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- Covalent organic framework assisted low-content ultrafine ru on porous N-doped carbon for efficient hydrogen evolution reactionPublication . Kong-Gang Qu; Zhi-Fei Chen; Li-Hui Wang; Hai-Bo Li; Su-Yuan Zeng; Rui Li; Li-Jian Meng; Hong-Yan Chen; Qing-Xia Yao(Excerpt) Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction (HER) of water splitting; the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy. Ru has aroused significant concern because of its Pt-like activity and much lower price. However, it’s still a top priority to minimize the Ru loading and pursue the most superior cost performance. Herein, N-rich covalent organic framework (COF) was employed to assist the preparation of ultrafine Ru, including nanoclusters and single atoms loaded onto porous N-doped carbon by a simple impregnation-pyrolysis process with a low Ru content of 6.60 wt%, exhibiting superior HER activity with mass activity of 21.86 and 11.52 A mg-1 Ru (@100 mV) in alkaline and acidic conditions, separately 14.7 and 2.12 times higher than that of commercial Pt/C.
- Microwave-assisted synthesis of hierarchical BiOBr/BiOF Z-scheme heterojunction for activating peroxymonosulfate toward photodegradation of the recalcitrant levofloxacinPublication . Guohua Dong; Dongzhe Zhang; Xinjia Zhang; Zhuangfang Zhang; Dong-feng Chai; Lijian Meng; Jinlong Li; Ming Zhao; Wenzhi ZhangHerein, a novel Z-scheme BiOBr/BiOF heterojunction was synthesized via one-step microwave-assisted hydrothermal method, which was integrated with peroxymonosulfate (PMS) to design a sulfate radical (•SO4−) based advanced oxidation processes (AOPs) system through PMS activation (BiOBr/BiOF-PMS) toward Levofloxacin (LFX) photodegradation. In order to achieving an optimal degradation efficiency, the formed BiOBr/BiOF-PMS was systematically investigated and the operational parameters for LFX photodegradation were thoroughly optimized. Thereby, the optimal BiOBr/BiOF exhibits a higher photodegradation efficiency of 89.8 % toward LFX via PMS activation compared to others including PMS alone, BiOBr, BiOF and BiOBr/BiOF with varied ratios. Furthermore, the BiOBr/BiOF has superior stability for multiple cycles and universal applicability for degrading various contaminants. This can mainly be attributed that the formed heterojunction between BiOBr and BiOF and the enhanced concentration of oxygen vacancies (OVs) of BiOBr/BiOF heterojunction, which can synchronously promote the separation and transmission of the photogenerated charges (e−/h+) and thereby lead to more reactive oxygen species (ROS). As well, the expanded optical responsiveness and increased specific surface area of BiOBr/BiOF are also mainly responsible for the improved photodegradation capability. Free radical capture experiments and ESR technique verify that the •O2− is the primary ROS and •SO4− and •OH play subordinative role. The photodegradation pathways of LFX were unraveled based on the identified intermediates with a liquid-chromatography-mass (LC-MS) technique. Consequently, this study offers a novel route by developing Bi-based heterojunction photocatalyst to activate PMS for refractory antibiotic photodegradation.
- Ir Nanoparticles Synergistically Regulated by B, N Co-Doping in Carbon for pH-Universal Bifunctional Electrocatalysts towards Energy-Efficient Hydrogen ProductionPublication . Huang, Hongli; Meng, Lijian; li, Haibo; Li, Rui; Zeng, Suyuan; Yao, Qingxia; Chen, Hongyan; Qu, Kong-GangThe ultralow-potential hydrazine oxidation reaction (HzOR) can be integrated with hydrogen evolution reaction (HER) to construct the overall hydrazine splitting (OHzS) system, thus realizing energy-saving hydrogen production. Meanwhile, the real electrocatalytic processes normally involve the constantly changed pH and also need to operate under different pH conditions. Therefore, designing advanced pH-universal electrocatalysts with high compatibility for HER and HzOR is of greatly practical significance. Herein, ultrafine Ir nanoparticles embedding in B, N-codoped carbon (Ir/BNC) were facilely synthesized with one Ir-based complex and boric acid by simple mixing and pyrolysis. To reach the current density of 10 mA cm−2, the bifunctional Ir/BNC merely demands the low potentials of −4.8/-6.3/-38.5 mV for HER, 7.5/157.8/330.1 mV for HzOR, and 19/236/358 mV for OHzS in the alkaline, neutral and acidic electrolytes, respectively, all greatly outperforming commercial Pt/C and displaying the huge energy-saving advantage for pH-universal hydrogen generation over the conventional water splitting. Underlyingly, the codoping of abundant B and N heteroatoms with different electronic modulation effects can play synergistical roles to Ir active sites, endowing with the pH-universal multifunctionality as well as the boosted intrinsic unit activity. Additionally, the large surface area, rich pores and highly graphitized carbon also collectively ensure the remarkable apparent performance for bifunctional HER and HzOR. This work supplies a promising strategy for exploiting pH-universal HER and HzOR bifunctional electrocatalysts, greatly potential to the practical energy-efficient hydrogen generation.
- Gold Single Atom Doped Defective Nanoporous Copper Octahedrons for Electrocatalytic Reduction of Carbon Dioxide to EthylenePublication . Zhao, Yang; Wang, Yanan; Yu, Zhipeng; Song, Chao; Wang, Jingwei; Huang, Haoliang; Meng, Lijian; Liu, Miao; Liu, LifengElectrocatalytic CO2 reduction into high-value multicarbon products offers a sustainable approach to closing the anthropogenic carbon cycle and contributing to carbon neutrality, particularly when renewable electricity is used to power the reaction. However, the lack of efficient and durable electrocatalysts with high selectivity for multicarbons severely hinders the practical application of this promising technology. Herein, a nanoporous defective Au1Cu single-atom alloy (DeAu1Cu SAA) catalyst is developed through facile low-temperature thermal reduction in hydrogen and a subsequent dealloying process, which shows high selectivity toward ethylene (C2H4), with a Faradaic efficiency of 52% at the current density of 252 mA cm−2 under a potential of −1.1 V versus reversible hydrogen electrode (RHE). In situ spectroscopy measurements and density functional theory (DFT) calculations reveal that the high C2H4 product selectivity results from the synergistic effect between Au single atoms and defective Cu sites on the surface of catalysts, where Au single atoms promote *CO generation and Cu defects stabilize the key intermediate *OCCO, which altogether enhances C−C coupling kinetics. This work provides important insights into the catalyst design for electrochemical CO2 reduction to multicarbon products.
- Piezo-photocatalysis synergy in γ-GeSe for highly efficient oxygen evolution reactionPublication . Zhang, Tianqi; Zhou, Long; Chen, Guobo; Wei, Songrui; Sun, Rong; Li, Yunping; Meng, Lijian; Zhang, Guanglong; Xia, Shuwei; Wang, Zhongchang; Qiu, MengSolar-driven semiconductor photocatalysts are highly appealing in applications of environmental remediation and energy conversion. However, photocatalytic reactions, particularly oxygen evolution reaction (OER), are often constrained by the swift recombination of electron–hole pairs, thereby resulting in low reaction efficiency. Although it is effective to separate charge carriers by constructing heterojunctions to form built-in electric field, the lattice mismatch and inefficient interlayer charge transfer of heterojunctions in the photocatalysts limit their further development. Here, we propose a new strategy by constructing an internal electric field for OER through an individual piezoelectric two-dimensional material. The results indicate that the piezoelectric effect regulates the electronic structure, reduces bandgap, improves light absorption efficiency, and that the displacement of positive and negative charge centers is the key factor in the enhanced OER. This research indicates the feasibility of combining piezoelectric properties of two-dimensional materials with OER (1.19 eV), providing new insights and guidance for applying the piezoelectric effect in the OER and opening up a way to promote efficient separation of charge carriers.
- Microwave-assisted hydrothermal synthesis of Ag/Bi2MoO6/ZnO heterojunction with nano Ag as electronic accelerator pump for high-efficienty photocatalytic degradation of levofloxacinPublication . Li, Jun; Nie, Xin; Meng, Lijian; Zhang, Xinjia; Bai, Liming; Chai, Dong-feng; Zhang, Wenzhi; Zhang, Zhuanfang; Dong, GuohuaThe fluoroquinolone antibiotics, as a category of emerging refractory organic pollutants, have triggered intensive attention due to their persistent ecotoxicology for aquatic environments. Herein, a novel Ag/Bi2MoO6/ZnO (Ag/BMO/ZnO) heterojunction was prepared using a two-step microwave-assisted hydrothermal method for photocatalytic degradation of levofloxacin (LFX). The optimal Ag/BMO/ZnO delivers higher photocatalytic degradation efficiency toward LFX reaching 86.4 %, which is 3 times and 7 times higher than those of neat Bi2MoO6 and ZnO, respectively. This can mainly be attributed that the existence of heterojunction between Bi2MoO6 and ZnO promotes the transmission of photogenerated charges (e−/h+). Furthermore, the introduction of Ag nanoparticles serves as an electron accelerator pump, which can also effectively accelerate the transport and separation of the photogenerated e−/h+. Both of these indirectly retard the recombination of e−/h+. The radical capture assays demonstrate that 1O2, radical dotOH, h+ and radical dotO2– are responsible for the the degradation of LFX and the 1O2 is the primary reactive oxygen species (ROS). Moreover, based on the identification of degradation intermediates via the liquid-chromatography-mass spectrometry (LC-MS) technique, the possible degradation routes of LFX were plausibly inferred. In conclusion, this work provides a new perspective toward antibiotics removal by developing novel heterojunction photocatalysts anchored with precious nanoparticles.
- Permittivity and electrical conductivity of copper oxide nanofluid (12 nm) in water at different temperaturesPublication . Coelho, M.F.; Rivas, M.A.; Vilão, G.; Nogueira, E.M.; Iglesias, T.P.The effective permittivity and electrical conductivity of copper oxide (12 nm) nanofluids in water are studied. The measurements were carried out at various concentrations (up to 2% in volume) and at six temperatures (from 298.15 K to 348.15 K). Empirical equations were used for describing the conductivity and the permittivity of the experimental data. The study shows the influence of the volume fraction, the temperature on relative permittivity and electrical conductivity. When compared with the previously published values for alumina (15 nm) in water, present results show the influence of the nanoparticle’s nature. The enhancement of both permittivity and electrical conductivity were calculated and their behaviour was analysed. It is discussed whether their positive values can be considered greater than what would be expected. The contributions to permittivity from volume, contrast and interactions are separated. Theoretical models are applied in the study of permittivity and electrical conductivity. The poor predictions of classical models for permittivity are attributed to the positive behaviour of the permittivity change on mixing for these nanofluids. The contributions to electrical conductivity from water and nanoparticles are separated.
- Sulfur and phosphorus co-doped FeCoNiCrMn high-entropy alloys as efficient sulfion oxidation reaction catalysts enabling self-powered asymmetric seawater electrolysisPublication . Yu, Zhipeng; Boukhvalov, Danil W.; Tan, Hao; Xiong, Dehua; Feng, Chuangshi; Wang, Jingwei; Wang, Wei; Zhao, Yang; Xu, Kaiyang; Su, Weifeng; Xiang, Xinyi; Lin, Fei; Huang, Haoliang; Zhang, Fuxiang; Zhang, Lei; Meng, Lijian; Liu, LifengSeawater electrolysis (SWE) represents a promising approach to green hydrogen (H2) production but currently faces substantial challenges such as the interference of chlorine chemistry and high energy consumption. In this work, we demonstrate that by replacing the energy-demanding oxygen evolution reaction (OER) with the sulfion oxidation reaction (SOR) and by implementing the concept of bipolar membrane (BPM) electrolysis in an acid-base dual electrolyte system, not only can the notorious chlorine evolution reaction (CER) be completely circumvented, but the energy consumption of SWE be significantly reduced. To do so, we develop a sulfur and phosphorus co-doped FeCoNiCrMn high entropy alloy (HEA-SP) catalyst, which shows good electrocatalytic performance for the SOR in alkaline-saline water. This can be attributed to the abundant lattice defects and strains in HEA-SP, leading to a high density of active sites and an optimized electronic structure favorable for the SOR. Moreover, density functional theory calculations and in situ Raman spectroscopy characterization reveal the crucial role of imperfect sulfur coverage on the HEA in facilitating the formation of Sx clusters during the SOR. Using the HEA-SP as anode catalysts, the SOR-assisted SWE only needs electrical energy of 0.253 kWh to produce one cubic meter of H2 at 100 mA cm−2, in the presence of a BPM. Impressively, chlorine-free H2 production from seawater and upgrading of sulfions to valuable sulfur can occur simultaneously and spontaneously at 10 mA cm−2, highlighting the great potential of the HEA-SP catalysts and the asymmetric cell design to enable energy- and cost-effective seawater electrolysis.
- One-step electrodeposition of bifunctional MnCoPi electrocatalysts with wrinkled globular-flowers-like structure for highly efficient electrocatalytic water splittingPublication . Yang, Fan; Dong, Guohua; Meng, Lijian; Liu, Lina; Liu, Xiangcun; Zhang, Zhuanfang; Zhao, Ming; Zhang, WenzhiThe development and exploration of electrocatalysts with the high reactive and abundant availability is still extremely crucial in electrocatalytic overall water splitting. Herein, a novel globular-flowers-like MnO2/Co3(PO4)2 (denoted as MnCoPi) electrocatalyst on nickel foam was successfully prepared through a simple one-step electrodeposition method. The MnCoPi electrocatalyst simultaneously delivers remarkable electrocatalytic activities for hydrogen evolution reaction (HER) with overpotentials (η10) reaching 102 mV and oxygen evolution reaction (OER) with overpotentials (η10) up to 225 mV in 1 M KOH solution. Furthermore, the assembled electrolyzer cell utilizing MnCoPi as the cathode and anode only requires a low voltage of 1.55 V to achieve a current density of 10 mA cm−2. Moreover, the developed MnCoPi electrocatalyst shows excellent stability during continuous operation for 48 h in OER, HER and overall water splitting process. Compared with the pristine MnO2, the significant electrocatalytic properties of MnCoPi can mainly be attributed to the improved physicochemical properties such as distinctive globular-flowers-like morphology, huge specific surface areas and abundant porosity structure, low electrochemical resistance, especially for the formed heterojunction between MnO2 and Co3(PO4)2, which can provide abundant reactive sites and accelerated electron transfer, etc. Consequently, this work provides a new avenue for the development of efficient and stable bifunctional electrocatalysts for overall water splitting.
- Cu(In,Ga)Se2 based ultrathin solar cells the pathway from lab rigid to large scale flexible technologyPublication . Lopes, T. S.; Teixeira, J. P.; Curado, M. A.; Ferreira, B. R.; Oliveira, A. J. N.; Cunha, J. M. V.; Monteiro, M.; Violas, A.; Barbosa, J. R. S.; Sousa, P. C.; Çaha, I.; Borme, J.; Oliveira, K.; Ring, J.; Chen, W. C.; Zhou, Y.; Takei, K.; Niemi, E.; Deepak, F. L.; Edoff, M.; Brammertz, G.; Fernandes, P. A.; Vermang, B.; Salomé, P. M. P.The incorporation of interface passivation structures in ultrathin Cu(In,Ga)Se2 based solar cells is shown. The fabrication used an industry scalable lithography technique—nanoimprint lithography (NIL)—for a 15 × 15 cm2 dielectric layer patterning. Devices with a NIL nanopatterned dielectric layer are benchmarked against electron-beam lithography (EBL) patterning, using rigid substrates. The NIL patterned device shows similar performance to the EBL patterned device.The impact of the lithographic processes in the rigid solar cells’ performance were evaluated via X-ray Photoelectron Spectroscopy and through a Solar Cell Capacitance Simulator. The device on stainless-steel showed a slightly lower performance than the rigid approach, due to additional challenges of processing steel substrates, even though scanning transmission electron microscopy did not show clear evidence of impurity diffusion. Notwithstanding, time-resolved photoluminescence results strongly suggested elemental diffusion from the flexible substrate. Nevertheless, bending tests on the stainless-steel device demonstrated the mechanical stability of the CIGS-based device.