In Situ Construction of Near-Infrared Response Hybrid Up-Conversion Photocatalyst for Degrading Organic Dyes and Antibiotics.

Unique nonlinear optical properties for converting low-energy incident light into high-energy radiation enable up-conversion materials to be employed in photocatalytic systems. An efficient near-infrared (NIR) response photocatalyst was successfully fabricated through a facile two-step method to load BiOBr on the Nd3+, Er3+@NaYF4 (NE@NYF) up-conversion material. The NE@NYF can transform NIR into visible and UV light and promote charge-energy transfer in the semiconductor. Consequently, the as-obtained photocatalysts exhibit excellent photodegradation performance for rhodamine B dye (RhB) and tetracycline (TC) organic pollutants. About 98.9% of the RhB was decomposed within 60 min with the 20% NE@NYF-B sample, outperforming the pristine BiOBr (61.9%). In addition, the 20% NE@NYF-B composite could decompose approximately 72.7% of the organic carbon during a 10 h reaction, which was almost two-fold more than that of BiOBr. Meanwhile, a possible charge transfer mechanism is proposed based on the recombination of electron-hole pairs and reactive oxygen species. This work provides a rational hybrid structure photocatalyst for improving photocatalytic performance in the broadband spectrum and provides a new strategy for NIR light utilization.

Highly Water-Stable and Efficient Hydrogen-Producing Heterostructure Synthesized from Mn0.5Cd0.5S and a Zeolitic Imidazolate Framework ZIF-8 via Ligand and Cation Exchange.

Developing highly water-stable zeolitic imidazolate frameworks (ZIFs) for visible-light-driven photocatalytic hydrolysis is important and challenging. Herein, the Type II heterojunction catalyst Mn0.5Cd0.5S@ZIF-8 and its derivatives (including MCS@ZIF-8-Mn, MCS@ZIF-8-Br, and MCS@ZIF-8-MB) were successfully constructed using a facile strategy. Through dual postsynthetic ligand and cation exchange (PSE) treatments of Mn(Ac)2·4H2O and 4-bromo-1H-imidazole for ZIF-8, the hydrogen production efficiency of the MCS@ZIF-8-MB heterojunction catalyst can reach 5.450 mmol·g-1·h-1 and remain at 97.11% after 9 h of the stability test. Construction of heterojunctions can effectively improve the hydrogen production performance of Mn0.5Cd0.5S while maintaining excellent water stability. X-ray photoelectron spectroscopy results show that upon successful construction of the MCS@ZIF-8-MB heterojunction an interface forms between the surface of MCS and ZIF-8-MB, effectively weakening the photocorrosion of MCS. Density functional theory calculations also indicate that the induction of Mn can increase the electronic states of p and d orbitals near the Fermi level of ZIF-8, suggesting that Mn(II) attracts more electrons than Zn(II). This provides more powerful theoretical evidence for the electron cloud shift from the electron donor S2- to Mn2+.

Enhanced As(III) transformation and removal with biochar/SnS2/phosphotungstic acid composites: Synergic effect of overcoming the electronic inertness of biochar and W2O3(AsO4)2 (As(V)-POMs) coprecipitation.

The activation of carbon atoms in biochar is an important approach for realizing the reuse of discarded woody biomass resources. In this work, a strategy for the construction of carbon-based catalysts was proposed with Magnoliaceae root biomass as a carbon source, doped by SnS2 and further decorated with heteropoly acid. The introduction of SnS2 can activate the carbon atom and destroy the electronic inertness of the disordered biochar with 002 planes. In addition, the synergy between the Keggin unit of phosphotungstic acid and biochar/SnS2 can suppress recombination of e--h+ carriers. The adsorption and photocatalysis experiments results showed that the efficiency of removing As(III) by biochar/SnS2/phosphotungstic acid (biochar/SnS2/PTA) systems was 1.5 times that of biochar/SnS2 systems, and the concentration of total arsenic in the biochar/SnS2/PTA composite system gradually decreased during the photocatalysis process. The formation of As-POMs can simultaneously realize As(III) photooxidation and As(V) coprecipitation. The phase transfer of arsenic by As-POMs could significantly increase the As adsorption capacity. Specifically, the composites achieved the conversion of S atoms at the interface of biochar into SO4•- radicals to enhance the As(III) photooxidation performance.

Nitrogen-deficient g-C3Nx/POMs porous nanosheets with P-N heterojunctions capable of the efficient photocatalytic degradation of ciprofloxacin.

The direct shedding of piperazine rings is critical for the degradation of antibiotic persistent organic pollutants. In this work, nitrogen-deficient g-C3N4 loaded with polyoxometalates porous photocatalysts with P-N heterojunctions were carried out through the formation of chemical bonds between the nitrogen-deficient C+ in g-C3Nx and the bridging oxygen in polyoxometalates (POMs), including phosphomolybdic acid (PMA), phosphotungstic acid (PTA) and silicotungstic acid (STA). The adsorption and photocatalysis experiments confirm the ability of the g-C3Nx/POMs nanosheets to efficiently remove ciprofloxacin via the synergistic effects of adsorption and photo-catalysis. Approximately, g-C3Nx/POMs-30 exhibits the optimal degradation ability, and the degradation rates of g-C3Nx/PMA-30, g-C3Nx/PTA-30 and g-C3Nx/STA-30 could respectively reach 93.1%, 97.4% and 95.6% within only 5 min under visible light. The free radical scavenging experiment and ESR free radical capture experiments confirm that ·OH and ·O2- are free radicals that effectively degrade CIP. According to the results of the LC-MS analysis, the intermediates produced after CIP degradation and the efficient degradation pathway are proposed. The direct shedding of piperazine rings in the decarboxylation and defluorination process leads to the most efficient degradation of CIP into the small molecules.

Photoredox catalysis of As(III) by constructed CSnS bonds: Using biomass as templates leads to bio­carbon/SnS2 nanosheets capable of the efficient photocatalytic conversion of As(III) and calcium arsenate capture.

In this paper, a new interface design strategy for bio­carbon/SnS2 nanosheets equipped with CSnS bonds was proposed by using biomass as a template for the efficient photocatalytic conversion of As(III). The characterization results illustrated that the CSnS bonds could effectively prevent the agglomeration of SnS2, expand the photoresponse range and improve the hydrophilicity of the bio­carbon/SnS2 composites while reducing their transfer resistance. Therefore, the construction of CSnS bonds could more efficiently promote the photoredox catalysis of As(III) to As(V) compared with pure SnS2, attributing to the polarization and conjugation effects of the CSn bonds. Meanwhile, CaSO4·nH2O (n = 0, 0.5, 2) could rapidly convert AsO43- into Ca3(AsO4)2 precipitates to eliminate arsenic from the aqueous solution in one step. In particular, 7500 µg/L As(III) could not only be photocatalyzed into As(V) but also be converted to Ca3(AsO4)2 to achieve the removal of arsenic within only 55 min in the coexistence of CaSO4. In addition, the electron transfer path in the photocatalytic oxidation system on arsenite was proposed according to the Mott-Schottky (MS) plots of SnS2 and graphitic carbon. The electron paramagnetic resonance (EPR) results implied that O2- and h+ were the main active substances in the photooxidation arsenic system and the effect of OH could be negligible. Thus, the possible mechanism of the photocatalytic conversion of As(III) was discussed.

Silver-loaded In2S3-CdIn2S4@X(X=Ag, Ag3PO4, AgI) ternary heterostructure nanotubes treated by electron beam irradiation with enhanced photocatalytic activity.

Ternary heterostructure nanotubes of In2S3-CdIn2S4@X(X = Ag, Ag3PO4, AgI) were synthesized with enhanced photocatalytic activity for efficiently degrading pollutants. Electron beam irradiation was employed to artificially introduce interface defects to the heterostructure nanotubes. The experimental results for degrading carmine and Cr6+ under visible light irradiation showed that the photocatalytic efficiency of In2S3-CdIn2S4 was improved to some extent by the introduction of silver compounds. DRS results confirmed that the band gaps of In2S3-CdIn2S4 were reduced to 1.62 eV and 1.58 eV by introducing Ag3PO4 and AgI, respectively. Interestingly, the band gap of In2S3-CdIn2S4@AgI after electron beam irradiation was further reduced to 1.56 eV, resulting in that the degradation time of both Cr6+ and carmine by In2S3-CdIn2S4@AgI after high-energy electron beam irradiation was shortened to only 5 min. The XRD spectra of the photocatalysts after five cycles could maintain the original crystal form to a large extent. The OH stretching vibration peaks of In2S3-CdIn2S4@AgI after electron beam irradiation at 3387 cm-1 became wider and sharper, thus indicating that the number of free hydroxyl groups on the heterostructure surface significantly increased. PL results showed that electron beam irradiation could significantly reduce the PL emission peak and enhance the utilization of photogenerated charge carriers. EIS results further confirmed that In2S3-CdIn2S4@AgI processed by electron beam irradiation had higher photogenerated electron-hole separation efficiency. Based on the experimental results, a feasible reaction pathway and photocatalytic mechanism for the degradation of carmine was investigated. ESR results showed that the main active groups in the whole photocatalytic system were •O2- and h+.