Transient-State Self-Bipolarized Organic Frameworks of Single Aromatic Units for Natural Sunlight-Driven Photosynthesis of H2 O2.

Constructing π-conjugated polymer structures through covalent bonds dominates the design of organic framework photocatalysts, which significantly depends on the selection of multiple donor-acceptor building blocks to narrow the optical gap and increase the lifetimes of charge carriers. In this work, self-bipolarized organic frameworks of single aromatic units are demonstrated as novel broad-spectrum-responsive photocatalysts for H2 O2 production. The preparation of such photocatalysts is only to fix the aromatic units (such as 1,3,5-triphenylbenzene) with alkane linkers in 3D space. Self-bipolarized aromatic units can drive the H2 O2 production from H2 O and O2 under natural sunlight, wide pH ranges (3.0-10.0) and natural water sources. Moreover, it can be extended to catalyze the oxidative coupling of amines. Experimental and theoretical investigation demonstrate that such a strategy obeys the mechanism of through-space π-conjugation, where the closely face-to-face overlapped aromatic rings permit the electron and energy transfer through the large-area delocalization of the electron cloud under visible light irradiation. This work introduces a novel design concept for the development of organic photocatalysts, which will break the restriction of conventional through-band π-conjugation structure and will open a new way in the synthesis of organic photocatalysts.

Artificial Photosynthetic System with Spatial Dual Reduction Site Enabling Enhanced Solar Hydrogen Production.

Although S-scheme artificial photosynthesis shows promise for photocatalytic hydrogen production, traditional methods often overly concentrate on a single reduction site. This limitation results in inadequate redox capability and inefficient charge separation, which hampers the efficiency of the photocatalytic hydrogen evolution reaction. To overcome this limitation, a double S-scheme system is proposed that leverages dual reduction sites, thereby preserving energetic photo-electrons and holes to enhance apparent quantum efficiency. The design features a double S-scheme junction consisting of CdS nanospheres decorated with anatase TiO2 nanoparticles coupled with graphitic C3 N4 . The as-prepared catalyst exhibits a hydrogen evolution rate of 26.84 mmol g-1  h-1 and an apparent quantum efficiency of 40.2% at 365 nm. This enhanced photocatalytic hydrogen evolution is ascribed to the efficient charge separation and transport induced by the double S-scheme. Both theoretical calculations and comprehensive spectroscopy tests (both in situ and ex situ) affirm the efficient charge transport across the catalyst interface. Moreover, substituting the reduction-type catalyst CdS with other similar sulfides like ZnIn2 S4 , ZnS, MoS2 and In2 S3 further confirms the feasibility of the proposed double S-scheme configuration. The findings provide a pathway to designing more effective double S-scheme artificial photosynthetic systems, opening up fresh perspectives in enhancing photocatalytic hydrogen evolution performance.

Facile synthesis of CoOx@C/Ti-Fe2O3 photoanodes for efficient photoelectrochemical water oxidation.

The development of photoelectrochemical (PEC) water splitting is hindered by the slow kinetics of four-electron processes for the oxygen evolution reaction (OER) and severe charge recombination. Amorphous carbon was chosen as a carrier for the active sites due to its exceptional conductivity and strong loading capacity. In addition, this enhanced performance was attributed to the loading of oxides of cobalt. Here, amorphous carbon-covered cobalt oxides chosen as a co-catalyst loaded on α-Fe2O3 (noted as CoOx@C/Ti-Fe2O3) have been synthesized, and they show a high current density (2.86 mA cm-2 under 1.23 V vs. RHE), and a low onset potential (0.611 V vs. RHE). Experimental analysis demonstrates that the charge transfer and separation leading to accelerated OER dynamics and improved PEC performance are enhanced by CoOx@C effectively. This study provides new ideas for designing high-performance photoelectrochemical electrodes based on amorphous carbon co-catalysts.

Unraveling the Synergistic Mechanism of Boosted Photocatalytic H2 O2 Production over Cyano-g-C3 N4 /In2 S3 /Ppy Heterostructure and Enhanced Photocatalysis-Self-Fenton Degradation Performance.

In this work, cyano contained g-C3 N4 comodified by In2 S3 and polypyrrole (C≡N─CN/IS/Ppy) materials are synthesized for the photocatalytic production of H2 O2 and photocatalysis-self-Fenton reaction for highly efficient degradation of metronidazole. The results from UV-vis spectrophotometry, surface photovoltage, and Kelvin probe measurements reveal the promoted transport and separation efficiency of photoinduced charges after the introduction of In2 S3 and Ppy in the heterojunction. The existence of a built-in electric field accelerates the photoinduced charge separation and preserves the stronger oxidation ability of holes at the valence band of C≡N─CN. Linear sweep voltammetry measurements, zeta potential analyzations, nitroblue tetrazolium determination, and other measurements show that Ppy improves the conversion ratio of • O2 - to H2 O2 and the utilization ratio of • O2 - , as well as suppresses decomposition of H2 O2 . Accordingly, the H2 O2 evolution rate produced via a two-step single-electron reduction reaction reaches almost 895 µmol L-1 h-1 , a value 80% and 7.2-fold higher than those obtained with C≡N─CN/IS and C≡N─CN, respectively. The metronidazole removal rate obtained via photocatalysis-self-Fenton reaction attains 83.7% within 120 minutes, a value much higher than that recorded by the traditional Fenton method. Overall, the proposed synthesis materials and route look promising for the H2 O2 production and organic pollutants degradation.

Evidence for an Interface of Hybrid Cocatalysts Favoring Photocatalytic Hydrogen Evolution Kinetics.

Hybrid cocatalysts have great application potential for improving the photocatalytic hydrogen evolution performance of semiconductors. The interfaces between components of hybrid cocatalysts make a great contribution to the improvement, but the associated mechanisms remain unclear. Herein, we prepared and tested three comparative CdS-based photocatalysts with NiS, NiS/Ni9S8, and Ni9S8 as the cocatalysts separately. The emphasis is placed on investigating the effect of the NiS/Ni9S8 interfaces on the photocatalytic hydrogen evolution performance of CdS. NiS/Ni9S8 exhibits a higher ability than NiS and Ni9S8 in making CdS a more active photocatalyst for water splitting. It shows that NiS, NiS/Ni9S8, and Ni9S8 perform similarly in terms of promoting the charge transfer and separation of CdS based on steady-state and time-resolved photoluminescence studies. At the same time, the linear sweep voltammetry and electrochemical impedance spectroscopy tests combined with the density functional theory calculations reveal that the component interfaces of NiS/Ni9S8 enable us to lower the water splitting activation energy, the charge-transfer resistance from the cocatalyst to sacrificial agent, and hydrogen adsorption Gibbs free energy. It is evidenced from this work that component interfaces of hybrid cocatalysts play a vital role in accelerating the dynamics of hydrogen evolution reactions.

Enhancing Photocatalytic Hydrogen Evolution by Synergistic Benefits of MXene Cocatalysis and Homo-Interface Engineering.

Photocatalytic water splitting holds great promise as a sustainable and cost-effectiveness alternative for the production of hydrogen. Nevertheless, the practical implementation of this strategy is hindered by suboptimal visible light utilization and sluggish charge carrier dynamics, leading to low yield. MXene is a promising cocatalyst due to its high conductivity, abundance of active sites, tunable terminal functional groups, and great specific surface area. Homo-interface has perfect lattice matching and uniform composition, which are more conducive to photogenerated carriers' separation and migration. In this study, a novel ternary heterogeneous photocatalyst, a-TiO2 /H-TiO2 /Ti3 C2 MXene (MXTi), is presented using an electrostatic self-assembly method. Compared to commercial P25, pristine anatase, and rutile TiO2 , as-prepared MXTi exhibit exceptional photocatalytic hydrogen evolution performance, achieving a rate of 0.387 mmol h-1 . The significant improvement is attributable to the synergistic effect of homo-interface engineering and Ti3 C2 MXene, which leads to widened light absorption and efficient carrier transportation. The findings highlight the potential of interface engineering and MXene cocatalyst loading as a proactive approach to enhance the performance of photocatalytic water splitting, paving the way for more sustainable and efficient hydrogen production.

Investigation of charge dynamics in dinuclear cobalt phthalocyanine ammonium sulfonate (PDS) modified Ti-Fe2O3 photoanodes for photoelectrochemical water oxidation.

The kinetic competition between water oxidation/electron extraction processes and recombination behaviors is a key consideration in the development of efficient photoanodes for solar-driven water splitting. Investigating the photogenerated charge behaviors could guide the construction of high-efficiency photoanodes. In this study, the charge carrier kinetics involved in photoelectrochemical water oxidation of PDS/Ti-Fe2O3 were analyzed using surface photovoltage (SPV), transient photovoltage (TPV), short-pulse transient photocurrent (TPC) and photoelectrochemical impedance spectra (PEIS). The TPC results indicate the interfacial electric field introduced by the PDS loading increases the electron extraction and suppresses the bulk recombination, enhancing the spatial separation of photogenerated charges, which is consistent with the SPV and TPV results. Besides, the surface recombination of the back electron (BER) is also attenuated, which enhances the long-lived holes at the surface of PDS/Ti-Fe2O3 photoanode. Similarly, as obtained by PEIS fitting, the loading of PDS accelerates holes transfer at the photoanode/electrolyte interface, and increases the utilization of long-lived holes. In other word, the recombination behaviors of photogenerated charges are restrained both in the bulk and surface of the photoanode after the deposition of PDS, leading to enhanced PEC performance. These findings highlight the importance of understanding charge carrier dynamics in the design of high-efficient photoanodes.

Interface designing of efficient Z-scheme Ti-ZnFe2O4/In2O3 photoanode toward boosting photoelectrochemical water oxidation.

Ti-ZnFe2O4 photoanode has attracted extensive attention in photoelectrochemical (PEC) water oxidation due to its narrow band gap and good photostability. However, its low efficiency limits its development. Herein, we designed and constructed direct Z-scheme Ti-ZnFe2O4/In2O3 (Ti-ZFO/In2O3) photoanode. Under the interface electric field, photogenerated holes with stronger oxidation capacity on In2O3 are retained to participate in the water oxidation reaction, and the photocurrent density of Ti-ZFO/In2O3 is much higher than that of pure Ti-ZFO, reaching 2.2 mA/cm2 at 1.23 V vs. RHE. Kelvin Probe, steady-state photovoltage spectroscopy (SPV), transient photovoltage spectroscopy (TPV) and in-situ double beam strategy were used to demonstrate the Z-scheme charge transfer mechanism of Ti-ZFO/In2O3 photoanode. Our work provides an effective scheme and technical means for further understanding the mechanism of interfacial charge transfer.

A Twin S-Scheme Artificial Photosynthetic System with Self-Assembled Heterojunctions Yields Superior Photocatalytic Hydrogen Evolution Rate.

Designing heterojunction photocatalysts imitating natural photosynthetic systems has been a promising approach for photocatalytic hydrogen generation. However, in the traditional Z-Scheme artificial photosynthetic systems, the poor charge separation, and rapid recombination of photogenerated carriers remain a huge bottleneck. To rationally design S-Scheme (i.e., Step scheme) heterojunctions by avoiding the futile charge transport routes is therefore seen as an attractive approach to achieving high hydrogen evolution rates. Herein, a twin S-scheme heterojunction is proposed involving graphitic C3 N4 nanosheets self-assembled with hydrogen-doped rutile TiO2 nanorods and anatase TiO2 nanoparticles. This catalyst shows an excellent photocatalytic hydrogen evolution rate of 62.37 mmol g-1 h-1 and high apparent quantum efficiency of 45.9% at 365 nm. The significant enhancement of photocatalytic performance is attributed to the efficient charge separation and transfer induced by the unique twin S-scheme structure. The charge transfer route in the twin S-scheme is confirmed by in situ X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) spin-trapping tests. Femtosecond transient absorption (fs-TA) spectroscopy, transient-state surface photovoltage (TPV), and other ex situ characterizations further corroborate the efficient charge transport across the catalyst interface. This work offers a new perspective on constructing artificial photosynthetic systems with S-scheme heterojunctions to enhance photocatalytic performance.

Engineering the synthesized colloidal CuInS2 passivation layer in interface modification for CdS/CdSe quantum dot solar cells.

Interface modification is an important means to enhance the photovoltaic performance of quantum dot sensitized solar cells (QDSCs). The TiO2/CdS/CdSe solar cells are sensitized with CdS QDs and CdSe QDs, which inevitably introduces a new interface to form a recombination center. Therefore, it is necessary to coat a passivation layer in order to effectively inhibit charge recombination at the CdS/CdSe interface. In this work, CuInS2 (CIS) has been introduced into the CdS/CdSe QD system as an inner passivation layer and the CdS/CIS/CdSe photoanode structure has been fabricated in an environmentally friendly manner. The extracted charge amount (Q) is used to express the charge separation efficiency, indicating that we have obtained outstanding charge extraction efficiency in CIS based CdS/CdSe QDSCs. As a result, the photocurrent density of the TiO2/CdS/CIS/CdSe photoanode significantly has increased from 19.01 mA cm-2 to 22.74 mA cm-2 (TiO2/CdS/CdSe photoanode), which demonstrates a higher photoconversion efficiency of 4.52% in comparison with that of TiO2/CdS/CdSe photoanode.