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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Engineering Z-Scheme FeOOH/PCN with Fast Photoelectron Transfer and Surface Redox Kinetics for Efficient Solar-Driven CO2 Reduction

Shangcong Sun,Bo Peng,Ye Song,Ruoyu Wang,Haitao Song,Wei Lin

Solar-driven conversion of carbon dioxide (CO2) without sacrificial agents offers an attractive alternative in sustainable energy research; nevertheless, it is often retarded by the sluggish water oxidation kinetics and severe charge recombination. To this end, a Z-scheme iron oxyhydroxide/polymeric carbon nitride (FeOOH/PCN) heterojunction, as identified by quasi in situ X-ray photoelectron spectroscopy, is constructed. In this heterostructure, the two-dimensional FeOOH nanorod provides rich coordinatively unsaturated sites and highly oxidative photoinduced holes to boost the sluggish water decomposition kinetics. Meanwhile, PCN acts as a robust agent for CO2 reduction. Consequently, FeOOH/PCN achieves efficient CO2 photoreduction with a superior selectivity of CH4 (>85%), together with an apparent quantum efficiency of 2.4% at 420 nm that outperforms most two-step photosystems to date. This work offers an innovative strategy for the construction of photocatalytic systems toward solar fuel production.

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RSC Advances · 2023 ·Vol. 13 ·期 12 ·8227-8237 · IF 3.9

Interfacial S–O bonds specifically boost Z-scheme charge separation in a CuInS2/In2O3 heterojunction for efficient photocatalytic activity

Xiaofei Fu,Junwu Tao,Zizhou Zhao,Siwen Sun,Lin Zhao,Zuming He,Yong Gao,Yongmei Xia

Reducing the recombination rate of photoexcited electron–hole pairs is always a great challenging work for the photocatalytic technique. In response to this issue, herein, a novel Z-scheme CuInS2/In2O3 with interfacial S–O linkages was synthesized by a hydrothermal and subsequently annealing method. The Fourier transform infrared (FT-IR) and X-ray photoelectron spectrometer (XPS) measurements confirmed the formation of covalent S–O bonds between CuInS2 and In2O3. The quenching and electron spin resonance (ESR) tests revealed the Z-scheme transfer route of photogenerated carriers over the CuInS2/In2O3 heterojunctions, which was further verified theoretically via density functional theory (DFT) calculations. As expected, the CuInS2/In2O3 heterojunctions showed significantly boosted photocatalytic activities for lomefloxacin degradation and Cr(VI) reduction under visible light illumination compared with the bare materials. Accordingly, a synergistic photocatalytic mechanism of Z-scheme heterostructures and interfacial S–O bonding was proposed, in which the S–O linkage could act as a specific bridge to modify the Z-scheme manner for accelerating the interfacial charge transmission. Furthermore, the CuInS2/In2O3 heterojunction also exhibited excellent performance perceived in the stability and reusability tests. This work provides a new approach for designing and fabricating novel Z-scheme heterostructures with a high-efficiency charge transfer route.

CAS / MDL: 98079-51-7
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Journal of Environmental Chemical Engineering · 2023 · IF 7.7

The performance and mechanism of persulfate activation boosted MoO2@LDHs Z-scheme heterojunction for efficient photocatalytic degradation of tetracycline

Xun Li,Yue Meng,Jinhua Li,Lianyang Zhang,Bo Xie,Zheming Ni,Shengjie Xia

Photocatalytic activation of persulfate for the synergistic degradation of pollutants has become a major research hotspot, but the activation effect is poor due to the problems of low catalyst carrier separation efficiency and insufficient active sites. In this study, direct Z-Scheme heterojunctions of MoO 2 @CoFe LDHs were prepared by a simple hydrothermal method and a Co and Fe dual active site system was constructed to activate Na 2 S 2 O 8 (PS) for the synergistic degradation of tetracycline under visible light. The results showed that the synergistic degradation of tetracycline was 3.7 times and 2.7 times more efficient than the original heterojunction and PS, respectively. Combining material characterisation, photovoltaic performance tests and theoretical calculations revealed that the high efficiency is attributed to the formation of an internal electric field under the Z-Scheme heterostructure type generating effective electron-hole separation, with more photo-generated electrons converted into radicals acting together with holes to degrade the TC and activate the PS. More importantly, Co(II) and Fe(II) provide electrons to synergistically activate PS, and a portion of the photogenerated electrons and PS activation intermediates can facilitate cycling between Co(II)/Co(III) and Fe(II)/Fe(III) to accelerate PS activation. This paper's work on activating PS-assisted Z-Scheme heterojunctions for the efficient degradation of TC provides a reference for the study of high-performance photocatalytic catalysts for the degradation of organic pollutants .

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Journal of Environmental Sciences · 2023 · IF 6.9

Enhanced photocatalytic performance of Bi2O2CO3/Bi4O5Br2/reduced graphene oxide Z-schemehe terojunction via a one-pot room-temperature synthesis

Xiaoge Wu,Lei Yan,Rongrong Qin,Qikai Zhang,Wei Yang,Xiaozhi Wang,Yongcai Zhang,Min Luo,Jianhua Hou

Bi 2 O 2 CO 3 (BOC)/Bi 4 O 5 Br 2 (BOB)/reduced graphene oxide (rGO) Z-scheme heterojunction with promising photocatalytic properties was synthesized via a facile one-pot room-temperature method. Ultra-thin nanosheets of BOC and BOB were grown in situ on rGO. The formed 2D/2D direct Z-scheme heterojunction of BOC/BOB with oxygen vacancies (OVs) effectively leads to lower negative electron reduction potential of BOB as well as higher positive hole oxidation potential of BOC, showing improved reduction/oxidation ability. Particularly, rGO is an acceptor of the electrons from the conduction band of BOC. Its dual roles significantly improve the transfer performance of photo-induced charge carriers and accelerate their separation. With layered nanosheet structure, rich OVs, high specific surface area, and increased utilization efficiency of visible light, the multiple synergistic effects of BOC/BOB/rGO can achieve effective generation and separation of the electron-holes, thereby generating more •O 2 − and h + . The photocatalytic reduction efficiency of CO 2 to CO (12.91 µmol/(g·hr)) is three times higher than that of BOC (4.18 µmol/(g·hr)). Moreover, it also achieved almost 100% removal of Rhodamine B and cyanobacterial cells within 2 hours.

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VACUUM · 2022 · IF 4.11

Improved photocatalytic performance of Z-scheme heterostructured SnS2/Sg-C3N4 composite: A new route to increasing specific surface area

Dafeng Gao,Dayi Jiao,Fuming Chen,Yuheng Liang,Yinzhen Wang,Guannan He,Wei Li,Qinyu He

In this study, SnS 2 /S-doped g-C 3 N 4 (Sg-C 3 N 4 ) composite with SnS 2 and Sg-C 3 N 4 in the weight ratio of 9:1 was prepared by a hydrothermal method . For comparison, composites of SnS 2 /Sg-C 3 N 4 with weight ratios of 9:0.05 and 9:1.5, pure SnS 2 , Sg-C 3 N 4 , and g-C 3 N 4 were also prepared using the same processing parameters. Microstructural characterization showed that nano-sized SnS 2 particles were deposited on Sg-C 3 N 4 to form a Z-scheme photocatalyst . The chemical valence of the doped S in Sg-C 3 N 4 was +6, allowing the surface of Sg-C 3 N 4 in the composite to be considerably uneven for the deposition of SnS 2 . The uneven surface of Sg-C 3 N 4 resulted in a rough surface of the SnS 2 /Sg-C 3 N 4 composite, which significantly enhanced the specific surface area and light absorption over a wide wavelength range of 200–1000 nm. The carrier transfer capability and lifetime of g-C 3 N 4 were improved after S doping. The lifetime and transfer ability of the photoproduced carriers in the composite were improved by the Z-scheme heterojunction . Consequently, the rate constant of the composite is thrice that of pure SnS 2 and 57 times that of Sg-C 3 N 4 . This work demonstrates a novel route to enhance light absorption over a wide wavelength range: depositing a semiconductor on a base semiconductor with an uneven surface charge distribution can produce a composite with a rough surface, i.e., a large specific surface area.

CAS / MDL: 7439-98-7
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MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING · 2023 · IF 4.1

Fabrication of magnetically recyclable Fe3O4/BiOCl/BiOBr nanocomposite with Z-scheme heterojunction for high-efficiency photocatalytic degradation of tetracycline

Jingjing Dang,Jianxu Zhang,Yun Shen,Liping Wang,Feng Guo,Yuliang Li,Weisheng Guan

The establishment of Z-scheme heterojunction with ascendant redox ability presents a potential application prospect in the development of efficient photocatalysts for environmental purification. Herein, the Z-scheme Fe 3 O 4 /BiOCl/BiOBr heterostructure composite with preeminent retrievability was obtained using a facile solvothermal method. The various physicochemical properties of the acquired materials were explored through systematic characterizations. The Fe 3 O 4 /BiOCl/BiOBr ternary photocatalyst possessed excellent photocatalytic degradation efficiency (85%) towards tetracycline (TC) under simulated sunlight irradiation. Given the results of capturing experiments, superoxide radicals (·O 2 − ) and holes (h + ) made predominant contributions to the photodegradation reaction. The enhanced photocatalytic activity of Fe 3 O 4 /BiOCl/BiOBr was mostly resulted in the framework of Z-scheme heterojunction, which led to the efficient migration of the photoinduced carriers. In addition, Fe 3 O 4 /BiOCl/BiOBr exhibited good recyclability and stability while retaining its high photocatalytic activity. It was expected that this work would create a new opportunity to fabricate magnetically recyclable photocatalysts with Z-scheme heterojunction for efficient removal of antibiotic pollutants.

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Catalysis Science & Technology · 2023 ·Vol. 13 ·期 15 ·4400-4408 · IF 5

Enhanced adsorption of oxygen species on c/h-In2O3 Z-scheme heterophase junctions for oxygen-mediated photocatalytic hydrogen production

Zhengxin Peng,Xiangbowen Du,Nan Lu,Jing Sui,Xiaofan Zhang,Renhong Li,Xiaoqing Yan

The rational design and fabrication of junction-based photocatalysts is of great importance to enhance the photocatalytic efficiency of water splitting. Herein, a new heterophase junction photocatalyst consisting of cubic bixbyite and rhombohedral corundum In2O3 (c-In2O3 and h-In2O3) was readily prepared by directly annealing an InOOH precursor in an inert atmosphere. The resulting c/h-In2O3 heterophase junction photocatalyst showed an optimal hydrogen production rate of 0.73 mmol g−1 h−1 in a 6 h period reaction from alkaline formaldehyde solution in the presence of molecular oxygen under visible light irradiation, which was approximately 5.6 and 3.4 times higher than that of single-component c-In2O3 and h-In2O3, respectively. The superior photocatalytic activity of the c/h-In2O3 heterophase junction was partially attributed to its appropriate band gap and band positions. Spectroscopic characterization and photoelectrochemistry experiments indicated that the heterophase junction photocatalyst could effectively enhance charge separation and transfer abilities between h-In2O3 and c-In2O3. Furthermore, molecular O2 was found to play a key role in mediating the photocatalytic H2 evolution from formaldehyde oxidation as a catalytic electron scavenger, and O2 was not consumed throughout the reaction. Thus, the photocatalytic activity was also greatly enhanced because the adsorption ability of oxygen species was effectively improved after the formation of heterophase junctions.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Enhanced artificial nitrogen fixation efficiency induced by construction of ternary TiO2/MIL-88A(Fe)/g-C3N4 Z-scheme heterojunction

Qun Ding,Xuejun Zou,Jun Ke,Yuying Dong,Yubo Cui,Hongchao Ma

Herein, a ternary TiO 2 /MIL-88A(Fe)/g-C 3 N 4 heterojunction is successfully constructed through a facile hydrothermal strategy for enhancing solar energy harvesting and efficiency of catalytic nitrogen reduction induced by enlarged light absorption range, increasing interfacial charge transfer ability and desirable stability. Under the simulated sunlight irradiation, the N 2 fixation experiment shows that the yield of NH 3 reaches 1084.31 μmol/(g·h) over the TiO 2 /MIL-88A(Fe)/g-C 3 N 4 photocatalyst, and the yield is significantly enhanced, which is 33.68 and 13.94 times that is higher than the pure TiO 2 and g-C 3 N 4 , respectively. In a mean time, the excellent performance of the photocatalytic N 2 fixation over the ternary TiO 2 /MIL-88A(Fe)/g-C 3 N 4 is verified based on density function theory calculation and the decisive step over the composite is investigated by calculating Gibbs free energies of nitrogen reduction paths. The performance enhancement mechanism of TiO 2 /MIL-88A(Fe)/g-C 3 N 4 is speculated, which indicates that the hybridized three-component system presents a desirable Z-scheme band alignment, resulting in the improvement of separation and transfer efficiency of photoinduced charge carriers. The article shows a new and high-efficiency TiO 2 /MIL-88A(Fe)/g-C 3 N 4 photocatalysis for excellent nitrogen reduction ability.

CAS / MDL: 110-17-8
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CHEMOSPHERE · 2023 · IF 8.8

Bi0·5Na0·5TiO3/ZnO Z-scheme heterojunction for piezo-photocatalytic water remediation: Mechanical energy harvesting and energy band configuration

Peng Wang,Wanqian Cai,Fangyuan Yu,Ping Zhou,Mei Lin,Cong Lin,Tengfei Lin,Min Gao,Chunlin Zhao,Xiangqi Li,Xiao Wu

The decaying photocatalytic rate caused by carrier recombination is a thorny problem that has not been properly solved. Improvement of photocatalysis can be achieved through structural innovation, diversification of catalytic modes, or a combination of both. Herein, effective separation of photo-generated carriers in Bi 0·5 Na 0·5 TiO 3 /ZnO composites was achieved by heterojunction construction for energy band regulation and synchronously mechanical energy harvesting from piezoelectric effect. The formation of heterojunctions between Bi 0·5 Na 0·5 TiO 3 and ZnO was confirmed by electron microscopy and analysis of X-ray photoelectron spectroscopy spectra. The degradation performance of Rhodamine B, a representative industrial dye contaminant, was optimized through the formation of Bi 0·5 Na 0·5 TiO 3 /ZnO heterojunctions and ultrasonic vibration harvesting. Their band structures were described in detail and electrochemical tests were performed to substantiate a novel Z-scheme heterostructure that can explain the carrier separation and transfer processes in catalysis. The piezoelectric polarization field generated by the piezoelectric effect of both Bi 0·5 Na 0·5 TiO 3 and ZnO coordinates perfectly with the photocatalysis , enabling the piezo-photocatalysis. Our research opens a promising avenue in alleviating charge carrier complexation through heterojunction construction and mechanical strain for future pollutants degradation via catalysis.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

In-situ synthesis of direct Z-scheme 2D/2D ZnIn2S4@CeO2 heterostructure toward enhanced photodegradation and Cr(VI) reduction

Qiang Gao,Junxi Li,Bin Liu,Chenguang Liu

The rationally designed semiconductor photocatalytic materials have attracted significant attention because of their huge advantages in the use of solar light. Herein, a series of direct Z-scheme heterojunction nanocomposites were synthesized via in situ growth of zinc indium sulfide nanosheets on ceria nanosheets (ZnIn 2 S 4 @CeO 2 ) and employed for effective photodegradation and Cr(VI) reduction. Advanced characterizations such as XPS , EPR spectra, and DFT calculations verified that the formation of direct Z-scheme charges transfer mechanism promoted rapid charge separation and retained strong redox capacity. As a result, the optimized ZnIn 2 S 4 @CeO 2 sample showed significantly promoted photocatalytic removal rates for tetracycline (TC) and Cr(VI) at a 3.7 and 4.5 times enhancement by comparison with the pristine ZnIn 2 S 4 , respectively. Additionally, after four consecutive cyclic tests, the as-synthesized nanocomposite exhibited remarkable photocatalytic activity and stability. The present work provides an integrated engineering strategy for Z-scheme photocatalyst systems with high photocatalytic efficiency and extensive applications.

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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2022 · IF 10.319

Constructing a Z-scheme Fe-MOF-based heterostructure for visible-light-driven oxidation of aromatic alcohol in ambient air

Lu Zhang,Jianhao Qiu,Guanglu Xia,Dingliang Dai,Xiang Zhong,Jianfeng Yao

Photocatalytic oxidation of aromatic alcohol into aromatic aldehyde using O 2 has received huge attention, while the reaction that occurred in ambient air is rarely studied but follows the green-chemistry principles. Herein, spindle-shaped MIL-53(Fe)-NH 2 @ZnIn 2 S 4 photocatalysts with a Z-scheme heterostructure were facilely developed for photocatalytic oxidation of aromatic alcohol in air under visible light. The benzyl alcohol conversion can be notably enhanced to 73% over the optimal MIL-53-NH 2 @ZnIn 2 S 4 sample with a benzaldehyde production rate of 1825 μmol g –1 h –1 . However, in the O 2 atmosphere, the benzyl alcohol conversion is only 56%, indicating that O 2 is not required and has an adverse effect on the reaction. The hierarchical structure and Z-scheme heterojunction of MIL-53-NH 2 @ZnIn 2 S 4 impart an efficient separation and strong redox abilities of photo-induced electrons and holes, which are responsible for the impressive photocatalytic performance. This study could motivate the ingenious design of Z-scheme heterostructures for green organic conversion based on MOFs.

CAS / MDL: 10312-55-7
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Enwrapping g-C3N4 on In2O3 hollow hexagonal tubular for photocatalytic CO2 conversion: Construction, characterization, and Z-scheme mechanism insight

Ruijie Chen,Haotian Yin,Lei Wang,Zhiqiang Zhang,Jing Ding,Jinfeng Zhang,Hui Wan,Guofeng Guan

The reduction of CO 2 achieved by photocatalysis can simultaneously alleviate the energy crisis and solve environmental issues. Nevertheless, it remains challenging for the rational design of photocatalysts with high-efficiency carrier migration ability. Herein, the Z-scheme g-C 3 N 4 /In 2 O 3 (CN/INO) heterostructure was fabricated via metal–organic frameworks (MOFs) assisted thermal deposition which could form a fully encapsulated hollow tubular structure. The unique structure was based on the MOFs-derived hollow hexagonal In 2 O 3 tubular integrated with ultrathin g-C 3 N 4 . The Z-scheme CN/INO heterojunction exhibited a larger specific surface area and excellent charge separation efficiency. Benefiting from the above features, the Z-scheme CN/INO heterojunction demonstrated superior performance on photocatalytic CO 2 reduction. The formation of CO and CH 3 OH over the optimized CN/INO-2 catalyst was 7.94 and 1.44 µmol⋅g −1 ⋅h −1 , respectively. Moreover, the density functional theory (DFT) calculations and Kelvin probe force microscopy (KPFM) was carried out to further investigate the situation of charge transfer on the interface of CN/INO. The in-situ Fourier transform infrared spectroscopy (FTIR) was measured to confirm the immediate products and the possible mechanism of photocatalytic CO 2 reduction was proposed. This work provided a MOFs-assisted strategy to construct a Z-scheme system for photocatalytic CO 2 reduction.

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