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electrolysis_03
The resulting spectra were converted to the photoelectron wave vector k, and the resulting χ(k) functions were weighted with k2 to compensate for the dampening XAFS amplitude with increasing k.
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electrolysis_03
train2
electrolysis
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Electrochemical analysis in half cell.
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electrolysis_03
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electrolysis
electrolysis_03
The electrochemical characterization of WP-structured Ir and Ir black nanoparticles (Premetek Co., product number P40V010) was performed in a half-cell setup equipped with a glassy carbon working electrode, platinum counter electrode, and a reversible hydrogen electrode (RHE).
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Working electrode rotation was controlled with a modulated speed rotator (Pine Instruments, U.S.) and electrochemical measurements were taken with Interface 1000E potentiostat (Garmry, USA).
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electrolysis_03
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The commercial
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electrolysis_03
train2
electrolysis
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Ir black catalysts were prepared as a suspension ink using 3.5 mg of catalyst, 2.0 mL of deionized (DI) water, 8.0 mL of isopropyl alcohol, and 40 μL of Nafion® (5 wt%, Sigma Aldrich) solution.
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The ink suspension was sonicated for 30 min before pipetting 10 μL onto a polished glassy carbon disk electrode.
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electrolysis_03
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electrolysis
electrolysis_03
The area of the glassy carbon electrode was 0.196 cm2 and thus the Ir electrode loading of Ir black corresponds to 17.8 μg/cm2.
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electrolysis_03
train2
electrolysis
electrolysis_03
The composition of the ink was optimized based on the mass activity for Ir loading and Nafion® content.
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electrolysis_03
train2
electrolysis
electrolysis_03
For the stack of WP NW arrays, the amount of Ir loading and the thickness were adjusted by controlling the number of stacked layers.
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electrolysis_03
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electrolysis
electrolysis_03
All potentials reported herein refer to the RHE scale and have been corrected for the Ohmic drop in solution.
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electrolysis_03
train2
electrolysis
electrolysis_03
The 0.05M H2SO4 electrolyte was prepared from 98% H2SO4 (Sigma Aldrich) and was saturated with synthetic air during all measurements.
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electrolysis_03
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electrolysis
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Following 5 cycles of cyclic voltammetry (CV) ranging 0.05–0.6
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V for electrochemical reduction of surface iridium oxide, CVs ranging 0.05–1.4 V was conducted at 50 mV/s until the metallic Ir on the surface of the catalyst had been transformed to a hydrated Ir oxide film (HIROF), which is indicated by the disappearance of the HUPD peak.
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electrolysis
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Linear polarization curves were completed in a potential range of 1.2–1.7 V at 5 mV/s and a rotation speed of 2500 rpm.
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Catalyst activities were evaluated at 1.55 V.
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electrolysis
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Mass activities were defined as the OER activity normalized to the mass of Ir loaded on the working electrode.
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electrolysis_03
train2
electrolysis
electrolysis_03
The ECSA-specific activities were defined as OER activities normalized by the ECSA.
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electrolysis_03
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electrolysis
electrolysis_03
The ECSA of each sample was derived by integration of the current response (normalized to the substrate geometric surface area) from the CV in a potential range of 1.0–1.4 V.
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electrolysis_03
train2
electrolysis
electrolysis_03
In this voltage range, there is no peak caused by the kinetic polarization and the current density of the flat region increases linearly with a scan rate 10 mV s−1.
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electrolysis_03
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electrolysis
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Stability of WP catalysts was evaluated with repeating chronoamperometry, which
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electrolysis_03
train2
electrolysis
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was performed by stepping between an open circuit potential (1.00 V), where no OER current is observed, and a potential (1.6 VRHE: an overpotential of 0.27 V from the equilibrium potential of 1.23 VRHE), where an appreciable OER current is obtained.
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electrolysis_03
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electrolysis
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Each potential was maintained for 10 s.
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electrolysis_03
train2
electrolysis
electrolysis_03
During 500 cycle of the stability test, the 0.5 mL of the electrolyte was collected every 50 cycles, and ICP-MS analysis was applied to measure the concentration of Ir dissolved from the electrode to the electrolyte.
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electrolysis
electrolysis_03
All reported measurements were repeated at least three times to ensure reproducibility.
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electrolysis_03
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electrolysis
electrolysis_03
The error bars in the plots indicate the standard deviation of the measurements.
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electrolysis_03
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electrolysis
electrolysis_03
Scanning electrochemical microscopy.
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41,480
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electrolysis_03
train2
electrolysis
electrolysis_03
The SECM tip was a Pt-disk microelec- trode with a diameter of 25 μm.
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electrolysis_03
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An Ag/AgCl electrode was employed as a reference and the counter electrode was a Pt-wire.
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electrolysis_03
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electrolysis
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Before each measurement, the micro- electrode was polished with 0.3 μm alumina paste, cleaned by ultrasonication in a deionized water bath, and then rinsed with deionized water.
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train2
electrolysis
electrolysis_03
SECM experiments were performed by using a four-electrode system consisting of CE, RE, and two WEs (tip and sample) controlled by a bipotentiostat (CHI 920D).
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electrolysis_03
train2
electrolysis
electrolysis_03
The position of the tip was adjusted in the x, y, and z directions by a stepper motor-based SECM system.
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train2
electrolysis
electrolysis_03
The SECM tip was placed 7 μm away from the surface of the catalyst electrode, confirmed by SECM feedback mode.
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electrolysis_03
train2
electrolysis
electrolysis_03
The potential applied to the tip was −0.05 V (reduced enough to collect evolved O2), while the WP and WP samples were polarized in the potential range between 1.1 and 1.4 VAg/AgCl.
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42,374
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electrolysis_03
train2
electrolysis
electrolysis_03
Single-cell measurements.
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electrolysis_03
train2
electrolysis
electrolysis_03
MEAs were fabricated and tested to demonstrate the performance of a single cell when the WP
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electrolysis_03
train2
electrolysis
electrolysis_03
Ir samples were applied as the anode catalyst.
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electrolysis_03
train2
electrolysis
electrolysis_03
An MEA was prepared by loading WP Ir on the Nafion® 212 as the anode catalyst.
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electrolysis_03
train2
electrolysis
electrolysis_03
The WP samples were prepared with three types of building blocks, P1200, P400, and P200, varying the stacking number (10, 20, and 30).
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electrolysis_03
train2
electrolysis
electrolysis_03
For comparison, for an MEA using Ir black nanoparticles (Premetek Co., product number P40V010) as the anode catalyst, the nanoparticle slurry was spray-coated on the membrane.
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electrolysis_03
train2
electrolysis
electrolysis_03
The cathode was prepared by spraying the catalyst mixture, consisting of isopropyl alcohol, water, Nafion® ionomer, and Pt/C 46.2 wt%, on 10 BC (SIGRACET®, product number 10 BC, 385 ± 50 microns in thickness).
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electrolysis_03
train2
electrolysis
electrolysis_03
Pt/C catalysts with a loading amount of 0.4 mgpt cm−2 were loaded with 30 wt% Nafion® content.
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electrolysis_03
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electrolysis
electrolysis_03
A nanoparticle-type
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electrolysis_03
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electrolysis
electrolysis_03
Ir black anodic catalyst was spray-coated on the Ti GDL (Bekaert, 250 μm) with a loading amount of 0.1 and 0.05 mg cm−2 with 10 wt% Nafion® content at the opposite site of the cathode.
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electrolysis_03
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electrolysis
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Hot pressing was performed at 140 °C for 2 min to combine the prepared cathode and anode as a device.
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The MEAs were characterized with a high-current potentiostat (HCP-803, Bio- Logic).
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The cell was operated at 80 °C with water fed to the anode at a rate of ~15 mLmin−1 without back pressure.
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I–V curves were plotted with the average current measured for 1 min at 0.05 voltage increments in the range of 1.25–2.0 V.
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Durability of PEMWE loading WP1200 structures as anode was tested at current density of 100 mA cm−2.
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Data availability
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Data supporting the plots and other findings in this article are available from the authors upon reasonable request.
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OPEN ARTICLE
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Facilely synthesized nitrogen-doped reduced graphene oxide functionalized with copper ions as electrocatalyst for oxygen reduction
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Nitrogen-doped reduced graphene oxide is successfully synthesized and functionalized with hydroxylated copper ions via one-pot microwave-assisted route.
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The presence of cationic Cu coordinated to the graphene layer is fully elucidated through a set of experimental characterizations and theoretical calculations.
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Thanks to the presence of these hydroxyl-coordinated Cu2+ active sites, the proposed material shows good electrocatalytic performance for the oxygen reduction reaction, as evidenced by an electron transfer number of almost 4 and by high onset and half-wave potentials of 0.91 V and 0.78 V vs. the reversible hydrogen electrode, respectively.
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In addition, the N-doped Cu-functionalized graphene displays a superior current retention with respect to a commercial Pt/C catalyst during the stability test, implying its potential implementation in high-performance fuel cells and metal-air batteries.
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INTRODUCTION
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To date, several efficient and smart technologies for energy conversion and storage are emerging as suitable strategies to build a green and sustainable future.
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Among them, fuel cells1,2 and metal-air batteries3,4 attract particular worldwide interest, due to their high energy density, enabling an increasing driving autonomy in electric vehicles, to be comparable to that of gasoline-supplied vehicles, and supporting the development of small advanced portable electronic devices as well as auxiliary power units5.
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However, both these electrochemical devices suffer from kinetically sluggish oxygen reduction reaction (ORR) at the oxygen/air cathode6,7.
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In order to boost ORR for practical and large-scale applications, active, stable and low-cost electrocata- lysts are highly desirable.
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During the last decades, extensive efforts have been focused on the discovery and development of such ORR active materials8–12.
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Among many platinum group metal-free catalysts, carbon-based materials, doped with heteroatoms and/or transition metals, are considered the most promising alternatives to the state-of-the-art for ORR due to their encouraging platinum-based catalysts performance13–16.
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In particular, many research groups reported heteroatom-doped graphene, such as nitrogen-doped17,18, boron- doped19, edge- halogenated (Cl, Br or I) graphene22, as efficient and robust ORR electrocatalyst23.
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Moreover, graphene materials with binary, ternary and quaternary doping of various heteroatoms were also widely investigated as ORR catalysts, such as boron/nitrogen-doped24, nitrogen/sulfur-doped25, nitrogen/phosphorous-doped26,27, nitro- gen/boron/phosphorous-doped28 and boron/nitrogen/phosphorus/ sulfur-doped graphene29.
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To date, incorporating metal into graphene-based materials is considered an effective strategy to further improve the catalytic performance toward ORR30–35.
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In biological systems, sites copper centers (Cu2+), such as those present in cytochrome c oxidase and laccase, can bind molecular oxygen and efficiently reduce it to water.
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Taking the cue from nature, Wang et al36 reported a bioinspired catalyst, with the coexistence of Cu0 and Cu2+ connected to N atoms in reduced graphene oxide (rGO), exhibiting superior catalytic activity (onset potential 0.978 V vs. the reversible hydrogen electrode (RHE) and electron transfer number in the range from 3.7 to 4) with respect to conventional Pt/C in alkaline media.
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Shakhseh et al30 studied sulfur and copper modified graphene, showing an onset potential of 1.09 V vs. RHE and a high selectivity for the four-electron ORR.
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Li et al37 reported single atomic Cu anchored to an ultrathin two-dimensional carbon matrix, demonstrating impressive ORR activity, with an electron transfer number of 3.97 and a half-wave potential of 0.869 V vs. RHE.
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Despite the remarkable ORR activity, it is worth noticing that most of the above-mentioned doped and Cu-modified graphene catalysts were prepared through pyrolysis and thermal annealing at high temperatures, which are time- and energy-consuming.
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In this work, we propose to achieve surface functionalization of N-doped rGO with active copper ions through a simple and fast route with microwave irradiation, using graphene oxide (GO), urea and copper sulfate as chemical precursors.
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Under microwave radiation at 180 °C, GO was reduced and N atoms were simultaneously bonded to the graphitic lattice, forming N-doped rGO (denoted as N-rGO in this work).
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With the addition of copper precursor, the metal ions are forced to bind to the residual oxygen-containing functional groups present at the rGO surface, generating additional catalytic Cu active sites for ORR on the carbonaceous N-rGO.
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This sample is indicated as Cu-N-rGO.
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The prepared materials were carefully characterized utilizing field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS).
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Thanks to the comparison between experimental and
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simulated extended X-ray absorption fine structure (EXAFS) spectra with density functional theory (DFT) calculations, the the high electrocatalytic molecular structure responsible for activity of this complex toward ORR has been identified and characterized
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.
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Various electrochemical techniques were employed to evaluate the activity and durability of the electrocatalysts for ORR in atmospheric environment in alkaline solution.
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The Cu-N- rGO demonstrated superior catalytic activity to the counterpart N-rGO, and enhanced durability compared to commercial Pt/C.
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Physical and chemical characterizations FESEM and TEM characterizations were performed to evaluate the morphology and structural properties of the as prepared Cu-N- rGO samples (see Fig. 1).
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FESEM images (Fig. 1a, b) show that the obtained flakes exhibit smooth surfaces, large area, and are easily found well spread over the surface.
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They exhibit the characteristic morphology of the 2-dimensional graphene structure, with no modification or damage induced to the original GO by the preparation technique.
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This is also confirmed by TEM character- ization.
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Bright field TEM (BFTEM) (Fig. 1c) and scanning TEM images confirm the good quality of the (STEM) obtained rGO, and at the same time show that no copper oxide particles or metallic aggregates are present.
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The selected area electron diffraction pattern, shown in Fig. 1f, presents a well- defined spot pattern, composed of elongated bright spots in a hexagonal configuration.
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graphene_01
train1
graphene
graphene_01
This corresponds to rGO in [001] axis zone; the points are elongated because the signal is generated by a small number of stacked rGO layers.
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O
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graphene_01
train1
graphene
graphene_01
There is no detectable evidence of copper in the form of metallic phase or other solid rings appear in the compounds, since no discrete spots or (Fig. 1d, e) the interplanar spacings are diffraction pattern; consistently, unchanged with respect to those observed in pristine rGO.
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['Results']
O
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graphene_01
train1
graphene
graphene_01
However, the presence of copper in these samples was confirmed by energy dispersive X-ray spectroscopy (EDX) (shown in Fig. 1g): signals from C, O, N, Cu, Si and Au (the last two being due to the experimental set-up) were detected in the area where no particles or aggregation was observed.
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6,980
7,270
['Results']
MEASUREMENT
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graphene_01
train1
graphene
graphene_01
Semi-quantitative elemental analysis was achieved via XPS measurements.
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7,271
7,342
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MEASUREMENT
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graphene_01
train1
graphene
graphene_01
The survey spectrum (see Fig. 2a) highlights the presence of C (77.5 at.%), O (17.2 at.%), N (2.4 at.%) and Cu (2.2 at. %), and traces of S, Cl, Na (<0.4 at.%) due to precursors.
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7,343
7,521
['Results']
MEASUREMENT
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graphene_01
train1
graphene
graphene_01
To search for specific signals induced by the presence of Cu atoms in the rGO matrix, we compared the N-rGO high resolution (HR) spectra to those of the Cu-N-rGO.
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MEASUREMENT
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graphene_01
train1
graphene
graphene_01
C 1s HR spectra (see Supplementary Fig. 1a) were normalized and overlapped, and showed no substantial changes.
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7,685
7,795
['Results']
MEASUREMENT
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graphene_01
train1
graphene
graphene_01
This suggests that Cu atoms are not bonded directly to C atoms, since no perturbation to their chemical environment is detectable.
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7,796
7,926
['Results', 'Explanation']
O
{ "text": [ "Cu", "atoms", "C", "atoms" ], "id": [ 92752, 92761, 92770, 92779 ], "value": [ "MAT", "FORM", "MAT", "FORM" ], "begin": [ "19", "22", "55", "57" ], "end": [ "21", "27", "56", "62" ], "tokenIndices": [ [ 3, 3 ], [ 4, 4 ], [ 10, 10 ], [ 11, 11 ] ] }
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graphene_01
train1
graphene
graphene_01
The C 1s deconvolution procedure applied to Cu-N- rGO sample (see Fig. 2b) shows the well-known peaks due to sp2 carbon, three peaks due to carbon oxygen/nitrogen bonds and the π−π* shake up satellite38.
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7,927
8,130
['Background', 'Results', 'Background_PriorWork']
MEASUREMENT
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graphene_01
train1
graphene
graphene_01
Performing a comparable analysis for the N 1s peak (see Supplementary Fig. 1b), we achieved the same conclusion obtained for the C 1s peak: no distortions are visible in the curves of the two samples.
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['Results']
QUAL_MEASUREMENT
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graphene_01
train1
graphene
graphene_01
From N 1s deconvolution procedure applied to the HR spectra of both N-rGO and Cu-N-rGO, we obtained two components that can be assigned to N atoms implanted in the graphene lattice, one is attributed to pyrrolic-like nitrogen (399.1–399.6 eV) and the other is due to a quaternary or graphitic configuration (400.9–401.7 eV), as already reported in our previous work9.
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8,332
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['Results']
MEASUREMENT
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graphene_01
train1
graphene