ChemSusChem
·
2023
·Vol. 16
·期 19
·e202300601
·
IF 8.4
Jilin Liu,Kai Yu,Zhiyuan Qiao,Qianlong Zhu,Hong Zhang,Jie Jiang
Graphical A tandem catalyst, Cu 2 O NCs-C-Copc, consisting of acetylene black, cobalt phthalocyanine (Copc) and Cu 2 O nanocubes was developed for efficient converting of CO 2 to C 2 H 4 . We propose the Cu 2 O NCs-C-Copc mechanism suppressing side reactions and simultaneously enriching CO. Here, we report faradaic efficiencies of C 2 H 4 formation of up to 58.42 % at −1.1 V vs. RHE in 0.1 M KHCO 3 and 70.31 % at −0.76 V vs. RHE in 1.0 M KOH. Suppressing side reactions and simultaneously enriching key intermediates during CO 2 reduction reaction (CO 2 RR) has been a challenge. Here, we propose a tandem catalyst (Cu 2 O NCs-C-Copc) consisting of acetylene black, cobalt phthalocyanine (Copc) and cuprous oxide nanocubes (Cu 2 O NCs) for efficient CO 2 -to-ethylene conversion. Density-functional theory (DFT) calculation combined with experimental verification demonstrated that Copc can provide abundant CO to nearby copper sites while acetylene black successfully reduces the formation energies of key intermediates, leading to enhanced C 2 H 4 selectivity. X-ray photoelectron spectroscopy (XPS) and potentiostatic tests indicated that the catalytic stability of Cu 2 O NCs-C-Copc was significantly enhanced compared with Cu 2 O NCs. Finally, the industrial application prospect of the catalyst was evaluated using gas diffusion electrolyzers. The of Cu 2 O NCs-C-Copc can reach to 58.4 % at −1.1 V vs. RHE in 0.1 M KHCO 3 and 70.3 % at −0.76 V vs. RHE in 1.0 M KOH. This study sheds new light on the design and development of highly efficient CO 2 RR tandem catalytic systems.
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INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Xiao-Hui Wang,Zheng-Min Wang,Qing-Ling Hong,Ze-Nong Zhang,Feng Shi,Dong-Sheng Li,Shu-Ni Li,Yu Chen
The electrocatalytic nitrate reduction reaction (NO3–-ERR) to ammonia (NH3) is a promising strategy for NH3 production. Cu-based nanomaterials have been regarded as a kind of effective NO3–-ERR catalysts. In this work, high-quality hollow Cu2O nanocubes (Cu2O h-NCs) are facilely synthesized by a simple one-step reduction method. The as-prepared Cu2O h-NCs reveal high selectivity and activity for NO3–-ERR, which is ascribed to abundant oxygen vacancies, high surface area, hollow architecture, low mass transfer resistance, and strong adsorbing ability toward NO3–. In fact, Cu2O h-NCs can achieve a Faradic efficiency of 92.9% and an NH3 yield of 56.2 mg h–1 mgcat–1 for NH3 production at −0.85 V (vs RHE) potential, which exceeds those of other transition-metal-based NO3–-ERR electrocatalysts.
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ACS Biomaterials Science & Engineering
·
2022
·
IF 5.395
Le Gao,Yibo Song,Jun Zhong,Xiaofeng Lin,Shu-Feng Zhou,Guowu Zhan
Two-dimensional (2D) metal–organic frameworks (MOFs) could serve as multifunctional nanoplatforms to load small-molecule drugs and enzyme-mimicking nanoparticles (NPs) with a high efficiency for combined cancer therapy. Herein, we have prepared novel 2D Cu-tetrakis (4-carboxyphenyl) porphyrin (TCPP) nanosheets with an average thickness of 1.2 ± 0.1 nm using Cu2O nanocubes (50 nm) as a template and solid copper ion supplier. Cu2O nanocubes can be consumed and hybridized with the obtained Cu-TCPP, depending on the molar ratio of Cu2O and TCPP linker. The resultant Cu2O/Cu-TCPP could serve as nanoplatforms for co-loading of Pt and Au NPs to construct multifunctional Cu2O/Cu-TCPP/(Pt–Au) nanomedicines, which showed a superior anticancer effect via multiple therapeutic modes. For instance, Cu(II)-TCPP can produce 1O2 in the presence of acidic H2O2 by the Russell mechanism and the intrinsic Cu(I) ions (derived from the residual Cu2O) could mediate a Fenton-like reaction in tumorous tissues to generate toxic hydroxyl radicals (•OH). Moreover, the loaded Pt NPs with catalase (CAT)-mimic activity could decompose hydrogen peroxide (H2O2) into O2 within the tumor cells, increasing the local O2 concentration, modulating the tumorous hypoxia atmosphere, and promoting the O2-dependent glucose oxidation reaction. Furthermore, Au NPs with glucose oxidase (GOx)-mimic activity could accelerate the consumption of glucose and cut nutrient supply to induce starvation therapy. Consequently, our designed 2D MOF-based therapeutic nanomedicines would be a promising candidate for future smart and combined cancer therapy.
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MATERIALS RESEARCH BULLETIN
·
2021
·
IF 4.641
Chuanfu Song,Kunyuan Chen,Xin Jin,Xinyu Zhao,Guangrong Liu,Feifei He,Qiang Huang
The biochar-supported Cu 2 O/Cu composite (Cu 2 O/Cu/BC) was fabricated by direct pyrolysis of hemp hurds pretreated with KOH and CuCl 2 , in which the synchronous carbonization-activation-functionalization was achieved to produce copper-modified biochars. Cu 2 O/Cu/BCs were characterized by XRD , Raman, XPS , SEM and N 2 adsorption-desorption techniques. The adsorption methyl orange by Cu 2 O/Cu/BCs showed that the incorporation of Cu 2 O/Cu has improved the adsorption capacity. The adsorption obeyed the pseudo-second-order kinetic model and Langmuir isotherm. The maximum adsorption capacity reached 379.4 mg∙g -1 at 303.5 K. Furthermore, assisted with the photoactivity of Cu 2 O/Cu heterojunction the saturated adsorbent can be regenerated under simulated sunlight, and the re-adsorption capacity was still as high as 77.1% of the fresh adsorbent after six cycles. The regeneration efficiency was much better than traditional thermal regeneration and solvent treatment. This work should allow to provide a convenient preparation of functionalized biochars and to develop solar-driven, self-regenerative sorbents for water decontamination with high efficiency.
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CERAMICS INTERNATIONAL
·
2021
·
IF 4.527
Sitong Liu,Wenzhong Wang,Ying Cheng,Lizhen Yao,Yuhong Liu,Mingjuan Lin,Huabin Chen,Yujie Liang,Junli Fu,Lijuan Wang
In this study, we demonstrate for the first time the construction of a ternary BiVO 4 /FeVO 4 /Cu 2 O nanorod array (NRA) photoelectrode via seed-assisted refluxing, hydrothermal and successive ionic-layer adsorption and reaction (SILAR) method and its photoelectrochemical (PEC) water oxidation performance. The energy band structures of the BiVO 4 , FeVO 4 and Cu 2 O show that two type-II band alignments with a ladder-like structure are formed in the constructed ternary BiVO 4 /FeVO 4 /Cu 2 O NRA photoelectrode, enabling the photoelectrode to display substantially enhanced PEC performance. The constructed ternary photoelectrode loaded with the optimized Cu 2 O nanoparticles achieves a zero-bias photocurrent density of 50 μA cm −2 , 5 times higher than that of the pure BiVO 4 NRA photoelectrode. The measurements of optical property reveal that the constructed BiVO 4 /FeVO 4 /Cu 2 O nanorod arrays (NRAs) demonstrate improved light absorption capability. The electrochemical impedance and photoluminescence measurements confirm that the charge carriers of the BiVO 4 /FeVO 4 /Cu 2 O heterojunction NRAs are transferred and separated effectively. The substantially boosted PEC water oxidation activity of the constructed ternary BiVO 4 /FeVO 4 /Cu 2 O heterojunction NRA photoelectrode is ascribed to the improved light harvesting and effective charge separation.
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JOURNAL OF NANOPARTICLE RESEARCH
·
2023
·Vol. 25
·期 11
·1-12
·
IF 2.5
Li Fangyuan,Yao Niu,Yuan Huiyu,Cui Junyan,Jia Quanli
The redox properties of electrode materials play a vital role in electrochemical performance. Fabrication of electrode materials with multiple oxidation species is highly desired for ultrasensitive glucose sensing. Herein, multivalent Cu/Cu 2 O/CuO/C (Cu/C) nanocomposites were successfully prepared for non-enzymatic glucose sensing by in situ pyrolysis of Cu metal-organic framework (Cu 3 (BTC) 2 ·3H 2 O, Cu-BTC) at a critical temperature. Structure characterizations showed that the nanocomposites maintained the original morphology of Cu-BTC crystals and exhibited mesoporous structures. Meanwhile, multiple Cu species containing Cu, Cu 2 O and CuO were generated simultaneously, which were tightly pinned on the ligand-derived carbon layers. Thus, under the synergistic effect of multivalent Cu species, mesoporous structure and intense interface contact, the sensing platforms based on Cu/C nanocomposites exhibited good glucose detection performance with a wide linear range of 0.005-2.0 mM, ultrasensitivity of 147.65 μA mM -1 cm -2 , low detection limit of 6.31 μM (S/N = 3), and favorable anti-interference properties and stability. Especially, the Cu/C sensing platform showed excellent recoveries of glucose when used to monitor glucose in real sample of honey. The good electrochemical activities of Cu/C nanocomposites render them promising candidates for sensors and other applications. Graphical abstract
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Nano Energy
·
2023
·
IF 17.6
Hao Zhang,Ying Wang.,Qiong Lei,Ying Wang,Chiu Tang,Jun Yin,Tsz Woon Benedict Lo
Tracking the evolution of electrocatalysts over oxide-derived Cu materials during the electrochemical CO 2 reduction reaction (eCO 2 RR) is pivotal for optimizing the product selectivity toward desired multi-carbon (C 2+ ) products. However, the identification of the true intermediate active catalyst is still unclear. Here, we adopted a multi-modal characterization approach, primarily based on operando powder X-ray diffraction and operando micro-Raman spectroscopy, to study three Cu 2 O precursors with different morphologies, namely, octahedral (O-), cubic (C-), and nanowire (N-Cu 2 O). This multi-modal approach allows us to investigate the Cu 2 O nano-crystallites from the interface to the bulk structure. The results suggested notably different electrochemical reduction kinetics. 26.1% O-Cu 2 O and 90.6% C-Cu 2 O were reduced to much smaller Cu(0) domains after two hours of time-on-stream; N-Cu 2 O, with notably higher surface-to-volume ratio, was completely reduced within 45 min of time-on-stream. We accordingly observed a structure-reactivity correlation where a more intricate Cu 2 O/Cu grain network (and hence Cu + -Cu 0 junctions) as observed in O-Cu 2 O, can lead to stable and quantitative production of ethylene at the Faradic efficiency of around 40% (in stark contrast to those of C- and N-Cu 2 O). The synergy between the Cu 2 O and Cu phases was also verified by density functional theory calculations. The upshifted d -band center of Cu 2 O/Cu in O-Cu 2 O is the most conducive toward the production of ethylene, whereas the downshifted d -band center of Cu 2 O/Cu in C-Cu 2 O leads to a decreased production of ethylene in the expense of unwanted production of hydrogen. We envisage that system optimization and design of new catalysts will become more facile and efficient using a related multi-modal operando characterization philosophy.
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Journal of Materials Chemistry B
·
2021
·Vol. 9
·期 16
·3533-3543
·
IF 6.331
Ying Zhu,Zhilu Zhang,Xinyu Song,Yuxiang Bu
Due to the unique advantages, developing a rapid, simple and economical synthetic strategy for porous nanomaterials is of great interest. In this work, for the first time, using sodium hypochlorite as a green oxidant, urea was oxidized to CO2 as a carbon source to prepare the fine-particle crosslinked Cu-precursors, which could be further reduced by sodium ascorbate into pure Cu2O nanospheres (NPs) with a porous morphology at room temperature. Interestingly, our study reveals that introduction of an appropriate amount of MgCl2 into the raw materials can tune the pore sizes and surface area, but has no influence on the phase purity of the resulting Cu2O NPs. Significantly, all the synthesized Cu2O NPs exhibited intrinsic peroxidase-like activity with higher affinity towards both 3,3,5,5-tetramethylbenzidine (TMB) and H2O2 than horseradish peroxidase (HRP) due to the highly porous morphology and the electrostatic attraction towards TMB. The colorimetric detection of glucose based on the resulting porous Cu2O NPs presented a limit of detection (LOD) of 2.19 μM with a broad linear range from 1–1000 μM, much better than many recently reported composite-based nanozymes. Meanwhile, this nanozyme system was utilized to detect L-cysteine, exhibiting a LOD value as low as 0.81 μM within a linear range from 0 to 10 μM. More interesting, this sensing system shows high sensitivity and excellent selectivity in determining glucose and L-cysteine, which is suitable for detecting serum samples with reliable results. Therefore, the present study not only develops a simple strategy to prepare Cu2O NPs with controllable porous structure, but also indicates its promising applications in bioscience and disease diagnosis.
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EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2021
·Vol. 2021
·期 24
·2353-2364
·
IF 2.524
Xuerui Cao,Guangwei Cao,Mei Li,Xinli Zhu,Jinyu Han,Qingfeng Ge,Hua Wang
Graphical Novel Au x Cu 2 O electrocatalysts were synthesized via the galvanic replacement reaction between Cu 2 O nanocubes and HAuCl 4 solution, and the pre-reduction by linear voltammetry (LSV). The Au 0.02 Cu 2 O pre-reduced by LSV significantly boosted C 2 H 4 selectivity in CO 2 electrocatalytic reduction, which were 5 and 2 times higher than those of bare Cu 2 O and Au 0.02 Cu 2 O pre-reduced by chronoamperometry at high potential, respectively. Electrochemical reduction of carbon dioxide to fuels has been recognized as a perspective way to address the environmental and energy issues. Herein, the novel Au decorated Cu 2 O electrocatalysts were synthesized via the galvanic replacement reaction and the successive pre-reduction by linear voltammetry (LSV) method. In contrast to Cu 2 O, CO formation became dominant over HCOOH and H 2 on Au x Cu 2 O, and a remarkably enhanced selectivity of C 2 H 4 was obtained beyond −1.1 V vs. RHE. Among them, Au 0.02 Cu 2 O exhibited the highest Faraday efficiency (FE) of C 2 H 4 of 24.4 % at −1.3 V vs. RHE, which was as high as 2∼2.5 and 5 times of those on other two Au x Cu 2 O and bare Cu 2 O, respectively. Meanwhile, it is demonstrated that the optimal ratio of Au/Cu was essential for effective sequential catalysis between Au and Cu 2 O to enhance C−C coupling. Furthermore, the effect of copper states resulting from different pre-reduction methods on the selectivity of C 2 H 4 was explored. A half decrease of C 2 H 4 FE was observed on HPR-Au 0.02 Cu 2 O (high potential reduced) relative to the LSV reduced Au 0.02 Cu 2 O, which was ascribed to the different content of Cu 0 and residual Cu + in two catalysts. Our results demonstrate an effective approach to construct Cu 2 O based bimetallic catalysts for ethylene formation from CO 2 .
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CRYSTENGCOMM
·
2020
·Vol. 22
·期 47
·8214-8220
·
IF 3.117
Tao-Tao Lv,Hui-Xiang Wang,Xiao-Bo Ren,Lian-Cheng Wang,Rui-Min Ding,Jing-Pei Cao,Bao-Liang Lv
For crystalline catalysts with special morphology, the corners and edges are usually of high activities due to the presence of unsaturated coordination sites, so it will be an ideal strategy to promote catalytic properties by only keeping the corners and edges of such kinds of catalysts. In this work, a Cu2O tetradecahedral nanocage with plenty of corners and edges was formed by selectively etching the (111) and (100) facets on the basis of a simple top-down method, in which SDS was used as a protective agent to keep the active corners and edges while hydroxylamine hydrochloride was used as a reducing agent and an etchant. The decomposition of ammonium perchlorate (AP) was used as a probe reaction to test its catalytic performance. It was found that the low temperature decomposition (LTD) and high temperature decomposition (HTD) were reduced by 27.1 °C and 107 °C, respectively, and the heat release increased by three times in comparison with pure AP. The Cu2O nanocage exhibits excellent activity and high catalytic performance in the reaction. This work provides us an effective AP thermal decomposition catalyst and a simple strategy to fabricate a hollow structure with low-energy facets etched and highly active facets exposed.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2020
·
IF 4.65
Tong Wu,Hui Zheng,Yichuan Kou,Shilei Jin,Yuhong Jiang,Ming Gao,Lei Chen,Naveen Reddy Kadasala,Yang Liu
In this study, 3D Fe 3 O 4 micro-flowers were synthesized by the self-assembly approach, then rhombic dodecahedral Cu 2 O was successfully loaded onto their surface by wet chemical method . Ag nanocrystals were reduced in situ on the surface of Fe 3 O 4 /Cu 2 O composites to prepare novel Fe 3 O 4 /Cu 2 O/Ag composites. The composites were characterized by SEM, TEM, XRD , XPS, VSM and UV–Vis diffuse reflectance spectroscopy. The effect of Ag nanocrystals on the photocatalytic performance of the Fe 3 O 4 /Cu 2 O composites was investigated by the degradation of methyl orange under visible light irradiation, and the Fe 3 O 4 /Cu 2 O/Ag composites showed higher photocatalytic efficiency than the Fe 3 O 4 /Cu 2 O composites. Photoelectrochemical and PL measurements were carried out to investigate the synergistic effect between the semiconductors and Ag nanocrystals and it was confirmed that the Fe 3 O 4 /Cu 2 O/Ag composites effectively inhibited the recombination of electron-hole pairs, thus improving the photocatalytic activity. The fact that the Fe 3 O 4 /Cu 2 O/Ag composites could be magnetically recycled and that they retained more than 90% of their original activity after six repeated experiments indicates, that they show great potential for wastewater treatment applications.
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Nanoscale Research Letters
·
2019
·Vol. 14
·期 1
·1-9
·
IF 3.159
Feng Yao,Jiao Tifeng,Yin Juanjuan,Zhang Lun,Zhang Lexin,Zhou Jingxin,Peng Qiuming
The effective synthesis and self-assembly of nanocomposites were of key importance for a broad range of nanomaterial applications. In this work, new carbon nanotube (CNT)-Cu 2 O nanocomposites were successfully synthesized via a facile approach. CNT was selected as the anchoring substrate to load Cu 2 O nanoparticles to prepare composite catalysts with well stability and good reusability. It is discovered that the prepared CNT-Cu 2 O nanocomposite materials could be effectively controlled via regulating preparation temperature and time without the use of any stabilizing agents. The nanostructures of synthesized composites were well characterized by many techniques, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). And the prepared CNT-Cu 2 O nanocomposites with optimized preparation conditions as new catalyst displayed excellent catalytic performance on the reduction reaction of p-nitrophenol, demonstrating potential applications for environmental governance and composite materials.
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