Hai Guo

Construction of highly efficient and stable ternary AgBr/Ag/PbBiO 2 Br Z-scheme photocatalyst under visible light irradiation: Performance and mechanism insight

In this work, the novel ternary AgBr/Ag/PbBiO2Br Z-scheme photocatalysts were synthesized via a CTAB-assisted calcination process. The AgBr/Ag/PbBiO2Br composites were employed for the degradation of rhodamine B (RhB) and antibiotic bisphenol A (BPA) under visible light irradiation. Results showed that the obtained AgBr/Ag-3/PbBiO2Br displayed optimal photocatalytic performance, which could remove almost all RhB within 25u202fmin and effectively decompose 82.3% of BPA in 120u202fmin. Three-dimensional excitation-emission matrix fluorescence spectra (3D EEMs) were utilized for the purposes of fully grasping the behaviors of RhB molecules during the reaction process. Meanwhile, the effects of initial RhB concentration and co-existent electrolytes were investigated from the viewpoint of practical application. In addition, there was no obvious loss in degradation efficiency even after four cycles. The enhanced photocatalytic performances of AgBr/Ag/PbBiO2Br could be credited to the accelerated interfacial charge transfer process and the improved separation of the photogenerated electron-hole pairs. The existence of a small amount of metallic Ag played a significant role in preventing AgBr from being further photocorroded, resulting in the formation of a stable Z-scheme photocatalyst system. This study demonstrated that using metallic Ag as an electron mediator to construct Z-scheme photocatalytic system provided a feasible strategy in promoting the stability of Ag-based semiconductors.

Enhanced Escherichia coli inactivation and oxytetracycline hydrochloride degradation by a Z-scheme silver iodide decorated bismuth vanadate nanocomposite under visible light irradiation

Novel Z-scheme AgI/BiVO4 photocatalysts were fabricated by a chemical deposition-precipitation approach. The photocatalytic activities of the obtained catalysts were evaluated by disinfection of Escherichia coli (E. coli) and degradation of oxytetracycline hydrochloride (OTC-HCl) under visible-light irradiation. The BA3 (contained 9.09% of AgI) exhibited the highest photocatalytic activity and maintained good stability. It could completely inactivate 7.0×107 CFU/mL of E. coli in 50u202fmin and degrade 80% of OTC-HCl in 60u202fmin. The enhanced photocatalytic activity of AgI/BiVO4 composites could be ascribed to the lower recombination rate of electron-hole pairs. Meanwhile, radical trapping experiments revealed that the superoxide radical (O2-) and holes (h+) were the dominant reactive species in photo-disinfection process. Furthermore, the effects of bacterial initial concentration and inorganic anions were also investigated to optimize the photocatalyst for practical application. This study will give a new insight to construct the effective Z-scheme system for bacterial inactivation and organic pollutants degradation.

Co-Mn layered double hydroxide as an effective heterogeneous catalyst for degradation of organic dyes by activation of peroxymonosulfate

In this study, Co-Mn layered double hydroxide (Co-Mn LDH) was synthesized, characterized, and tested as heterogeneous catalyst to activate peroxymonosulfate (PMS) for degradation of organic dyes. The results of characterization showed that Co-Mn LDH had high purity, uniform morphology and large specific surface area (49.9379u202fm2/g). The degradation experiments demonstrated that five different dyes with the concentration of 50u202fmg/L could be decomposed completely within 240u202fs using only 0.025u202fg/L of Co-Mn LDH and 0.1u202fg/L of PMS. Moreover, Co-Mn LDH/PMS system presented the highest decomposition efficiency for acid orange G (AOG) compared with other related materials under the same condition. Further investigation found that Co-Mn LDH/PMS system had an excellent adaptability in a wide pH range (from 3 to 10), and the best efficiency was achieved when the solution was natural (pHu202f=u202f6.87). The mineralization of AOG was assessed by Total Organic Carbon (TOC), and 52.2% of TOC was removed. Meanwhile, the good reusability and high stability of Co-Mn LDH were demonstrated by recycle tests and ion-leaching tests. The catalytic mechanism was explored through quenching tests as well as X-ray photoelectron spectroscopy (XPS) analysis. Finally, all of the results suggested that Co-Mn LDH/PMS system with high stability and decomposition efficiency was suitable for the remediation of organic dyes in wastewater.

Combination of efficient charge separation with the assistance of novel dual Z-scheme system: self-assembly photocatalyst Ag@AgI/BiOI modified oxygen-doped carbon nitride nanosheet with enhanced photocatalytic performance

Natural or artificial Z-scheme systems have been applied for tackling environment pollution and energy crisis owing to the high reduction and oxidation ability driven by the unique interface charge-pairs transfer. However, a dual Z-scheme system combining direct Z-scheme and indirect Z-scheme is seldom adopted for photocatalysis. In this study, the self-assembly photocatalyst Ag@AgI/BiOI/g-C3N4 was successfully fabricated based on the dual Z-scheme system combining direct and indirect Z-scheme systems. The synergistic effect of the dual Z-scheme system towards tetracycline (TC) degradation over the hybrid composites under visible light irradiation was investigated. Compared with single Z-scheme system composites of BiOI/g-C3N4 and AgI/BiOI, the as-synthesized composite of AgI/BiOI/g-C3N4 exhibited superior photocatalytic performance under identical conditions. The dual Z-scheme system was verified by active species generation (˙O2−, ˙OH and h+), trapping experiments and ESR analysis. Furthermore, the photostability and practical application were investigated based on a recycle experiment and controllable experiments. A possible dual Z-scheme mechanism for enhanced photocatalytic performance with ultra-fast charge-separation efficiency and high redox ability was proposed. This study will provide new insight to the design of novel heterojunction composites based on the dual Z-scheme system to deal with organic pollution and energy crisis.

Efficient removal of Cd2+ and Pb2+ from aqueous solution with amino- and thiol-functionalized activated carbon: Isotherm and kinetics modeling

In order to address the increasingly severe pollution issue caused by heavy metals, activated carbon-based absorbents have gained considerable attention. Herein, two novel adsorbents, amino-functionalized activated carbon (N-AC) and thiol-functionalized activated carbon (S-AC), were successfully synthesized by stepwise modification with tetraethylenepentamine (TEPA), cyanuric chloride (CC) and sodium sulfide. The pristine and synthesized materials were characterized by BET analysis, SEM, FTIR spectroscopy, elemental analysis and zeta-potential analyzer. Meanwhile, their adsorption properties for Cd2+ and Pb2+ and the effects of various variables on the adsorption processes were systematically investigated. The findings confirmed that amino-groups and thiol-groups endowed the AC with a strong affinity for metal ions and that the pH of solution affected the uptake efficiencies of the adsorbents by influencing their surface charges. Furthermore, six isotherm models (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Sips and Redlich-Peterson) and four kinetic models (pseudo-first-order, pseudo-second-order, Intra-particle diffusion and Elovich) were applied to interpret the adsorption process at three different temperatures (288u202fK, 298u202fK and 308u202fK). The results indicated that temperature played an important role and that the rate-limiting step was chemosorption. A better fit for all adsorption systems was obtained with Langmuir model, with the maximum adsorption capacities at 298u202fK of 79.20u202fmg Cd2+/g and 142.03u202fmg Pb2+/g for N-AC, 130.05u202fmg Cd2+/g and 232.02u202fmg Pb2+/g for S-AC, respectively. Subsequently, the thermodynamic parameters revealed the nature of the adsorption was endothermic and spontaneous under the experimental condition. The possible adsorption procedures and the underlying mechanisms comprising physical and chemical interactions were proposed. Moreover, the as-synthesized adsorbents exhibited excellent regeneration performance after five adsorption/desorption cycles. The overall results demonstrated that both N-AC and S-AC could be the promising efficient candidates for removing Cd2+ and Pb2+ from contaminated water.

A facile strategy to fabricate hollow cadmium sulfide nanospheres with nanoparticles-textured surface for hexavalent chromium reduction and bacterial inactivation

Exploring morphology and surface structure of semiconductor photocatalyst is crucial for researching their photocatalytic performance. In this paper, hollow CdS nanospheres (CdS-HSs) were successfully fabricated via simple template self-removal strategy. The prepared CdS-HSs were characterized by XRD, SEM, HR-TEM, UV-vis diffuse reflectance spectra (DRS), XPS, photocurrent response (I-T), photoluminescence (PL) and electrochemistry impedance spectroscopy (EIS). It was found that the prepared CdS-HSs have nanoparticles-textured surface composed of ultra-small CdS nanoparticles (∼20u202fnm) and large surface areas. DRS result demonstrated that the CdS-HSs exhibit strong visible light absorption capacity. The results of photocurrent response, photoluminescence and EIS revealed that hollow structure and nanoparticles-textured surface can effectively increase light reflection effect and decrease recombination rate of electrons and holes. Compared to the traditional CdS, the hollow CdS nanospheres exhibit higher photocatalytic activity on Cr(VI) reduction under visible light irradiation, which are primarily attributed to its rapid separation of electron-hole pairs and improved visible light absorption. Moreover, CdS-HSs was also demonstrated as an effective and potential material on photocatalytic disinfection. The result of mechanism experiments proved that h+, e- and O2- play important roles on the bacteria inactivation.

Construction of 2D heterojunction system with enhanced photocatalytic performance: Plasmonic Bi and reduced graphene oxide co-modified Bi5O7I with high-speed charge transfer channels

The efficient electron-hole charge pair separation, ultra-fast electron migration and excellent light harvest capacity are essential for semiconductor photocatalyst with superior photocatalytic performance. In this study, we constructed layered 2D/2D heterojunction composite of Bi@Bi5O7I/rGO (BiBGOI) through a facile surface charge mediated self-assembly strategy. The unique 2D/2D heterostructure with face to face contact can increase the contact area and generate a large amount of charge transfer nanochannels in the interfacial heterojunction, resulting in the enhancement of photocatalytic activity. Addition of semimetal Bi can enhance light absorption, and the local electromagnetic field dominated by SPR effect is favorable for photoinduced charge pair separation. The novel composite showed superior photocatalytic performance for decomposing levofloxacin (LVFX), which was attributed to the unique 2D/2D structure and SPR effect. The enhanced mineralization ability of the novel composite was ascribed to the strong oxidization ability of photoinduced holes, further evaluating high charge pair separation efficiency. In addition, the strong adsorption capacity of rGO for LVFX molecules can enable active radicals transfer into the surface to decompose it. This work will shed light on constructing 2D/2D heterojunction system assisted with SPR effect for the practical application in removal of organic pollutants.

Fabrication of visible-light-driven silver iodide modified iodine-deficient bismuth oxyiodides Z-scheme heterojunctions with enhanced photocatalytic activity for Escherichia coli inactivation and tetracycline degradation

At present, various organic pollutants and pathogenic microorganisms presented in wastewater have severely threatened aquatic ecosystem and human health. Meanwhile, semiconductor photocatalysis technology for water purification has attracted increasingly significant attention. Herein, we successfully constructed a series of novel visible-light-driven (VLD) Bi4O5I2/AgI hybrid photocatalysts with different AgI amounts. Compared with pristine AgI and Bi4O5I2, Bi4O5I2/AgI with the optimal AgI contents exhibited remarkably enhanced photocatalytic performance in probe experiment for Escherichia coli (E. coli) disinfection and tetracycline (TC) degradation. The efficiency for TC degradation and E. coli inactivation reached 82% and 100% in 30u202fmin, respectively. The enhanced electron-hole separation efficiency was responsible for improved photocatalytic activity. In addition, the destruction process of the chemical structure of TC molecules was further investigated by three-dimensional excitation-emission matrix fluorescence spectra (3D EEMs). The activity and crystal phase of the catalysts did not change significantly after four cycles, demonstrating their excellent recyclability and stability of catalysts. The Ag+ ion leaking experiments, radical trapping experiments and ESR tests demonstrated that OH, O2- and h+ were the main active species in photocatalytic disinfection processes. Furthermore, the photocatalytic mechanism of Bi4O5I2/AgI nanomaterials was discussed in detail in conjunction with the energy band structure, and a reasonable Z-scheme interfacial charge transfer mechanism was proposed. This work is expected to provide an efficient water disinfection method.

Enhanced photocatalytic activity of CdS/SnS2 nanocomposite with highly-efficient charge transfer and visible light utilization for selective reduction of 4-nitroaniline

Photocatalytic reduction can be an effective and promising technology for the selective reduction of aromatic nitro organics. In this paper, a novel Z-scheme CdS/SnS2 photocatalyst was well-designed and fabricated via simple in-site reaction process containing thioacetamide as a sulfur sources and cubic CdSnO3 as template. The resulting CdS/SnS2 composite has well-constructed cubic nanostructure of strong adhesion between CdS and SnS2, presenting high absorption to visible light. Importantly, strong charge transfer between the contacting regions of CdS and SnS2 through the intermediate sulfur atoms combined with both metals was generated, which speeds up separation of photogenerated electron and hole. The advantageous combination of high light-harvesting and effective charge transfer is responsible for the excellent photocatalytic activity at the CdS/SnS2 heterointerface. Resultantly, the prepared CdS/SnS2 composites exhibit high conversion efficiency and selectivity on 4-nitroaniline (4-NA) reduction in the aqueous solution containing ammonium formate under visible light irradiation, which can reduce almost all 4-NA within 12u202fmin. Trapping experiments and ESR analysis demonstrated that ammonium formate not only can effectively decrease recombination of photogenerated charge carriers but also react with holes to generate CO2- radicals possessing strong reduction ability. The 4-NA are effectively photo-reduced by the synergistic effect of electrons and CO2- radicals. According to the experimental results, a possible Z-scheme charge transfer mechanism was proposed. Besides, the photo-reduction of aromatic nitro organics possessed different para-groups (p-nitrophenol, nitrobenzene, and p-nitrobenzaldehyde) was also investigated. It is found that the electron-drawing group can decrease the electron density of its para-position nitryl, which quickens the nitro reduction.