three-step activation method. The obtained K-thAC materials had a high specific surface area, reaching 3119 m2/g. Dynamic adsorption experiments demonstrated a superior adsorption capacity of up to 501 mg/g (K-thAC-25) for gasoline vapor compared with other documented carbon adsorbents. Moreover, adjusting the ratio of raw materials with a series of active ingredients could further improve the pore properties of the obtained K-thACs and their adsorption performance for gasoline vapor. Furthermore, the K-thAC materials were also characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), synchronous thermogravimetry (STA), X-ray powder diffraction (XRD), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption tests. This study synthesized a novel plant-based material to treat gasoline vapor pollution efficiently.

Defect-Engineered VS2 Electrocatalysts for Lithium-Sulfur Batteries.

Defective two-dimensional transition metal dichalcogenides can be effective electrocatalysts for Li-S batteries, but the relationship between defect types and battery performance is unclear. In this work, we designed S vacancy-type SV-VS2 and V self-intercalated-type VI-VS2 and measured their catalytic activities in Li-S batteries. Compared with self-intercalating V atoms, S vacancies accelerated Li+ diffusion and SV-VS2 as a Li+ "reservoir" promoted the sulfur conversion kinetics significantly. In addition, the presence of sulfur vacancies promoted the lithiation behavior of SV-VS2 during discharge, leading to an enhancement of the catalytic ability of SV-VS2. However, this lithiation phenomenon weakened the catalytic activity of VI-VS2. Overall, SV-VS2 had better adsorption and catalytic activity. Li-S batteries with SV-VS2-coated separators delivered high rate performance and excellent cycling stability, with a capacity decay rate of 0.043% over 880 cycles at 1.0 C. This work provides an effective strategy for designing efficient Li-S battery electrocatalysts using defect engineering.

Light-assistance in nitrogen fixation to ammonia by highly dispersed Cs-promoted Ru clusters supported on ZrO2

Light-assisted N2 fixation to NH3 under mild conditions is attracting massive attention to circumvent energy crisis and global warming. Herein, highly dispersed Cs-decorated Ru sub-nanometric clusters supported on ZrO2 NPs have been prepared by means of MOF-templated transformation method. The obtained catalyst exhibited N2 hydrogenation activity of 1.6 mmolNH3 gcat−1 h−1 in the dark (350 °C, 0.1 MPa). Remarkably this value increased by over 300 %, reaching 5.1 mmolNH3 gcat−1 h−1 (204 mmolNH3 gRu−1 h−1) under 1 Sun power illumination (1080 W/m2) The influence of the incident light wavelength has been evaluated, revealing 81 % and 213 % enhancement in the NIR and visible region, respectively. DFT calculations were carried out to understand the static adsorption states of Ru sub-nanoclusters. Mechanistic studies have confirmed the co-existence of a photothermal and a nonthermal-hot electron mechanism. XPS, PXRD and FTIR analysis have determined that the Cs species block surface Zr4+ acidity, increasing the basicity of the ZrO2 support. Moreover, partially reduced Csδ+ (0 <δ < 1) species surrounding the Ru active sites are donating electron density to the adjacent Ru sites, favoring N2 adsorption and subsequent activation. Finally, this photocatalyst has shown an extended stability for 100 h irradiation under continuous flow.