Winterberries-like 3D network of

N-doped porous carbon anchoring on

N-doped carbon nanotubes for highly
efficient platinum-based catalyst in
methanol electrooxidation Tong Wang
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 Carbon 201 (2023) 200–211

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Winterberries-like 3D network of N-doped porous carbon anchoring on

N-doped carbon nanotubes for highly efficient platinum-based catalyst in
methanol electrooxidation
Tong Wang , Jianting He, Qin Wu **, Yunqi Yu, Kangcheng Chen ***, Daxin Shi , Yaoyuan Zhang ,
Hansheng Li *
School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, China

A R T I C L E I N F O A B S T R A C T

Keywords: A series of platinum-based catalyst Pt/Co/N-PC (N-doped porous carbon)/N-CNTs (N-doped carbon nanotubes)
N-doped porous carbon were prepared successfully by loading Pt nanoparticles on the winterberries-like 3D network of Co/N-PC/N-
N-doped carbon nanotubes CNTs, which was obtained from carbonization of in-situ grew ZIF-67/PPy (polypyrrole). The Pt nanoparticles
3D network
with about 2.5 nm in diameter uniformly dispersed on the Co/N-PC/N-CNTs. The prepared electrocatalyst Pt/
Methanol electrooxidation
Co/N-PC/N-CNTs exhibited excellent activity toward methanol electrocatalytic oxidation reaction. The mass
activity (583 mA⋅mg−Pt1) tested by the Cyclic voltammograms reached 2.1-fold greater than that of commercial
Pt/C. The steady-state current density (42.3 mA⋅mg−Pt1) tested by the chronoamperometric measurement reached
6.9-fold higher than that of commercial Pt/C. The outstanding methanol oxidation activity and stability of the
Pt/Co/N-PC/N-CNTs were ascribed to the rich nitrogen-containing sites, large specific surface area and 3D
conductive network of the winterberries-like carbon support Co/N-PC/N-CNTs, which displayed excellent sup­
port of Pt-based catalyst and has potential industrial applications.

1. Introduction
The severe environmental problems and growing energy crisis
prompt people to exploit new clean energy devices. Researchers have
more and more in-depth exploration and understanding of new clean
energy devices in recent years [1–3]. Direct methanol fuel cells (DMFCs)
have received increasingly extensive attention from researchers due to
its environmentally friendly, excellent energy density and easy opera­
tion [4,5]. However, the problems，such as slow oxidation kinetics of
methanol and CO poison， hindered the commercialization of DMFCs.
Researchers have focused on developing novel catalysts to solve the
problems [6–10]. Even if Pt-based catalysts show excellent electro­
chemical performance in a DMFC, high cost, low CO poisoning tolerance
and poor interaction with support are the serious issues urgent to
investigation. Therefore, developing suitable supports to reduce the
amount of precious metal or replace Pt with non-precious metals attract
extensive attention [11].
Carbon supports have become the preferred support due to the su­
perior corrosion resistance and stability [12–19]. Carbon nanotubes
(CNTs) are always thought as potential catalyst support for fuel cell on
account of the considerable specific area, high conductivity as well as
good electrochemical stability [20,21]. However, catalysts prepared
with conventional CNTs as supports showed poor performance [22],
Nitrogen-doped CNTs (N-CNTs) as supports enhance the methanol
oxidation activity of catalysts. Zhang et al. [23]. prepared Pt-based
catalysts with N-CNTs as the support, which was carbonized by poly­
pyrrole nanotubes (PPy-NTs), and the peak current of the prepared
catalyst Pt/N-CNTs for methanol electrocatalytic oxidation was 2.3
times higher than that of commercial catalyst.
The nitrogen-doped porous carbon (N-PC) prepared by carbonization
of zeolite imidazole frameworks (ZIFs) has been widely studied in
various electrocatalytic reactions because of its substantial nitrogen
content, diverse pore structure as well as large specific surface area
[24–27]. Zhang et al. [28] reported a Pt-based catalyst, with the

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: wuqin_bit@126.com (Q. Wu), chenkc@bit.edu.cn (K. Chen), hanshengli@bit.edu.cn (H. Li).

https://doi.org/10.1016/j.carbon.2022.08.058
Received 11 May 2022; Received in revised form 5 August 2022; Accepted 17 August 2022
Available online 22 August 2022
0008-6223/© 2022 Elsevier Ltd. All rights reserved.
T. Wang et al.
Co@N-CNTs-PC derived from ZIF-67 as support, showing excellent
electrocatalytic performance. Yang et al. [29] prepared the catalyst
Pt–CoO@NPC@SnO2 using ZIF-67 as the precursor, showing good
methanol oxidation performance. However, the poorly inter-connecting
N-PC derived from ZIFs or ZIFs derivatives result in insufficient elec­
trical conductivity. The conductive network structure of N-CNTs con­
nects N-PC in series and improve the poor conductivity of individual
N-PC. ZIF-67/PPy-NTs as precursors studied in methanol oxidation is
barely shown in the literatures.
In this work, the winterberries-like Co/N-PC/N-CNTs with rich ni­
trogen content prepared by calcining ZIF-67/PPy-NTs, was synthesized
by in-situ growth. The structure and properties of Co/N-PC/N-CNTs and
the corresponding carbon support was characterized by various tech­
niques. Methanol oxidation reaction activity of the electrocatalysts Pt/
Co/N-PC/N-CNTs was investigated. The correlation between electro­
chemical activity and the physicochemical properties for the Pt/Co/N-
PC/N-CNTs was studied.
2. Experimental
2.1. Materials
Cobalt nitrate hexahydrate (Co(NO3)2⋅6H2O), Pyrrole, 2-methylimi­
dazole (2-MeIM), ferric chloride hexahydrate(FeCl3⋅6H2O), methyl or­
ange, Sodium borohydride (NaBH4), methanol, ethanol were gained
from Sinopharm Group, Hexachloroplatinic acid (H2PtCl6⋅6H2O) was
purchased from Meryer Chemical Technology Co., Ltd. Nafion solution
(5 wt%) was received from Alfa Aesar (China) Chemical Co., Ltd,
Commercial Pt/C (20 wt%) catalyst was gained from Johnson Matthey
Company. They are of analytically grade and used as received.
2.2. Preparation of Co/N-PC/N-CNTs
The PPy-NTs were prepared according to the literature [30]. The
preparation of ZIF-67/PPy-NTs were described as follows. In a solution
of 6 mmol Co (NO3)⋅6H2O in 100 mL methanol, a certain amount of PPy
nanotubes was dispersed under ultrasound to form Mixture A. 100 mL
methanol with 24 mmol 2-MeIM as poured into Mixture An under
Scheme 1. The schematic diagram of Pt/Co/N-PC/N-CNTs catalyst.
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stirring for 30 min and maintained in still under 25 ◦ C for 24 h. The
product was washed completely with methanol, and dried at 60 ◦ C for
12 h under vacuum. The prepared ZIF-67/PPy-NTs was placed in tube
furnace and calcined under Ar atmosphere at 700 ◦ C for 2 h. After
cooling to room temperature naturally, the Co/N-PC/N-CNTs was ob­
tained (see Scheme 1).
2.3. Preparation of Pt/Co/N-PC/N-CNTs
Pt nanoparticles loaded on Co/N-PC/N-CNTs were obtained by the
modified NaBH4 reduction method [31–33]. In solution of 5 mL water
with 30 mg sodium citrate and 149 μL H2PtCl6⋅6H2O (33.6 mg/mL) was
drop wised into the mixture of 20 mg Co/N-PC/N-CNTs in 20 mL water,
which formed a homogeneous dispersion; 3 mg NaBH4 in water (43 wt
%) was added the solution described above and continuous stirring for
24 h. The Pt/Co/N-PC/N-CNTs was obtained through centrifugation,
washed thoroughly with a mixture of ethanol and water five times, then
dried at 60 ◦ C for 12 h under vacuum (see Scheme 1).
2.4. Characterization of Pt/Co/N-PC/N-CNTs and their intermediates
The crystalline structures of the supports and catalysts was charac­
terized by X-ray powder diffraction (XRD) conducted on a Rigaku Ultima
Ⅳ equipped with a Cu-Kα radiation. The external morphology and in­
ternal morphology and structure of the samples was observed through
scanning electron microscope (SEM, Hitachi S4800). The internal
morphology and structure of the samples was studied by transmission
electron microscope (TEM, JEM-2100, JEOL, Japan) and the high-
resolution transmission electron microscopy (HRTEM). X-ray photo­
electron spectrometry (XPS) is used to determine the chemical valence
state of the sample near the surface area. Raman characterizes the dis­
order and graphitization degree of the samples, and the N2 adsorption-
desorption experiment carried out at 77K is used for analyzing the
pore structure of the prepared supports (AUTOSORB IQ). The content of
metal was determined by inductively coupled plasma-optical emission
spectrometer (ICP-OES, Agilent725ES). TG curves was carried out under
air atmosphere by thermogravimetric analysis (TGA, STA449 F5) from
30 ◦ C to 900 ◦ C.
T. Wang et al.
2.5. Electrochemical measurements
We conducted the electrochemical measurements at the CHI604E
workstation by a standard three-electrode system, and Pt foil, saturated
calomel electrode and glassy carbon electrode with 5 mm in diameter
covered with a catalyst layer were respectively employed as the counter,
reference and working electrodes. The preparation method of the elec­
trocatalyst slurry was as follow: A catalyst slurry was formed by adding
2 mg the prepared electrocatalyst into 1 mL mixed solution consisting of
500 μL of ethanol, 480 μL of deionized water and 20 μL of Nafion so­
lution (5 wt%) under ultrasonication for 30 min. After that, 10 μL
electrocatalyst slurry was dripped on the glassy carbon electrode and
dried naturally. The test temperature was 25 ◦ C.
The electrochemical surface area (ECSA) calculated with the formula
ECSA = QH/(0.21MPt) was determined by the hydrogen adsorption/
desorption peaks of the cyclic voltammograms (CV) curves in acidic
medium. In the formula above, QH and MPt respectively represented the
charge of hydrogen adsorption/desorption (mC cm− 2) and the loading of
Pt (mg cm− 2) of the working electrode. In addition, 0.21 denoted the
charge which was connected with monolayer adsorption of hydrogen on
bright Pt [6].
3. Results and discussion
3.1. Morphology and structure of ZIF-67/PPy-NTs
The morphology of PPy-NTs and ZIF-67 were investigated by SEM
and TEM (Fig. 1). Average diameter of about 200 nm, hollow structure,
length of several micrometers and interconnect 3D conductive network
was observed for the PPy-NTs in Fig. 1(a) (b). The structure of synthe­
sized ZIF-67 in Fig. 1(c) (d) have a rhombohedral dodecahedron
morphology with a particle size of about 400 nm [34–36].
The morphology of ZIF-67/PPy-NTs were investigated by SEM and
TEM (Fig. 2). The SEM images for ZIF-67/PPy-NTs in Fig. 2(a) (b) dis­
played that the ZIF-67 with the similar size and morphology to that of
Fig. 1 were grown on the external surface of PPy-NTs. It was identified in
the TEM images shown in Fig. 2(c) (d) that PPy-NTs and ZIF-67
Fig. 1. (a,b)SEM images of PPy (inset:TEM image), (c,d) SEM images of ZIF-67. (A colour version of this figure can be viewed online.)
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displayed clearly position relationship. The novel structure of ZIF-67/
PPy-NTs was similar to winterberries, which were named as
winterberries-like ZIF-67/PPy-NTs. The formation of the winterberries-
like structure is attributed to that Co2+ were adsorbed on the external
surface of PPy-NTs by electrostatic attraction [37,38].
As can be seen in Fig. 3(a), ZIF-67 grew almost entirely on the surface
of PPy nanotubes at a scale of 10 μm, and almost no individual ZIF-67
appeared. The color contrast image of ZIF-67/PPy and PPy was shown
in Fig. 3(c). The color of ZIF-67/PPy, which showed purple black, was
different from that of ZIF-67, which was bright purple. In addition, the
abundant nitrogen sites on PPy surface provided a lot of nucleation sites
for growth of ZIF-67. So ZIF-67 preferentially grew on the surface of PPy
rather than bulk liquid phase. Thermogravimetric analysis of ZIF-67/
PPy and PPy was done to calculate the yield of ZIF-67 in ZIF-67/PPy
(Fig. 3(b)). PPy was decomposed completely and ZIF-67/PPy was
completely converted into Co3O4 during pyrolysis in air atmosphere, the
content of which was 25%.
The XRD patterns of the PPy-NTs, ZIF-67/PPy-NTs and ZIF-67 for
their crystal structures were shown in Fig. 4. PPy-NTs had a large broad
peak between 20 and 30◦ due to the amorphous properties of PPy with
the repeating unit of the pyrrole rings [39]. The XRD spectra of ZIF-67 in
Fig. 4 was highly consistent with the typical diffraction peaks of the
standard ZIF-67 [40]. Compared with PPy-NTs and ZIF-67, the diffrac­
tion peaks of ZIF-67/PPy-NTs were mostly from that of ZIF-67, and it
indicated the ZIF-67/PPy-NTs were prepared successfully.
3.2. Morphology and structure of Co/N-PC/N-CNTs
The morphology of N-CNTs and Co/N-PC were studied by TEM
(Fig. 5). The morphology of N-CNTs still presented hollow structure,
indicating the stability of the hollow PPy-NTs (Fig. 5(a)). Fig. 5(b)
showed that the surface of N-CNTs was smooth and pure. The TEM
images of Fig. 5(c) (d) for Co/N-PC showed that Co/N-PC boundary
slightly shrinks due to the increase of stress caused by outward diffusion
of organic ligand during carbonization process. In addition, the SEM of
Fig. 5(c) showed that the Co/N-PC became rough due to the accumu­
lation of Co nanoparticles.
T. Wang et al. Carbon 201 (2023) 200–211

Fig. 2. (a,b)SEM images of ZIF-67/PPy, (c,d)TEM images of ZIF-67/PPy.

Fig. 3. (a)SEM images of ZIF-67/PPy under large scale, (b) TG curves of ZIF-67/PPy and ZIF-67 in air atmosphere, (c) color contrast image of ZIF-67/PPy and PPy.

TEM images of Co/N-PC/N-CNTs were shown in Fig. 6. Fig. 6(a)(b)
exhibited that the structure of Co/N-PC/N-CNTs was the same as before
calcination, indicating the stability of the structure of ZIF-67/PPy-NTs.
The enlarged images of Co/N-PC/N-CNTs from Fig. 6(c) (d) showed
that Co nanoparticles existed on the surface of N-CNTs and Co/N-PC.
Due to the high-temperature carbonization process, Co nanoparticles
of Co/N-PC migrated, causing the existence of Co nanoparticles on the
surface of N-CNTs.
The XRD patterns of the series supports mentioned above for the
crystal structure were shown in Fig. 7(a). Strong diffraction peaks of Co/

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T. Wang et al.
Fig. 4. XRD patterns of ZIF-67, PPy-NTs and ZIF-67/PPy-NTs.
N-PC at 44.2◦ , 51.5◦ and 75.8◦ are correspond to (111), (200) and (220)
crystal planes of Co (JCPDS, No. 15–0806). At about 25◦ , the broad
diffraction peak of Co/N-PC was assigned to the graphitic plane (002) of
carbon. N-CNTs have only broad diffraction peak at about 25◦ , which
was assigned to the graphitic plane (002) of carbon. The diffraction
peaks of Co/N-PC/N-CNTs are basically the same as that of Co/N-PC,
indicating that ZIF-67/PPy-NTs was successfully transformed into Co/
N-PC/N-CNTs.
The Raman spectrum of the series supports mentioned above in Fig. 7
(b) showed that they all have sharp peaks at 1350 cm− 1 and 1580 cm− 1.
Generally speaking, the two typical peaks of 1580 cm− 1 and 1350 cm− 1
corresponded to the stretching of all sp2 carbon domains (G peak) and
Fig. 5. (a, b) TEM images of N-CNTs, (c,d)TEM images Co/N-PC(inset: SEM image).
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the sp3 defect sites (D peak), respectively. The peak intensities ratio
value of D peak to G peak (ID/IG) represented the level of disorder of
carbon materials [41]. The value of ID/IG for Co/N-PC/N-CNTs was 1.06,
larger than that of N-CNTs (1.0013) and Co/N-PC (0.99), suggesting that
the disorder and defect sites of Co/N-PC/N-CNTs were increased. It was
beneficial to the dispersion and anchoring of nano-sized Pt particles.
The pore structure of the supports mentioned above were investi­
gated and the pore size distribution was calculated by the DFT method
(Fig. 8). The isotherms of Co/N-PC showed type-I curve (Fig. 8(a)),
indicating the existence of micropores, and the pore size distribution
curve showed the presence of mesopores (Fig. 8(b)). The isotherms of N-
CNTs in Fig. 8(a) were type-IV curves, indicating the coexistence of
micropores and mesoporous, which was in accordance to the pore dis­
tribution curve in Fig. 8(b). Co/N-PC/N-CNTs showed typical type-IV
isotherm in Fig. 8(a), the pore distribution curve in Fig. 8(b) indicated
mesopores as the main pore structure. Table 1 showed the data of pore
structure for the different supports. The specific surface area of Co/N-
PC/N-CNTs was 336.7 m2 g− 1, much larger than that of N-CNTs (81.8
m2 g− 1) and was near to that of Co/N-PC (361.1 m2 g− 1). It was shown
that the specific surface area of Co/N-PC/N-CNTs was improved by the
introduction of Co/N-PC. The pore volume of Co/N-PC/N-CNTs was
0.386 cm3 g− 1, larger than that of Co/N-PC (0.113 cm3 g− 1) and N-CNTs
(0.295 cm3 g− 1), indicating that Co/N-PC/N-CNTs had rich pore struc­
ture. The large specific surface area of Co/N-PC/N-CNTs played a vital
role in the dispersion and deposition of Pt nanoparticles, and the
abundant pore structure of Co/N-PC/N-CNTs promoted mass transfer
process.
3.3. Morphology and structure of Pt/Co/N-PC/N-CNTs
Fig. 9 showed TEM images of the series Pt-based catalysts that we
prepared by loading Pt nanoparticles on the obtained supports.
Compared with transparent hollow N-CNTs in Fig. 5(b), Dense distrib­
uted Pt nanoparticles were anchored to the surface of N-CNTs (Fig. 9(a)).
T. Wang et al. Carbon 201 (2023) 200–211

Fig. 6. TEM images of Co/N-PC/N-CNTs.

Fig. 7. Co/N-PC/N-CNTs, N-CNTs and Co/N-PC (a) XRD patterns, (b) Raman spectrum.

There were Co nanoparticles besides the dense distributed Pt nano­
particles on Pt/Co/N-PC (Fig. 9(b)). As can be seen in Fig. 9(c)(d), Pt/
Co/N-PC/N-CNTs showed that it maintained winterberries-like struc­
ture, indicating that loading process of Pt did not damage the
morphology of Co/N-PC/N-CNTs. Compared with Co/N-PC/N-CNTs in
Fig. 6(b), the Pt nanoparticles were densely deposition on the Co/N-PC/
N-CNTs (Fig. 9(c)). Pt/Co/N-PC/N-CNTs was investigated by HRTEM as
shown in Fig. 9(e)(f) to verify the existence of Pt nanoparticles, the
lattice fringes were clear, and the crystalline interplanar spacing were
0.225 nm、0.207 nm and 0.34 nm, and they corresponded to the (111)
plane of Pt nanoparticles, (111) plane of Co nanoparticles and (002)
plane of graphitic carbon. The scattered white dotted circles in Fig. 9(e)
were dispersed Pt nanoparticles, and the diameter of Pt nanoparticles
was about 2.5 nm. It was clarified that Pt/Co/N-PC/N-CNTs was formed
by loading uniformly distributed Pt nanoparticles on Co/N-PC/N-CNTs
in Fig. 9.
The distribution of nitrogen element of Pt/Co/N-PC/N-CNTs was
characterized by the EDS elemental mapping and the corresponding
figure is shown in Fig. 10. It can be seen that nitrogen element was
uniformly distributed on the catalyst Pt/Co/N-PC/N-CNTs. It is worth
noting that Pt elements were also uniformly distributed on the catalyst
Pt/Co/N-PC/N-CNTs, and the distribution of Pt element is consistent
with that of nitrogen element, indicating that the successful loading of Pt
was closely related to the distribution of Nitrogen element.
The XRD patterns of the series Pt-based catalysts mentioned above
were displayed in Fig. 11. They all exhibited typical diffraction peaks of
Pt, including the peaks at 81.3◦ ,67.4◦ , 46.2◦ and 39.7◦ , which corre­
sponded to the (311), (220), (200) and (111) planes of Pt (JCPDS, No.

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Fig. 8. Co/N-PC/N-CNTs, N-CNTs and Co/N-PC (a) N2 adsorption-desorption isotherms (b) pore distribution curves.

Table 1
BET surface area and pore volume for different supports.
Sample Surface area/(m2⋅g− 1) Pore Volume/(cm3⋅g− 1)
Co/N-PC 361.1 0.113
N-CNTs 81.8 0.295
Co/N-PC/N-CNTs 336.7 0.386
04–0802), respectively. In addition, the peak at 25◦ was belonged to the
(002) plane of graphitic carbon. Compared with Pt/N-CNTs, Pt/Co/N-
PC/N-CNTs and Pt/Co/N-PC showed typical diffraction peaks of Co
(JCPDS, No. 15–0806) due to the Co element in ZIF-67. The results of
XRD corresponded to the HRTEM of Pt/Co/N-PC/N-CNTs. Moreover,
ICP of the Pt/Co/N-PC/N-CNTs showed that the content of Pt is 17.32 wt
%, which was nearly consistent with the theoretical content (20 wt%),
indicating the feasible method of reducing Pt.
XPS survey and High resolution XPS survey spectrum were displayed
for interrogating the surface element valence states and chemical
composition of as prepared catalysts (Fig. 12). N1s peaks appeared
except commercial Pt/C, indicating the presence of N element in the
other three Pt-based catalysts, and it was beneficial to the dispersion of
Pt nanoparticles [42]. The Co2p peak appeared in Pt/Co/N-PC and
Pt/Co/N-PC/N-CNTs, and the content was 1.49 wt% and 1.54 wt%,
respectively. The O1s peak may be caused by the surface oxidation due
to exposure to air. For the purpose of exploring the composition of Pt of
the obtained catalysts and the change of binding energy, the
high-resolution Pt 4f spectra of the series Pt-based catalysts as above
mentioned and commercial Pt/C were shown in Fig.12 (b), Fig.12 (c),
Fig. 12(d) and (e), respectively. All Pt 4f spectra of the above catalysts
were deconvoluted into two pairs of peaks, and they belonged to Pt2+
and Pt0. The binding energies of Pt2+ and Pt0 of the above catalysts were
shown in Table 2. The binding energies of Pt0 in Pt/Co/N-PC/N-CNTs,
Pt/Co/N-PC, Pt/N-CNTs and commercial Pt/C were 71.33 eV, 71.55
eV, 71.25 eV and 71.69 eV, respectively. Different with commercial
Pt/C, the binding energy of Pt0 in the other three Pt-based catalysts all
shifts negatively, the deviation of Pt/N-CNTs (0.44 eV) was higher than
Pt/Co/N-PC/N-CNTs (0.36 eV) and Pt/Co/N-PC (0.14 eV), the deviation
of Pt/Co/N-PC/N-CNTs was moderate, indicating that the interaction
between Pt and adsorption species was moderate. In addition, the slight
change of binding energies was because of the change of Pt electronic
structure, owing to the presence of N element [43].
High resolution N1s spectra of Pt/Co/N-PC/N-CNTs was displayed in
Fig. 12 (f), it was deconvoluted into three peaks located on 402.19 eV
(graphitic N), 400.05 eV (pyrrolic N) and 398.66 eV (pyridinic N),
respectively [44–46]. Undoubtedly, Reasonable distribution of different

Fig. 9. TEM images of (a) Pt/N-CNTs (b) Pt/Co/N-PC (c,d) Pt/Co/N-PC/N-CNTs; (e,f) HRTEM images of Pt/Co/N-PC/N-CNTs. (A colour version of this figure can be
viewed online.)

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T. Wang et al.
Fig. 10. EDS elemental mapping images of Pt/Co/N-PC/N-CNTs.
Fig. 11. XRD patterns of Pt/Co/N-PC/N-CNTs, Pt/N-CNTs and Pt/Co/N-PC
types of N elements was an important factor to achieve excellent elec­
trocatalytic performance. Table 3 showed the atomic percentages dis­
tribution of different nitrogen types of the three prepared catalysts. the
N content of Pt/Co/N-PC/N-CNTs is as high as 11.25 at. %, which is
greater than that of Pt/Co/N-PC (8.57 at. %) and Pt/N-CNTs (9.82 at.
%)). From the perspective of pyridine N, Pt/Co/N-PC (45.9 at.%) is
greater than Pt/N-CNTs (39 at.%) and Pt/Co/N-PC/N-CNTs (38.67 at.
%); From the perspective of pyrrole N, Pt/N-CNTs (45.33 at.%) has the
highest content, which is greater than Pt/Co/N-PC/N-CNTs (30.71 at.%)
and Pt/Co/N-PC (29.2 at.%); From the point of view of graphite N,
Pt/Co/N-PC/N-CNTs (30.62 at.%) is greater than Pt/Co/N-PC (24.9 at.
%), much greater than Pt/N-CNTs(15.67 at.%). From the distribution of
the three types of N elements, it was shown that Co nanoparticles
migrating to CNTs (Fig. 6(c)) promotes that the Pyridine N of N-CNTs
converted to graphite N, so the graphite N content of
Pt/Co/N-PC/N-CNTs increased. the electrical conductivity of the cata­
lyst can be enhanced because of the graphite N [47], and pyridine N and
pyrrole N can offer the primary nucleation sites for deposition of Pt
nanoparticles [48]. Therefore, the N distribution
Carbon 201 (2023) 200–211
Pt/Co/N-PC/N-CNTs was optimal, and it has good electrical conduc­
tivity and certain nucleation sites for Pt deposition.
3.4. Electrochemical performance
Methanol electrooxidation consists of the following three steps [49,
50]. The electrocatalytic oxidation process of the three steps is shown in
Equations (1.1) - (1.3). The total reaction of the anodic reaction is shown
in Equation (1.4). Firstly, methanol adsorbs on Pt and deprotonates
gradually to generate carbon contained species and electron. Secondly,
Pt dissociates water to produce oxygenated species, H+ and electron.
Lastly, oxygenated species oxidize the carbon contained species to
produce carbon dioxide, H+ and electron. Simultaneously, Pt is released.
The proton and electron transfer to the catalyst/electrolyte interface and
external circuit, respectively. Therefore, the number of active center Pt
and the electrical conductivity of catalyst play a vital role in the meth­
anol electrooxidation.
CH3 OH + Pt → Pt − COads + 4 H + + 4 e− (1.1)
Pt + H2 O → Pt − OHads + H + + e− (1.2)
Pt − COads + Pt − OHads → 2 Pt + CO2 + H + + e− (1.3)
CH3 OH + H2 O → CO2 + 6 H + + 6 e− (1.4)
The electrochemical activity of the synthesized electrocatalysts were
investigated by CV test. The CV curves of the series Pt-based catalysts as
above mentioned and commercial Pt/C in acidic solution were exhibited
in Fig. 13 (a). All those synthesized Pt-based catalysts exhibited the
typical peaks of Pt involving peaks of hydrogen adsorption and
desorption in CV curves [51], and it can determine the electrochemically
active surface area (ECSA). The ECSA of Pt/Co/N-PC/N-CNTs was 76.79
m2 g− 1, and it was obviously greater than commercial Pt/C catalyst
(33.10 m2 g− 1), Pt/N-CNTs (60.67 m2 g− 1) and Pt/Co/N-PC (66.95 m2
g− 1). The large ECSA further demonstrated that more intrinsic catalytic
active sites were exposed on the surface of Pt/Co/N-PC/N-CNTs,
consistent with the TEM images in Fig. 9. Methanol oxidation activity
most intuitively showed the electrochemical activity of the prepared
catalysts. The CV curves in the mixed acidic solution in Fig. 13 (b)
suggested that the forward peak current density for
Pt/Co/N-PC/N-CNTs was 583 mA⋅mg−Pt1 in methanol oxidation reaction,
of significantly greater than that of Pt/N-CNTs (366 mA⋅mg−Pt1) and
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T. Wang et al. Carbon 201 (2023) 200–211

Fig. 12. (a) XPS survey spectra of Pt/Co/N-PC/N-CNTs, Pt/Co/N-PC, Pt/N-CNTs and commercial Pt/C; High resolution XPS survey spectra of Pt 4f for(b) Pt/Co/N-
PC/N-CNTs, (c) Pt/Co/N-PC, (d) Pt/N-CNTs, (e) commercial Pt/C; High resolution XPS survey spectra of N 1s for(f) Pt/Co/N-PC/N-CNTs, (g) Pt/Co/N-PC, (h) Pt/
N-CNTs.

208
T. Wang et al. Carbon 201 (2023) 200–211

Table 2 large specific surface area, abundant N sites, high pyridine N and pyrrole
The binding energies of Pt0 and Pt2+ of the catalysts. N content of Co/N-PC/N-CNTs facilitate the formation of high-density
Catalysts Spin orbit Pt species Binding energy/eV and well-distributed Pt nanoparticles, resulting in improving the mass
0 activity of Pt/Co/N-PC/N-CNTs. Thus, Pt/Co/N-PC/N-CNTs exhibited
Pt/Co/N-PC/N-CNTs Pt4f7/2 Pt 71.33
Pt2+ 72.11 the largest ECSA and highest mass activity.
Pt/Co/N-PC Pt4f7/2 Pt0 71.55 Electrochemical impedance spectroscopy (EIS) was regarded as a
Pt2+ 72.31 helpful characterization to reflect charge transfer properties towards
Pt/N-CNTs Pt4f7/2 Pt0 71.25 methanol oxidation reaction. The Nyquist plots of the Pt-based catalysts
Pt2+ 72.00
Commercial Pt/C Pt4f7/2 Pt0 71.69
as above mentioned and commercial Pt/C were shown in Fig. 13 (c). The
Pt2+ 72.39 diameters of the capacitive reactance arc reflected the charge transfer
resistance (Rct) in the methanol oxidation process. The smaller the value
of Rct, the faster the electrochemical reaction rate, resulting in the
higher methanol oxidation activity [52,53]. Compared to the other three
Table 3
Atomic percentage distribution of different N types for different catalysts. catalysts, Pt/Co/N-PC/N-CNTs had the smallest diameters of the
capacitive reactance arc, revealing that Pt/Co/N-PC/N-CNTs had lower
Sample N (%) Pyridinic N Pyrrolic N Graphitic N
Rct of methanol oxidation reaction. Based on the analysis of section 3.2,
(%) (%) (%)
the hollow structure of N-CNTs is very favorable for the mass transport
Pt/Co/N-PC/N- 11.25 38.67 30.71 30.62
in the electrochemical reaction. The N-CNTs overlapped with each other
CNTs
Pt/Co/N-PC 8.57 45.9 29.2 24.9 as the base and Co/N-PC as the hub formed three-dimensional conduc­
Pt/N-CNTs 9.82 39 45.33 15.67 tive network structure of Co/N-PC/N-CNTs. The interesting structure
undoubtedly made a great contribution to the conductivity of the cata­
Note: “N” means the content of nitrogen element.
lysts. The micropore structure reduced the exposure of accessible active
sites. The pore structure of Co/N-PC/N-CNTs was dominated by meso­
Pt/Co/N-PC (363 mA⋅mg−Pt1), and its peak current density was 2.1-fold
porous structure, which increased the exposure of more accessible Pt
higher than that of commercial Pt/C (277 mA⋅mg−Pt1). The methanol
sites. In a word, owing to the hollow morphology of N-CNTs, the
oxidation activity of the above catalysts were corresponding to its ECSA
abundant pore of N-PC, and the winterberries-like conductive network
(Fig. 13(a)). The uniform distribution of nitrogen element of
structure obtained by in-situ growth, a highway-like channel for elec­
Pt/Co/N-PC/N-CNTs was better helpful for anchoring Pt in section 3.3
tron and ion transport in methanol oxidation was formed. In addition,
(Fig. 10), which can be distributed evenly on the support. Therefore, it
the high content of graphite N in Co/N-PC/N-CNTs improved the con­
increased the number of active centers and electrochemical active sur­
ductivity, which was in accordance to the results of XPS (Fig. 12).
face area. In addition, the appropriate nitrogen distribution improved
Therefore, Pt/Co/N-PC/N-CNTs had lower Rct of methanol oxidation
the conductivity of the support and provided a large number of nucle­
reaction.
ation sites for Pt deposition combined with XPS analysis (Fig. 12). The

Fig. 13. Cyclic voltammetry curves of Pt/Co/N-PC/N-CNTs, Pt/Co/N-PC, Pt/N-CNTs and commercial Pt/C(a) in N2 saturated 0.5 M H2SO4 and (b) in 0.5 M H2SO4 +
0.5 M CH3OH at a scan rate of 50 mv/s; (c) Nyquist plots of Pt/Co/N-PC/N-CNTs, Pt/Co/N-PC, Pt/N-CNTs and commercial Pt/C; (d) I-t curves of Pt/Co/N-PC/N-
CNTs, Pt/Co/N-PC, Pt/N-CNTs and commercial Pt/C in 0.5 M H2SO4 + 0.5 M CH3OH. (A colour version of this figure can be viewed online.)

209
T. Wang et al.
The stability and anti-poisoning ability of the catalysts were inves­
tigated through the chronoamperometric measurements. Fig. 13 (d)
showed the I-t curve of the series Pt-based catalysts as above mentioned
and commercial Pt/C at 0.4 V. The steady-state current density of Pt/Co/
N-PC/N-CNTs, Pt/N-CNTs, Pt/Co/N-PC and commercial Pt/C were 42.3
mA⋅mg−Pt1, 14.4 mA⋅mg−Pt1,12.6 mA⋅mg−Pt1 and 6.1 mA⋅mg−Pt1 respectively
after 7200 s, and the Pt/Co/N-PC/N-CNTs was 6.9-fold larger than
commercial Pt/C. The above data highlighted the remarkable long-term
stability of Pt/Co/N-PC/N-CNTs. Based on the analysis in Fig. 10 and
Table 3 of Section 3.3, uniform and abundant nitrogen sites of Co/N-PC/
N-CNTs played an important role in the dispersion and anchoring of Pt.
It was not easy for Pt to agglomerate and fall off during chro­
noamperometric measurements. Then the particle size of Pt did not
change greatly, resulting in the higher current density of the Pt/Co/N-
PC/N-CNTs. Moreover, the electron-accepting ability of nitrogen
enabled it to polarize adjacent carbon atoms, enhancing the binding
ability between carbon atoms and adsorbed water molecules. Therefore,
more oxygen-containing species are generated in methanol oxidation
reaction, which improved the anti-poisoning ability of the catalyst [54].
4. Conclusion
In summary, the winterberries-like 3D network of Pt/Co/N-PC/N-
CNTs with abundant nitrogen content have prepared successfully. Fine
Pt nanoparticles with about 2.5 nm in diameter uniformly dispersed on
Co/N-PC/N-CNTs, which was prepared by carbonizing the ZIF-67/PPy-
NTs obtained by in-situ growth method. The Pt/Co/N-PC/N-CNTs
exhibited excellent electrocatalytic activity for the methanol oxidation
reaction, including the amazing mass activity (583 mA⋅mg−Pt1), which
reached 2.1-fold greater than that of commercial Pt/C, and good sta­
bility with the steady-state current density of 42.3 mA⋅mg−Pt1 shown by
the chronoamperometric measurements, which was 6.9-fold higher than
that of commercial Pt/C. Abundant nitrogen content and large specific
surface area of the winterberries-like Co/N-PC/N-CNTs as support for
the Pt/Co/N-PC/N-CNTs catalyst, which was conducive to the anchoring
and dispersion of Pt nanoparticles to make it difficult to agglomerate and
fall off, lead to improving electrochemical performance for methanol
oxidation. Winterberries-like Co/N-PC/N-CNTs with Co/N-PC as the
connecting node formed the 3D conductive network with abundant pore
structure, which provide a highway transport path for ions and elec­
trons. Pt/Co/N-PC/N-CNTs is a promising electrocatalyst in direct
methanol fuel cells.
CRediT authorship contribution statement
Tong Wang: Data curation, Writing - original draft. Qin Wu: Soft­
ware. Kangcheng Chen: Methodology. Daxin Shi: Investigation.
Yaoyuan Zhang: Investigation. Hansheng Li: Resources.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors sincerely acknowledged the financial support from the
State Key Program of National Natural Science Foundation of China (No.
21736001). Furthermore, the authors thanked the technical support
from Analysis & Testing Center (Beijing Institute of Technology).
References
[1] D. Liu, N. Yang, Q. Zeng, H. Liu, D. Chen, P. Cui, L. Xu, C. Hu, J. Yang, Core-shell
Ag–Pt nanoparticles: a versatile platform for the synthesis of heterogeneous
210
Carbon 201 (2023) 200–211
nanostructures towards catalyzing electrochemical reactions, Chin. Chem. Lett. 32
(11) (2021) 3288–3297, https://doi.org/10.1016/j.cclet.2021.04.053.
[2] B. Zhou, N. Zhang, Y. Wu, W. Yang, Y. Lu, Y. Wang, S. Wang, An option for green
and sustainable future: electrochemical conversion of ammonia into nitrogen,
J. Energy Chem. 60 (2021) 384–402, https://doi.org/10.1016/j.
jechem.2021.01.011.
[3] J. Liu, H. Yuan, H. Liu, C.Z. Zhao, Y. Lu, X.B. Cheng, J.Q. Huang, Q. Zhang,
Unlocking the failure mechanism of solid state lithium metal batteries, Adv. Energy
Mater. 12 (4) (2021), https://doi.org/10.1002/aenm.202100748.
[4] H. Liu, C. Song, L. Zhang, J. Zhang, H. Wang, D.P. Wilkinson, A review of anode
catalysis in the direct methanol fuel cell, J. Power Sources 155 (2) (2006) 95–110,
https://doi.org/10.1016/j.jpowsour.2006.01.030.
[5] M. Winter, R.J. Brodd, What are batteries, fuel cells, and supercapacitors? Chem.
Rev. 105 (3) (2005) https://doi.org/10.1021/cr040110e, 1021-1021.
[6] Y. Sun, C. Du, G. Han, Y. Qu, L. Du, Y. Wang, G. Chen, Y. Gao, G. Yin, Boron,
nitrogen co-doped graphene: a superior electrocatalyst support and enhancing
mechanism for methanol electrooxidation, Electrochim. Acta 212 (2016) 313–321,
https://doi.org/10.1016/j.electacta.2016.06.168.
[7] Y. Sun, C. Du, M. An, L. Du, Q. Tan, C. Liu, Y. Gao, G. Yin, Boron-doped graphene as
promising support for platinum catalyst with superior activity towards the
methanol electrooxidation reaction, J. Power Sources 300 (2015) 245–253,
https://doi.org/10.1016/j.jpowsour.2015.09.046.
[8] Q. Zhou, Z. Pan, D. Wu, G. Hu, S. Wu, C. Chen, L. Lin, Y. Lin, Pt-CeO2/TiN NTs
derived from metal organic frameworks as high-performance electrocatalyst for
methanol electrooxidation, Int. J. Hydrogen Energy 44 (21) (2019) 10646–10652,
https://doi.org/10.1016/j.ijhydene.2019.01.231.
[9] Z. Li, S. Ji, B.G. Pollet, P.K. Shen, Supported 3-D Pt nanostructures: the
straightforward synthesis and enhanced electrochemical performance for methanol
oxidation in an acidic medium, J. Nanoparticle Res. 15 (10) (2013), https://doi.
org/10.1007/s11051-013-1959-9.
[10] H. Huang, Y. Wei, Y. Yang, M. Yan, H. He, Q. Jiang, X. Yang, J. Zhu, Controllable
synthesis of grain boundary-enriched Pt nanoworms decorated on graphitic carbon
nanosheets for ultrahigh methanol oxidation catalytic activity, J. Energy Chem. 57
(2021) 601–609, https://doi.org/10.1016/j.jechem.2020.08.063.
[11] A. Serov, C. Kwak, Review of non-platinum anode catalysts for DMFC and PEMFC
application, Appl. Catal. B Environ. 90 (3–4) (2009) 313–320, https://doi.org/
10.1016/j.apcatb.2009.03.030.
[12] L. Zhao, X.L. Sui, J.L. Li, J.J. Zhang, L.M. Zhang, Z.B. Wang, 3D hierarchical Pt-
Nitrogen-Doped-Graphene-Carbonized commercially available sponge as a
superior electrocatalyst for low-temperature fuel cells, ACS Appl. Mater. Interfaces
8 (25) (2016) 16026–16034, https://doi.org/10.1021/acsami.6b03520.
[13] W. Yuan, Y. Zhang, N. Zhang, C. Yin, X. Zhang, X. Liu, Carbon riveted Pt-MnO2/
reduced graphene oxide anode catalyst for DMFC, Catal. Commun. 100 (2017)
66–70, https://doi.org/10.1016/j.catcom.2017.06.030.
[14] X. Li, L. Luo, F. Peng, H. Wang, H. Yu, Enhanced activity of Pt/CNTs anode catalyst
for direct methanol fuel cells using Ni2P as co-catalyst, Appl. Surf. Sci. 434 (2018)
534–539, https://doi.org/10.1016/j.apsusc.2017.10.218.
[15] K. Wang, Z. Pan, F. Tzorbatzoglou, Y. Zhang, Y. Wang, T. Panagiotis, S. Song, An
investigation of WC stability during the preparation of Pt@WC/OMC via a pulse
microwave assisted polyol method, Appl. Catal. B Environ. 166-167 (2015)
224–230, https://doi.org/10.1016/j.apcatb.2014.11.025.
[16] M. Huang, J. Zhang, C. Wu, L. Guan, Networks of connected Pt nanoparticles
supported on carbon nanotubes as superior catalysts for methanol electrooxidation,
J. Power Sources 342 (2017) 273–278, https://doi.org/10.1016/j.
jpowsour.2016.12.054.
[17] H. Huang, S. Yang, R. Vajtai, X. Wang, P.M. Ajayan, Pt-decorated 3D architectures
built from graphene and graphitic carbon nitride nanosheets as efficient methanol
oxidation catalysts, Adv. Mater. 26 (30) (2014) 5160–5165, https://doi.org/
10.1002/adma.201401877.
[18] K. Cheng, K. Zhu, S. Liu, M. Li, J. Huang, L. Yu, Z. Xia, C. Zhu, X. Liu, W. Li, W. Lu,
F. Wei, Y. Zhou, W. Zheng, S. Mu, A spatially confined gC3N4-Pt electrocatalyst
with robust stability, ACS Appl. Mater. Interfaces 10 (25) (2018) 21306–21312,
https://doi.org/10.1021/acsami.8b03832.
[19] M. Li, Q. Jiang, M. Yan, Y. Wei, J. Zong, J. Zhang, Y. Wu, H. Huang, Three-
dimensional boron- and nitrogen-codoped graphene aerogel-supported Pt
nanoparticles as highly active electrocatalysts for methanol oxidation reaction,
ACS Sustain. Chem. Eng. 6 (5) (2018) 6644–6653, https://doi.org/10.1021/
acssuschemeng.8b00425.
[20] W. Yang, X. Wang, F. Yang, C. Yang, X. Yang, Carbon nanotubes decorated with Pt
nanocubes by a noncovalent functionalization method and their role in oxygen
reduction, Adv. Mater. 20 (13) (2008) 2579–2587, https://doi.org/10.1002/
adma.200702949.
[21] R. Chetty, W. Xia, S. Kundu, M. Bron, T. Reinecke, W. Schuhmann, M. Muhler,
Effect of reduction temperature on the preparation and characterization of Pt-Ru
nanoparticles on multiwalled carbon nanotubes, Langmuir 25 (6) (2009)
3853–3860, https://doi.org/10.1021/la804039w.
[22] W. Li, C. Liang, W. Zhou, J. Qiu, H. Li, G. Sun, Q. Xin, Homogeneous and
controllable Pt particles deposited on multi-wall carbon nanotubes as cathode
catalyst for direct methanol fuel cells, Carbon 42 (2) (2004) 436–439, https://doi.
org/10.1016/j.carbon.2003.10.033.
[23] L.M. Zhang, X.L. Sui, L. Zhao, J.J. Zhang, D.M. Gu, Z.B. Wang, Nitrogen-doped
carbon nanotubes for high-performance platinum-based catalysts in methanol
oxidation reaction, Carbon 108 (2016) 561–567, https://doi.org/10.1016/j.
carbon.2016.07.059.
[24] G. Li, C. Zhang, Z. Wang, H. Huang, H. Peng, X. Li, Fabrication of mesoporous
Co3O4 oxides by acid treatment and their catalytic performances for toluene
T. Wang et al.
oxidation, Appl. Catal. Gen. 550 (2018) 67–76, https://doi.org/10.1016/j.
apcata.2017.11.003.
[25] J. Wei, Y. Hu, Y. Liang, B. Kong, Z. Zheng, J. Zhang, S.P. Jiang, Y. Zhao, H. Wang,
Graphene oxide/core–shell structured metal–organic framework nano-sandwiches
and their derived cobalt/N-doped carbon nanosheets for oxygen reduction
reactions, J. Mater. Chem. 5 (21) (2017) 10182–10189, https://doi.org/10.1039/
c7ta00276a.
[26] D. Ji, L. Fan, L. Tao, Y. Sun, M. Li, G. Yang, T.Q. Tran, S. Ramakrishna, S. Guo, The
Kirkendall effect for engineering oxygen vacancy of hollow Co3 O4 nanoparticles
toward high-performance portable Zinc-air batteries, Angew Chem. Int. Ed. Engl.
(2019), https://doi.org/10.1002/anie.201908736.
[27] Z. Wu, J. Wang, L. Han, R. Lin, H. Liu, H.L. Xin, D. Wang, Supramolecular gel-
assisted synthesis of double shelled Co@CoO@N-C/C nanoparticles with
synergistic electrocatalytic activity for the oxygen reduction reaction, Nanoscale 8
(8) (2016) 4681–4687, https://doi.org/10.1039/c5nr07929b.
[28] J. Zhang, R. Wang, X. Hu, Z. Sun, X. Wang, Y. Guo, L. Yang, M. Lou, P. Wen, MOF-
derived Co embedded into N-doped nanotube decorated mesoporous carbon as a
robust support of Pt catalyst for methanol electrooxidation, Appl. Surf. Sci. 533
(2020), https://doi.org/10.1016/j.apsusc.2020.147319.
[29] Y. Yu, S. You, J. Du, Z. Xing, Y. Dai, H. Chen, Z. Cai, N. Ren, J. Zou, ZIF-67-derived
CoO (tetrahedral Co2+)@nitrogen-doped porous carbon protected by oxygen
vacancies-enriched SnO2 as highly active catalyst for oxygen reduction and Pt co-
catalyst for methanol oxidation, Appl. Catal. B Environ. 259 (2019), https://doi.
org/10.1016/j.apcatb.2019.118043.
[30] Y. Li, X. Liu, H. Li, D. Shi, Q. Jiao, Y. Zhao, C. Feng, X. Bai, H. Wang, Q. Wu,
Rational design of metal organic framework derived hierarchical structural
nitrogen doped porous carbon coated CoSe/nitrogen doped carbon nanotubes
composites as a robust Pt-free electrocatalyst for dye-sensitized solar cells, J. Power
Sources 422 (2019) 122–130, https://doi.org/10.1016/j.jpowsour.2019.03.041.
[31] Y. Wang, C. Du, Y. Sun, G. Han, F. Kong, G. Yin, Y. Gao, Y. Song, The enhanced CO
tolerance of platinum supported on FeP nanosheet for superior catalytic activity
toward methanol oxidation, Electrochim. Acta 254 (2017) 36–43, https://doi.org/
10.1016/j.electacta.2017.09.099.
[32] J. Ding, L. Ma, M. Gan, W. Zhan, C. Zhou, D. Wei, S. Han, J. Shen, F. Xie, X. Zhong,
Facile fabrication of ultrafine Pt nanoparticles supported on 3D macro-/oversized
mesoporous N-doped carbon for efficient methanol oxidation, Int. J. Hydrogen
Energy 44 (57) (2019) 30388–30400, https://doi.org/10.1016/j.
ijhydene.2019.09.182.
[33] M.H. Jiang, L. Ma, M.Y. Gan, L.Q. Hu, H.M. He, F. Xie, H.H. Zhang, Worm-like PtP
nanocrystals supported on NiCo2Px/C composites for enhanced methanol
electrooxidation performance, Electrochim. Acta 293 (2019) 30–39, https://doi.
org/10.1016/j.electacta.2018.10.022.
[34] D. Shao, C. Wang, L. Wang, X. Guo, J. Guo, S. Zhang, Y. Lu, A N-doped Cobalt@
graphitized carbon material derived from ZIF-67 assisted polyvinylidene fluoride
hollow fiber membrane for supercapacitors, J. Alloys Compd. 863 (2021), https://
doi.org/10.1016/j.jallcom.2021.158682.
[35] P. Dai, Y. Yao, E. Hu, D. Xu, Z. Li, C. Wang, Self-assembled ZIF-67@graphene oxide
as a cobalt-based catalyst precursor with enhanced catalytic activity toward
methanolysis of sodium borohydride, Appl. Surf. Sci. 546 (2021), https://doi.org/
10.1016/j.apsusc.2021.149128.
[36] Y. Tao, W. Zeng, ZIF-67 MOF-derived Co3O4/NiCo2O4/CC unique layered
structure with excellent gas performances, Ceram. Int. 47 (6) (2021) 8441–8446,
https://doi.org/10.1016/j.ceramint.2020.11.209.
[37] L.-H. Xu, S.-H. Li, H. Mao, A.-S. Zhang, W.-W. Cai, T. Wang, Z.-P. Zhao, An
advanced necklace-like metal organic framework with an ultrahighly continuous
structure in the membrane for superior butanol/water separation, J. Mater. Chem.
9 (19) (2021) 11853–11862, https://doi.org/10.1039/d1ta01736e.
211
Carbon 201 (2023) 200–211
[38] Q. Zhou, Z. Zhang, J. Cai, B. Liu, Y. Zhang, X. Gong, X. Sui, A. Yu, L. Zhao, Z. Wang,
Z. Chen, Template-guided synthesis of Co nanoparticles embedded in hollow
nitrogen doped carbon tubes as a highly efficient catalyst for rechargeable Zn-air
batteries, Nano Energy 71 (2020), https://doi.org/10.1016/j.
nanoen.2020.104592.
[39] X. Du, T. Yang, J. Lin, T. Feng, J. Zhu, L. Lu, Y. Xu, J. Wang, Microwave-Assisted
synthesis of SnO2@polypyrrole nanotubes and their pyrolyzed composite as anode
for lithium-ion batteries, ACS Appl. Mater. Interfaces 8 (24) (2016) 15598–15606,
https://doi.org/10.1021/acsami.6b03332.
[40] W. Xia, J. Zhu, W. Guo, L. An, D. Xia, R. Zou, Well-defined carbon polyhedrons
prepared from nano metal–organic frameworks for oxygen reduction, J. Mater.
Chem. 2 (30) (2014) 11606–11613, https://doi.org/10.1039/c4ta01656d.
[41] X.X. Yang, J.W. Li, Z.F. Zhou, Y. Wang, L.W. Yang, W.T. Zheng, C.Q. Sun, Raman
spectroscopic determination of the length, strength, compressibility, Debye
temperature, elasticity, and force constant of the C-C bond in graphene, Nanoscale
4 (2) (2012) 502–510, https://doi.org/10.1039/c1nr11280e.
[42] Y. Zhou, K. Neyerlin, T.S. Olson, S. Pylypenko, J. Bult, H.N. Dinh, T. Gennett,
Z. Shao, R. O’Hayre, Enhancement of Pt and Pt-alloy fuel cell catalyst activity and
durability via nitrogen-modified carbon supports, Energy Environ. Sci. 3 (10)
(2010), https://doi.org/10.1039/c003710a.
[43] X. Zhao, J. Zhu, L. Liang, C. Li, C. Liu, J. Liao, W. Xing, Biomass-derived N-doped
carbon and its application in electrocatalysis, Appl. Catal. B Environ. 154-155
(2014) 177–182, https://doi.org/10.1016/j.apcatb.2014.02.027.
[44] H. Park, S. Oh, S. Lee, S. Choi, M. Oh, Cobalt- and nitrogen-codoped porous carbon
catalyst made from core–shell type hybrid metal–organic framework (ZIF-L@ZIF-
67) and its efficient oxygen reduction reaction (ORR) activity, Appl. Catal. B
Environ. 246 (2019) 322–329, https://doi.org/10.1016/j.apcatb.2019.01.083.
[45] Y. Zhao, H.-M. Zhang, Y. Zhang, M. Zhang, J. Yu, H. Liu, Z. Yu, B. Yang, C. Zhu,
J. Xu, Leaf-like 2D nanosheet as efficient oxygen reduction reaction catalyst for Zn-
air battery, J. Power Sources 434 (2019), https://doi.org/10.1016/j.
jpowsour.2019.226717.
[46] J. Ou, C. Gong, J. Xiang, J. Liu, Noble metal-free Co@N-doped carbon nanotubes as
efficient counter electrode in dye-sensitized solar cells, Sol. Energy 174 (2018)
225–230, https://doi.org/10.1016/j.solener.2018.09.018.
[47] S.H. Lim, R. Li, W. Ji, J. Lin, Effects of nitrogenation on single-walled carbon
nanotubes within density functional theory, Phys. Rev. B 76 (19) (2007), https://
doi.org/10.1103/PhysRevB.76.195406.
[48] S.C. Roy, A.W. Harding, A.E. Russell, K.M. Thomas, Erratum:
spectroelectrochemical study of the role played by carbon functionality in fuel cell
electrodes [J. Electrochem. Soc., 144, 2323 (1997).], J. Electrochem. Soc. 158 (2)
(2011), https://doi.org/10.1149/1.3529355.
[49] T. Iwasita, Electrocatalysis of methanol oxidation, Electrochim. Acta 47 (22–23)
(2002) 3663–3674, https://doi.org/10.1016/s0013-4686(02)00336-5.
[50] A. Hamnett, Mechanism and electrocatalysis in the direct methanol fuel cell, Catal.
Today 38 (4) (1997) 445–457, https://doi.org/10.1016/s0920-5861(97)00054-0.
[51] S. Gilman, Anion adsorption on platinum by the multipulse potentio-dynamic
method, Nature 203 (4950) (1964) 1130–1131, https://doi.org/10.1038/
2031130a0.
[52] I.M. Hsing, X. Wang, Y.-J. Leng, Electrochemical impedance studies of methanol
electro-oxidation on Pt/C thin film electrode, J. Electrochem. Soc. 149 (5) (2002),
https://doi.org/10.1149/1.1467940.
[53] J.T. Müller, P.M. Urban, W.F. Hölderich, Impedance studies on direct methanol
fuel cell anodes, J. Power Sources 84 (2) (1999) 157–160, https://doi.org/
10.1016/s0378-7753(99)00331-6.
[54] G. Yang, Y. Li, R.K. Rana, J.-J. Zhu, Pt–Au/nitrogen-doped graphene
nanocomposites for enhanced electrochemical activities, J. Mater. Chem. 1 (5)
(2013) 1754–1762, https://doi.org/10.1039/c2ta00776b.
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*** START OF THE PROJECT GUTENBERG EBOOK THE BUILDER,

NO. 1, DECEMBER 31, 1842 ***
The Builder, No. 1, December 31,
1842.

THE BUILDER.
PRECURSOR NUMBER.
THIRD IMPRESSION OF FIVE THOUSAND.

No. 1.] LONDON, DECEMBER 31, 1842. PRICE. {Unstamped, 1½ d.

{Stamped, 2½ d.
 ADDRESS.
Upon the occasion of addressing, for the first time, a particular
class, and that too through the medium of a decidedly class-paper, it
seems to us that the views and intentions of its conductor should be
unreservedly stated. We commence, then, in the spirit that will
characterize our future advocacy of the varied interests enumerated
in another page. It is avowed that we enter upon this portion of the
wide field of literature and science as our legitimate province,
inasmuch as we were brought up, educated, and have long wrought
in it; mere qualification for any undertaking is, however, but one
amongst the elements of success, and unless combined with well-
timed efforts, frequently disappoints the possessor:—we invite the
reader to judge of the timeliness of our own by the following incident,
the explanations it gives rise to, and of the result in the publication
before him.
Conversing a few months since with a leading bookseller and
publisher in this metropolis, we had occasion to remark upon the
costly, not to say exorbitant, price of Architectural books; this fact
was not disputed, and the cause at once ascribed to the smallness
of the number of readers, which made it impossible it should be
otherwise. We almost held up our hands in astonishment, as we
repeated his words “smallness of the number of readers!” Call you
five hundred thousand a small number? Can a class of half a million
male adults, whom we may emphatically term all readers, and
members of reading families; a class of half a million of the pick of
British Artisans; a class of the highest intelligence, and (measured by
their wages and numbers) highest in wealth: can we talk of the
smallness of the number of readers, and assume to know any thing
of this large and influential body? It was in this strain that we
interrogated our friend the bookseller; it was a burst of somewhat
indignant feeling, for we had long thought on the subject, and felt
convinced that the fault lay, not with the reader, but rather with the
writer and publisher. We have since put the case in a familiar way to
other parties, as we will now proceed to do to our readers.
Suppose the Grocers, whose business it is to supply the
commodities of their shops in a way suited to the daily wants of
customers, were to act upon the principle of refusing to parcel out
their tea and sugar, or to dispose of it in less quantities than a chest
of the former, or a hundred weight of the latter; or, bringing the
parallel nearer, suppose the Bakers, in dispensing the “staff of life,”
were to set themselves above the standard of purveying the
quartern, and half-quartern loaf; or again, that the Butcher should
sell his meat in nothing less than the carcase; or that these
tradesmen were to study only the palate and appetite of dainty and
refined stomachs; what, let us ask, would be the condition of men of
moderate means, and homely requirements? Why, just that which in
regard to the food of the mind is the condition of the Working Builder.
There are in England, Scotland, and Wales, one hundred and
twenty thousand Carpenters, of full age, and we may assume for
Ireland (the compiled accounts not assisting us here) thirty thousand
more, making a total of one hundred and fifty thousand, exclusive of
apprentices, in this trade alone, who, in common with the other co-
operating Building Artificers, require to read and study (and in some
instances to abstruseness) on all subjects connected with their craft.
For these hundreds of thousands there has hitherto been no retailing
of proper food for the mind; no books at moderate prices, and in
suitable parcels; and if we except the issue in parts and numbers of
works such as those of Mr. Peter Nicholson, the large sale of which
confirms the truth of our convictions, nothing in the shape of a trade
instructor, or magazine, adapted to their several pursuits has yet
been offered to this immense body. The “Architectural Magazine,” by
Mr. London, indeed, did wonders in its way; and other journals which
have followed in its track are, no doubt, well adapted to the particular
departments whose cause they espouse, and promote;[1] but what is
there, we ask again, for the work-shop, and for the fire-side circle of
the Building Artisan?
Examine our Prospectus, and contemplate the numbers forming
an array of what we have advisedly termed “the pick of British
Artisans.” Be it remembered, however, that we do not use these
words in an invidious sense, or in disparagement of other bodies of
the industrious citizens of the empire; but, considering the standard
of perfection, in body and mind, required for the proper practising of
the Building Arts, and considering also the healthful nature of their
occupations, it will not be deemed arrogant in us to speak thus of the
class to which we have the honour to belong; in addition, we have
the influence which numbers, intelligence, and wealth, if united, must
ever secure to us. With all these advantages present to literary eyes
and ears, in an age of professed catering, printing, and publishing, is
it not one of the greatest marvels—a huge paradox—that there is no
such thing as a Builder’s Newspaper and Magazine?
We have just said Newspaper and Magazine, for it has occurred to
us (rather happily, we opine and trust), to combine them; that is to
say, the particular features which distinguish either. We would relieve
the Working Builder from a double charge for matter less available to
him in practice, as well as from the still greater evil, in many
instances, of a dry magazine at home, and a well moistened
newspaper at a public-house. We have an eye to the superior
household and domestic economy which prevails, and which we
would have still more constant in the Builder’s Circle. We would give
him a book on his trade, worth preserving, and a newspaper for the
reading of his wife and family, as well as for himself; and, finally, we
would make the weekly pence set apart from his earnings, for the
gratification of a common feeling of curiosity, not begrudged by the
partner of his cares on the one hand, or to be regretted by the most
thrifty economist on the other, since, even the news will be the
vehicle of trade knowledge, and consequently of the means of trade,
with its advantages and profits.
In designating our paper, we use the word “Builder” in its most
extended sense—instancing a house, or other edifice, we regard it
from the procurement and preparation of the materials, to the fixing
upon its site, and to its full completion for the residence, use, and
enjoyment of man, and which includes the making of the design or
plan, “breaking” ground, as it is termed; the erection, or building up;
decorating, fitting, and furnishing; the supply of water and drainage;
and even the laying out of the garden, pleasure grounds, and park.
This is the whole art of building, or, in other words, of providing and
perfecting human habitations. To all, therefore, who are engaged in
the Art so defined, we address ourselves without distinction, and
without preference; the interests of all will, to the best of our power,
be consulted, promoted, and advocated.
It now becomes us to say a few words as to how far this step (that
is, the issuing of the “Precursor Number”) is to be considered on
our part as an experiment; for, without being clear and explicit, we
should, in case of failure, or rather abandonment, of our enterprise
(for failure there can be none, where provision is made against that
result), incur the blame of not having given our friends, the Building
Classes, a clear view of the part which we humbly conceive it is their
duty and interest to take in the business.
The “Precursor” is a trial number; and we make the avowal plainly
and distinctly. Our part of the affair is to make every effort to supply
what we consider a useful and most desirable public object. The part
of the building fraternity, to whom it is particularly addressed, and the
part of those who regard as a duty all the exertions they are making
in the cause of public education; and also of those who pursue the
arts out of a pure love and liking, is to support our humble efforts if
they deem them worthy of appreciation. The less the sacrifice called
for on either side the better. Let the covenants between us be of an
equitable nature, and as we start upon the principle of
discountenancing, as far as practicable, all lottery and riskful
speculation (of which we will say more presently), so in the basis of
this compact with our friends and readers, we would remove all
unnecessary hazard, or complexion of adventure. We give our best
exertion in what appears to us a work of common good; if our friends
think well and approvingly of these exertions, and that work, let them
contribute their part, were it alone for economy and fairness sake.
We do not rely upon the leviathan power of capital for our success;
but we purpose building it up by an honest and diligent pursuit of the
objects defined, aided by a fair share of judgment, and other
necessary qualifications; and we anticipate it in the cheerful and
generous response of our countrymen: and this Precursor Number,
as its name implies, has its office in searching out the way, and
exploring the track which its successor “The Builder” is designed to
follow. If the Precursor finds a ready passport, and a significant
welcome, of which we have no doubt, it will be promptly followed by
that of which it will have been the harbinger.
We invite, therefore, an active dispersion of the Precursor
amongst our friends; but, above all, we respectfully invite
communications from the many distinguished patrons and favourers
of works of this class. We invite also the Architect, Engineer,
Landscape Gardener, Master Builder, Manufacturers in ornamental
processes, and proprietors generally, Clerks of Works, Foremen, and
Workmen, to avail themselves of the ready means of the penny-
postage, to aid us by their supporting voices, and by any
suggestions they can commit to paper. A Supplement will be issued
with a subsequent impression of the Precursor (without increase of
price), and in that Supplement our correspondence, and additional
advertisements will appear; we, therefore, scarcely need say that the
more promptly our friends reply to the invitation the better.
It now remains for us to say something of the peculiar character
proposed to be given to the “Builder.” The Prospectus, which serves
as the basis of this exposition, sets forth that the trade essays and
descriptions will be accompanied by illustrations and diagrams: that
is, we shall supply drawings, to render clearer the accounts we may
give of mechanical inventions and processes; drawings of ornament,
or enrichment in Plasterwork, Painting, Sculpture, Carving, Iron, and
other metals; drawings of Mouldings, and Moulded work, for the
Carpenter, Mason, and Bricklayer; drawings of construction, in roofs,
floors, trusses, and framing, hand-railing, &c., centering of arches
and groining; drawings of Buildings, both ancient and modern; plans,
elevations, sections, and details: drawings of Architectural orders
and styles; drawings for instruction in perspective, geometry, and the
like; and, occasionally, coloured printing, in such matters as pertain
to painting and staining.
We shall also give patterns for the paperhanger and upholsterer,
and designs for furniture; and a comprehensive range of constructive
and ornamental design suited to that immense territory of British pre-
eminence, the Iron-foundry and its workshops: as connected with
these, we come to that creative and directing science, Civil
Engineering, and here drawings of constructed works, of Engines
and Machinery, will have a prominent place, accompanying the
descriptive treatises and essays.
From this enumeration it must be evident that a large space will be
devoted to the sciences in the nature of connected and consecutive
essays; another part to the record of progress in the Building Art;
and a third to news relating to Building and Builders.
Reviews and notices of publications intended for or likely to be
useful to Builders, will also be given, and biographical sketches of
eminent men connected with science and the arts. These separate
heads, together with correspondence and inquiries, will constitute
the peculiarities of our Journal, and the remaining space will assume
the aspect of the general weekly press—home and foreign news;
digest of Parliamentary reports; political opinions of the leading
Journals; dramatic notices; general literary reviews; police and law
reports; markets, and advertisements.
So ample is the field before us, that there can be no lack of matter
or subjects; our business will be to cull the choicest for the literary
banquet of our friends. Much that is valuable we hope and look for in
the shape of correspondence; one of the chief merits of “The
Builder” being, that it is a direct and fitting medium for conveying
instruction from the liberal and enlightened of every department—a
free exchange of knowledge—which we anticipate may result in
mutual good service to all.

[1] We would instance the Civil Engineer and Architect.

 WILLIAM OF WYKEHAM.
We have selected the portraiture of this illustrious man, whose
fame lives in national works, as the first wherewith to embellish our
Gallery of Architects—a man who was eminent, not only as an
architect, but as a liberal patron of the arts—not only as a builder of
colleges, but as a munificent donor to the cause of education, and
whose institutions still flourish among the proudest in the land. “Many
there are,” says Bishop Lowth, in his Life of Wykeham, “who have
felt the influence of his liberality, or who are actually partakers of his
bounty.”
It is rarely that instances approaching in interest to that of our
subject present themselves; of successful talent we have many, but
they are limited to its mere exercise for ordinary reward; others,
where ambition and ostentation, as in the case of Wolsey, stimulated
to a patronage of great works, while in that of Wykeham we have a
memorable example of true nobility of mind, soaring from humble
origin to the most elevated stations in church and state, and fulfilling
its duties by an active exercise of all the kindred virtues.
William of Wykeham was born at the village of that name in
Hampshire, in the year 1324, of reputable but poor parents, whose
deficiency of means to afford him education was supplied by the
generous intervention of Nicholas Uvedale, lord of the manor of
Wykeham, and constable of Winchester Castle, then one of the great
offices of the kingdom. After going through the course of study
afforded by the school at Winchester, we find him officiating as
secretary to Uvedale, and subsequently executing commissions of
trust as attorney for Edyngdon, Bishop of Winchester, his immediate
predecessor in that see, in whose service he appears at that time to
have been engaged.
The piety, diligence, and early acquirements of Wykeham had
recommended him to the notice of many patrons, both lay and
ecclesiastical, and paved the way for his introduction to that of the
reigning monarch, Edward III., and of his son, the renowned Black
Prince; he had already entered the subordinate ranks of the clergy,
and the fitness of his choice was confirmed in after times by the
dignities he attained to; that elevation was, however, preceded by
the execution of works which have stamped his fame as an
Architect.
It is natural that we should ask, how was this talent in architecture
acquired? We find no account of the preparation or training, beyond
that of the general knowledge he had gained at the school of
Winchester, aided by the intuitive genius and taste proper to
comprehensive intellectual powers. No record exists of his having
studied at either of the universities, and if it had been so, the regard
and confidence of the King must be attributed to acquirements very
superior to those at that time current at Oxford or Cambridge, where
theological controversy was the leading and absorbing theme. We
are told, indeed, that Wykeham had studied “arithmetic,
mathematics, divinity, and, above all, the canon and civil law;” and
we see no reason to the contrary. The school of Winchester, a city
then second to none in the kingdom in splendour and opulence,
would scarcely be deficient of teachers in these courses of study; in
the mode, and according to the then understanding of their relative
uses and value.
It is, upon the whole, probable that Wykeham gave the first proofs
of skill as an Architect in the extension and reparation of Winchester
Castle, during his employment by Nicholas Uvedale. That it was a
fortress of considerable extent and consequence, history abundantly
proves; and it continued so down to the period of the civil strife
between the adherents of Charles I. and the Parliamentary armies;
but whatever may have been the extent or description of building
previously executed by him, it led to his appointment, by patent,
dated May 10th, 1356, of Clerk of all the King’s works in the manors
of Henley and Yesthampstead; and by a second patent, under date
30th October of the same year, he was made Surveyor of all the
King’s works at the Castle and Park of Windsor; and subsequently of
all the royal castles south of Trent.
 In these capacities he was furnished with extensive powers; such
as directing the issue of the King’s writ to the sheriffs of counties,
requiring them to impress workmen, who were compelled to labour
at fixed wages; to purvey and apply all material fitted for building; to
hold courts for pleas of trespass and misdemeanours; and to inquire
of the King’s liberties and rights within his demesne lands. The
prelude to the erection of Windsor Castle was the assembling of 360
impressed workmen, by forties, from nine adjoining counties, in
addition to those voluntarily engaged; the original Norman building
was levelled, and on its site, under the eye of a warlike monarch who
delighted in embattled towers and gorgeous halls fitted for the
display of chivalric institutions, was reared this far-famed fortress
and palace of our kings.
Windsor Castle occupied from ten to twelve years of continued
labour, and comprised the King’s palace; the great hall of St.
George; buildings for various purposes, on the east and south sides
of the upper ward; the keep, or tower; the chapel of St. George; the
residences of the custos and canons, in the lower ward, with the
whole circumference of the walls, towers, and gates. Many parts of
the original building remain, but the lapse of nearly five hundred
years, frequent repairs, the enlargements and alterations required to
meet the conveniences or tastes of successive kings, most of whom
have expended immense sums in real or fancied improvements,
have, in a great degree, obliterated a plan and style which was, in
Castellated Architecture, the perfection of the fourteenth century.
His second work was the Castle of Queenborough, in the Isle of
Sheppy, which, from the lowness of the site, and nature of the
foundations, required unusual skill in the Architect. It was
commenced in 1361, and completed in about six years, when the
King, holding his court there, made the town a free borough, naming
it Queenborough, in honour of his Queen Philippa. Of this structure
no part remains; but its position and extent are ascertained by the
moat which surrounded it. There can be no doubt this was one of the
principal castles of the kingdom, designed both as a means of
defence against invasion, and as a point for the assembling of fleets
and armies for offensive purposes. We are told of this building, that it
was “large, strong, and magnificent;” a fitting residence for royalty,
and one of the strongholds of the realm; and its importance may be
estimated by the rank of its constables, who were, in the reign of
Edward III., John of Gaunt, Duke of Lancaster; Richard II., Robert de
Vere, Earl of Oxford; Henry IV., John Cornwall, Baron Fanhope;
Henry VII., Humphry Stafford, Duke of Buckingham; Edward IV.,
George, Duke of Clarence, &c. The last repairs were done in the
reign of Henry VIII., 1536.
Pending these works, Wykeham grew into high favour with his
royal master, and church preferment was heaped upon him with a
lavish hand; he filled also in succession the offices of Secretary of
State, Keeper of the Privy Seal, and Chancellor of England; and
upon the death of Edyngdon, Bishop of Winchester, in 1366, he
succeeded to that see, one of the richest and most influential in the
kingdom. With his career as a prelate or a statesman, we can have
little to do in this sketch, but we may be permitted to notice that it
was replete with great and disinterested actions. Prosperity so
brilliant had, however, its hour of adversity, but which only served to
place in bolder relief the virtues of the Christian and the dignity of the
man. In the dotage of Edward III., charges of malversation, in the
execution of his high offices, were preferred against the Bishop of
Winchester, at the instigation of John of Gaunt, Duke of Lancaster,
who had always manifested an irreconcilable jealousy of his
influence with the king. This proceeding was followed by an arbitrary
sequestration of the temporalities of the bishop, and he retired to the
monastery of Merton, and subsequently to the Abbey of Waverly,
near Farnham, amid the universal regrets of the nation. The
aspersion of a character so singularly exempt from the besetting sin
of avarice, and its twin vices, peculation and sensualism, could not,
however, be long sustained; and at the end of seven months he was
happily restored to the means of carrying forward magnificent
designs for the benefit of posterity.
From this period Wykeham seems, as much as possible, to have
relieved himself from the burthen of secular affairs, although we find
him again Chancellor in the unsettled reign of Richard II., but which
office he took the earliest occasion to resign. Long and faithful
services to the state had entitled him to repose; but there was no
cessation in the activity of a mind fraught with benevolent purposes.
Possessed of great wealth, he seems to have considered himself but
as a steward intrusted with a useful application of it, and he devised,
with as much judgment as human foresight is permitted to exercise,
the establishments we are now to mention.
With the year 1373 began the formation of a school at Oxford, that
of Winchester having much earlier been taken under his especial
care; at each, masters were provided, and scholars, to the number of
seventy, lodged and boarded at his sole charge. These were,
however, but preliminary steps to the great and original plans
contemplated, namely, the founding of colleges at Oxford and
Winchester, with buildings, masters, and suitable appointments, and
a perpetual maintenance for two hundred scholars, who, while
receiving the advantage of liberal support, were trained from
elementary learning through the whole circle of the sciences. So
costly was this undertaking, that no individual, with a single
exception, has had the means or generosity to emulate the example.
This occurred in the person of King Henry VI., whose colleges at
Eton and Cambridge were founded upon principles scarcely varying
from these models.
Wykeham was now fifty-five years old, and, in realizing his plans,
found full scope for the display of matured genius. Neither the cares
of state which he had encountered, nor the personal ease which so
frequently inclines even great minds to passive inaction, could
obliterate his predilections for architecture. Under this master of his
art were perfected improvements in Gothic style which have
procured for examples of this period the distinction of the pure or
decorated English. These consist in increased boldness, highly
wrought and varied sculpture, and enriched vaultings, with exterior
ornaments of statuary, niched or canopied, upon the western or
great entrance fronts of ecclesiastical buildings. With the taste to
dictate and the wealth to execute such magnificent designs, he
entered upon his tasks, and, in 1379, personally laid the first stone of
the college familiarly termed New College, Oxford, but by himself
“Sainte Marie College of Winchestre in Oxenford,” which was
completed and its establishment inducted with much ceremony in
1386.
We may here be permitted to observe, that with every disposition
to dwell upon the details and beauties of this and his succeeding
works, want of space compels us, for the moment, to relinquish an
intention to do so; but, as subjects of national interest, we shall recur
to them, aided by illustrations calculated to render many peculiarities
of this style available in modern practice.
But to resume our brief notices. Scarcely a year elapsed before
the second, or St. Mary’s College, at Winchester, was in progress,
and in six years fitted for the reception of its professors and students.
In extent and style this edifice bears the strong impress of its
founder, whose memory lives freshly in the veneration of his
children, for such we may term those who are here nurtured and
taught, and from amongst whom have stood forth many worthies of
the church, and others of the highest attainments in science.
The next, and last, work of this eminent and excellent prelate, the
construction of the western front, and the nave and aisles of his
cathedral at Winchester, was commenced in 1394, and the 70th of
his age; and in this instance the unimpaired vigour of his
conceptions, and the extreme liberality with which he appropriated
his resources, are equally subjects for lasting admiration. It was built
by Walklyn, the first Norman bishop after the conquest; and in its
governing features, extent and massiveness, is in the style so called.
We have before mentioned the western front as the work of
Wykeham, which, though mutilated by barbarian fanaticism, retains
much of its splendour, and is a marked example of his manner.
Entering by this door-way, we are at once upon the scene of his
mightiest achievement;—the eye becomes fixed for a moment by the
gorgeous colouring of the eastern window, then wanders upwards
amidst the infinite tracery and adornment of the vault, and, having
scanned the vastness of the pile, seeks repose in a more leisure
examination of the isolated, but not less beautiful, objects of
sculpture below.
 Apart from associations and impressions induced by the aspect of
Gothic temples upon the great scale, we here find the elements of
solidity, propriety, and uniformity carefully preserved, and the
enrichments distributed with a masterly hand; the groining of the roof
springs from single shafts rising from octangular bases; the capitals
are highly embellished with busts and foliage, and the frieze charged
with bold and finely-sculptured bosses; in fact, we have here before
us an era in the Gothic style, and a perfect adaptation of its
capabilities, carried out with all the originality that distinguished the
genius of the architect.
The various writers who have treated on the antiquities of
Winchester agree that the effect produced by the columnar vista of
the nave, in combination with the group of chantries and screens, is
not surpassed by any spot in England, or in Europe. In minute
Gothic, or shrine-work, it is also unrivalled. The tomb of Wykeham,
executed, according to the practice of the middle ages, under his
own direction, is the purest of all authorities in this style: it is placed
within the mortuary chapel, or chantry, occupying the fifth arch from
the west end, and is rich in canopies and tabernacle work; the latter
originally contained statues of saints, particularly that of the Virgin,
which stood against the same pillar, when in his youth he had
worshipped here; but these have long since been destroyed, and the
tomb despoiled also of the enchased escutcheons which adorned it.
The marble figure represents the prelate as possessing full features,
and a placid, benign, and intelligent countenance; it is clothed in full
episcopal costume, the head resting upon a pillow supported by
angels, and at the feet are three figures of one of the religious
orders, in the attitude of prayer.
The life so usefully spent closed in the year 1404, leaving more
durable and splendid memorials than it has been the lot of any other
individual to rear. Having, for nearly half a century, held the highest
stations, and possessed almost unbounded influence, we find it to
have been exerted in a spirit far in advance of his times; and
personal aggrandizement grew upon him as a consequence of
undeviating integrity and universal benevolence; these great and
marked qualities were evinced in pure and unabated loyalty to his
prince, courtesies and services to his equals of the church and the
nobles of the land; and, above all, in the kindness, forbearance, and
mercy which he caused to be exercised towards the people of a yet
unenlightened age.
William of Wykeham expired at his manor house, or palace, of
Waltham, Hants, A.D. 1404, in the eightieth year of his age, and his
remains rest under the tomb we have described. His life affords,
perhaps, the most brilliant example on record of the combined power
of industry and genius; the industry to acquire knowledge, and the
genius to apply it in advance of preceding theories. His earliest
employments seem to have been merely such as a tolerably well-
educated man of the fourteenth century would find little difficulty in
obtaining. Architecture was his diverging point from the monotony of
ordinary life towards the greatness he achieved, his first essays
appearing to have resulted from opportunities which casually fell in
his way, but embraced with an alacrity inspired by self-confidence.
Having once engaged in it, his fondness for the science knew no
abatement, for however lofty his position in the state, or onerous his
duties as a churchman, he found leisure to cultivate it; and having
engrafted new and more impressive features upon the style he
delighted in, may be said to have died in the exercise of this
profession, just before the completion of his cathedral at Winchester.
So exalted were the stations and so extensive the influence he
possessed, that the spirit of benevolence by which he was actuated
had full scope for exertion. While serving his prince with unswerving
loyalty, he found means to protect the people from oppression and
exactions, and by numerous courtesies and services to the nobility,
won them to a milder exercise of their territorial privileges; while in
the relations of private intercourse, we are told that he was “the
kindest and most generous of patrons, and the most constant and
affectionate friend, rarely changing his officers or domestics, none
leaving, or being deserted by him, and all receiving in their turn
testimonies of his favour.”
By his hand the revenues of the church were disbursed in her
service and to her honour, and, to use the words of Lowth, the whole
period from the meridian of life to the end of his days was employed
“in one continued series of generous actions and great designs, for
the good of his friends, of the poor, and of his country.”