Improved methanol electrooxidation

catalyzed by ordered mesoporous

Pt-Ru-Ir alloy nanostructures with trace
Ir content Sabarinathan Ravichandran
& Narayanamoorthy Bhuvanendran &
Qian Xu & Thandavarayan Maiyalagan &
Huaneng Su
Visit to download the full and correct content document:
https://ebookmass.com/product/improved-methanol-electrooxidation-catalyzed-by-ord
ered-mesoporous-pt-ru-ir-alloy-nanostructures-with-trace-ir-content-sabarinathan-ravi
chandran-narayanamoorthy-bhuvanendran-qian-xu-thandavaraya/
 Electrochimica Acta 394 (2021) 139148

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Improved methanol electrooxidation catalyzed by ordered mesoporous

Pt-Ru-Ir alloy nanostructures with trace Ir content
Sabarinathan Ravichandran a,b,1, Narayanamoorthy Bhuvanendran a,1, Qian Xu a,
Thandavarayan Maiyalagan c,∗, Huaneng Su a,∗
a
Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China
b
School of Material Science and Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China
c
Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur, 603203 Tamil Nadu, India

a r t i c l e i n f o a b s t r a c t

Article history: Mesoporous nanostructures of Pt alloy with Ru-Ir as trimetallic electrocatalyst exhibits significant perfor-
Received 29 June 2021 mance for direct methanol fuel cell (DMFC). In this study, the ordered mesoporous nanostructure (OMNs)
Revised 12 August 2021
of Pt-Ru-Ir catalyst was prepared through the KIT-6 mesoporous silica template-assisted chemical re-
Accepted 22 August 2021
duction method. The OMN of Pt-Ru-Ir possesses high Pt utilization and a low Ir content, resulting in
Available online 26 August 2021
promoted MOR kinetics by the bi-functional mechanism of its oxophilic nature. In addition, the oxides
Keywords: of both Ru and Ir further enhanced the electrocatalytic efficiency of Pt by producing more active sites
Ordered mesoporous catalyst owing to its ordered mesoporous morphology and bifunctional mechanism. Furthermore, the OMNs of
Oxophilic metals Pt0.7 Ru0.25 Ir0.05 electrocatalyst has a substantial electrochemical surface area (ECSA) of 78.35 m2 g−1 with
Trace Iridium 1721 mA mg−1 of mass activity, which is comparatively 2-3 times higher than all other catalysts re-
Electronic effect ported here. Notably, the ECSA loss (19.5 %) after 50 0 0 durability cycles was found much lesser than
MOR
other compositions, Pt/C and Pt0.7 Ru0.3 catalyst owing to the synergistic effect between Pt and Ru with
a trace amount of Ir, smaller particle size, and unique ordered mesoporous morphology. Another signifi-
cant factor is the rate of CO poisoning during MOR, which was found to be much lesser than others for
the Pt0.7 Ru0.25 Ir0.05 catalyst (∼0.0047 %) studied by chronoamperometry test. The results indicate that the
unique OMNs of Pt-Ru-Ir is an excellent MOR catalyst for DMFC applications.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction
The newly emerged methanol economy is playing an important
role as an alternative to conventional energy sources, particularly
internal combustion engines, by entering the direct methanol fuel
cell, a promising renewable energy system with clear features of
eco-friendly operation at low temperature and high energy con-
version efficiency [1-3]. The methanol oxidation reaction (MOR) is
an important electrochemical reaction that requires an active cat-
alyst material to improve the slow kinetics and multi-step reac-
tion mechanism [4,5]. Pt-based materials are still considered as the
most promising MOR catalysts for increasing electrocatalytic per-
formance [5,6]. The key drawback is the high cost of the Pt cat-
alyst, as well as the fact that it rapidly adheres to the poisonous
CO intermediate on active sites during the reaction [3,7]. Bimetallic
∗
Corresponding authors.
E-mail addresses: maiyalagan.t@ktr.srmuniv.ac.in (T.
suhuaneng@ujs.edu.cn (H. Su).
1
Equal contribution.
(Pt-M) and trimetallic (likely Pt-Ru-M) based alloy catalysts (M= Ir,
Pd, Cu, Mn, Fe, and Rh) have been extensively studied for MOR be-
havior in acidic medium [6,8,9]. A Pt-Ru based catalyst was estab-
lished to be the most suitable and active catalyst for MOR through
a bifunctional mechanism.
Furthermore, the catalyst’s structural morphology is the most
influential factor, determining the substantial electrocatalytic effi-
ciency through various aspects of its size, shape, crystalline facets,
surface properties, and, most importantly, the synergism between
catalyst components [6,10,11]. A wide range of platinum-based
multi-metallic alloys with morphology-controlled nanostructures
such as core-shell, nanorods, nanowires, nanodendrites, nanocubes,
and ordered mesoporous, and others, have been studied exten-
sively for MOR. Depending on the requirements, various types of
templates such as PVP, F123, F127, CTAB, P123, F108, SBA-15, and
KIT-6 [11-15] are being used to produce these well-designed elec-
trocatalysts. PVP-assisted concave octahedron nanocrystals of Pt-
FeCu were developed by reducing PtCl6 2− , Fe3+ , and Cu2+ ions
Maiyalagan), with ascorbic acid, forming tiny spherical nanoparticles of Pt-
FeCu catalyst for MOR [16]. Pt-M (M= Co, Ni) mesoporous nan-

https://doi.org/10.1016/j.electacta.2021.139148
0013-4686/© 2021 Elsevier Ltd. All rights reserved.
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
otubes were prepared using a dual-template approach, i.e., using Te
nanowires and F127 micelles as self-sacrificial nanotubes and pore-
inducing templates to facilitate the construction of mesoporous
nanostructure for ORR and MOR [17].
Pt modified by Ru contributes lattice concentration, which in-
creases the activity of multimetallic PtFe@PtRuFe core-shell nanos-
tructures. These nanostructures have excellent MOR efficiency and
are resilient to CO poisoning [18]. Similarly, the morphology-
controlled Pt-Ru nanodendrites was synthesized by one-pot reduc-
tion and exhibits an improved electrocatalytic performance due to
the well-spreading atoms of Pt and Ru with an average particle
size of 21 nm, reported by Xue et al [5]. Tunable hollow Pt@Ru
dodecahedra and deformed Pt@Ru dodecahedra catalysts have su-
perior specific activity (SA, 1.61 mA cmPt −2 ) and mass activity (MA,
800 mA mgPt −1 ) compared to Pt/C catalysts due to the bifunctional
mechanism [19]. Trimetallic alloy of Pt-Ru-Cu hexapod catalyst was
successfully developed by a galvanic replacement through Stranski-
Krastanov growth mechanism and possesses good activity and sta-
bility for MOR with a synergetic effect and retains nearly 27 % of
its initial MA after 800 cycles compared to Pt/C (60 %) [11]. Surface
alloyed Ru with Pt could activate more Pt atoms in the Langmuir-
Hinshelwood (L-H) pathway than core-shell (Ru@PtNWs) and sig-
nificantly increase the anti-poisoning effect. Li et al. determined
that using a Pt-Ru alloy will improve MOR electron transfer kinet-
ics [20]. The Pt-Ru-NiTiO3 /C electrocatalyst reported by Thiyagara-
jan et al. showed high catalytic activity, which was attributable to
the synergistic effects of NiTiO3 and the bifunctional mechanism
of Ru metal [7]. Esteban et al. reported that the mesoporous Pt/Ru
catalysts were synthesized using the F127 copolymer template, and
found higher accessibility of active areas for MOR due to the large
pore diameter boost the catalyst performance [21].
In order to evaluate the influence of electrode catalytic activity
towards MOR, Bhuvanendran et al. reported the effect of Ir mate-
rial on Ptx Ir/MWCNT catalysts and described the impact of lattice
strain [22]. The inclusion of Ir in Pt-based bimetal alloy catalysts
can be used in terms of bifunctional mechanism due to secondary
metals’ oxophilic nature, which makes them affinitive to adsorption
of a large number of hydroxyl groups [23,24]. Furthermore, the
presence of Ir with Pt catalyst can boost oxidation activity by pro-
viding dual-enhanced electronic and CO tolerance compared to Pt-
Ru, resulting in improved methanol dehydrogenation. This may be
due to the weakening binding energy of Ir metal, which is caused
by the large electronic band distance [24]. On the other hand, the
coexistence of oxophilic metal oxides like RuO2 and IrO2 can in-
crease the utilization of Pt active sites, ultimately increasing cat-
alytic efficiency [22,25]. RuO2 particles are in very close contact
with the Pt-Ru catalyst due to the isolation and high use of Ru
metal, which could lead to the excellent CO-tolerance, higher ac-
tivity, and greater stability [26].
Furthermore, RuO2 content has a great influence on Pt/RuO2
for the electrocatalytic methanol oxidation activity due to elec-
tron conductivity and electron transfer between Pt and Ru [27].
Similarly, the mesoporous shell and hollow structure promote the
transport of the mass/charge to the internal surface of the cata-
lysts, allowing for good metal use [28]. Hence, the newly devel-
oped 3D porous Pt/RuO2 /G demonstrated enhanced catalytic per-
formance in terms of anti-poisoning rate and extended stability
against MOR [25]. Although Pt, Ru, and Ir are costly precious met-
als, Pt group metals (PGM) remain widely-used materials and es-
sential catalysts for fuel cell applications. As a result, there is a
growing trend toward creating expense new electrocatalysts with
less PGM or indeed PGM-free catalysts that may be used without
loss of performance by enhancing the utilization rate of noble met-
als catalysts [22,29].
In this work, trimetallic ordered mesoporous nanostructures of
Pt-Ru-Ir as a supportless catalyst were synthesized by chemical re-
2
Electrochimica Acta 394 (2021) 139148
duction utilizing KIT-6 as a surfactant and sodium borohydride as
a reducing agent. The Pt0.7 Ru0.25 Ir0.05 nanoparticles were applied
as an electrocatalyst with an average diameter of 3.59 nm and
shown electrooxidation of methanol activity and long-term dura-
bility. Moreover, the electrocatalytic activity of the Pt0.7 Ru0.25 Ir0.05
was higher than that of state-of-the-art Pt/C and Pt0.7 Ru0.3 cata-
lysts due to its rich mesoporosity and synergistic impact between
Pt, Ru, and trace amounts of Ir.
2. Experimental methods
2.1. Chemicals and materials
Potassium hexachloroplatinate (K2 PtCl6 , 99%), Ruthenium (III)
chloride hydrate (RuCl3 •xH2 O, 99.9%), and Hydrogen hexachloroiri-
date (IV) hydrate (H2 IrCl6 •xH2 O, 99.9%) were purchased from
Strem Chemicals. Pluronic P123 (PEG-PPG-PEG), n-Butyl alcohol,
Tetraethyl orthosilicate (TEOS), Ethanol (99.9%), Sodium borohy-
dride (NaBH4 ), and 5 wt. % of Nafion solution was acquired from
Sigma- Aldrich. Pt/C catalyst (20 % Pt loading) was obtained from
Sainergy Fuel Cell India Private Limited and Methanol, Sulfuric acid
(H2 SO4, 37 wt. %), hydrochloric acid (HCl, 38 wt. %), and hydrofluo-
ric acid (HF, 10 wt. %) solution were obtained from Rankem, India.
2.2. Synthesis of mesoporous silica KIT-6
A typical synthesis of ordered mesoporous silica template (KIT-
6) was followed using previously published literatures [30]. 6 g of
Pluronic P123 was mixed into 217 g of double-distilled (DD) wa-
ter and then mixed well by magnetic stirring for 30 min at room
temperature. After that, 6 g butanol and 1.628 g HCl were added
to the Pluronic P123 aqueous mixture with vigorous stirring. Once
the above mixture was fully dissolved, 12.9 g TEOS was added and
stirred for 24 hours at 35 °C. Then, the reaction mixture was trans-
ferred to a 250 ml Teflon stainless-steel autoclave and heated to
100 °C for 24 h. The final product was obtained by centrifugation
at 40 0 0 rpm and washed with water and ethanol several times
and dried overnight at 60 °C. The collected white colour powder
was distributed in a mixture of 300 ml ethanol and 6.2 ml HCl
under stirring for 15 min at room temperature. Finally, the yield
was washed numerous times with water and ethanol before being
dried at 60°C and calcined for 5 h at 550°C.
2.3. Synthesis of ordered mesoporous nanostructures (OMNs) of
Pt-Ru-Ir catalysts
Pt0.7 Ru0.25 Ir0.05 mesoporous were synthesized as follows: An
aqueous solution of K2 PtCl6 (25 mg, 0.0208 M), RuCl3 •xH2 O (32
mg, 0.046 M), and H2 IrCl6 •xH2 O (8 mg, 0.0527 M) were mixed
in a 50 ml beaker under continuous stirring for 1 h. In another
50 ml beaker, 360 mg of KIT-6 dissolved in 12.41 ml DD water.
Then, the Pt-Ru-Ir homogenous water mixture was gradually ap-
plied to the KIT-6 dispersion and stirred for 12 h. After that, 10
ml of freshly prepared 0.1 M NaBH4 aqueous solution added drop-
wise under vigorous stirring at room temperature for 1 h. Finally,
Pt-Ru-Ir/KIT-6 mixture was dried in the oven for 6 h at 100 °C, and
the dried sample was dissolved in 10 wt. % HF solution to remove
KIT-6 template by acid etching process overnight with continuous
stirring. Later, it was washed several times with water and ethanol
and before being dried for 6h at 80 °C. Similarly, other composi-
tions of Pt0.7 Ru0.2 Ir0.1 and Pt0.7 Ru0.15 Ir0.15 catalyst were prepared by
following the above synthesis procedure with an appropriate per-
centage of elemental compositions. All the catalysts were prepared
based on the atomic weight of each element. For Pt-Ru catalyst,
the same procedure was adopted without Ir content and the com-
position was fixed as Pt0.7 Ru0.3.
S. Ravichandran, N. Bhuvanendran, Q. Xu et al. Electrochimica Acta 394 (2021) 139148

Fig. 1. TEM and HRTEM images of Pt0.7 Ru0.25 Ir0.05 (a & b), Pt0.7 Ru0.2 Ir0.1 (c & d), and Pt0.7 Ru0.15 Ir0.15 (e & f) catalysts.

3
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
Fig. 2. XRD patterns of Pt0.7 Ru0.25 Ir0.05 , Pt0.7 Ru0.2 Ir0.1 , Pt0.7 Ru0.15 Ir0.15, Pt0.7 Ru0.3, and Pt/C (Comm.) catalysts.
2.4. Materials characterization
The morphology of Pt-Ru-Ir catalysts was analyzed using a
scanning electron microscope (SEM- FEI Quanta, 200) and) and
high-resolution transmission electron microscope (HRTEM, JEOL,
Japan). X-ray diffraction (XRD) examination was performed using
BRUKER instrument with Cu Kα radiation from 10 - 90°, X-ray pho-
toelectron spectroscopy (XPS) was carried out using physical elec-
tronics (PHI 50 0 0 VersaPobe III) to estimate the elemental com-
position. Inductively coupled plasma atomic emission spectroscopy
(ICP-AES) was used to estimate the elemental composition. Surface
area, size, and volume of pores were measured from Brunauer–
Emmett–Teller ((BET) method using by N- adsorption and desorp-
tion isotherm (Quantachrome Autosorb AS-1Version-1.55).
2.5. Electrochemical measurements
The electrochemical tests were conducted on a three-electrode
electrochemical cell coupled with an electrochemical workstation
(AUTOLAB, The Netherlands). Rotating disk electrode (GC-RDE) was
used as a working electrode, platinum wire and Ag/AgCl (3 M
KCl) were used as a counter and reference electrode respectively.
All the potential was converted against reversible hydrogen elec-
trode (RHE) for universality convenience. For each electrocatalyst, a
homogeneous catalyst ink solution was prepared in the following
manner. 2 mg catalyst was dispersed in 4220 μl of solvent mix-
ture (4.2 ml C2 H5 OH + 20 μl 5 wt. % Nafion) using ultrasonica-
tion until homogeneity was achieved. Then, 10 μl of catalyst ink
4
Electrochimica Acta 394 (2021) 139148
(16. 92 μg cm−2 of Pt) was coated on the GC-working electrode
and dried at room temperature. Initially, the cyclic voltammetry
(CV) was measured in N2 saturated 0.5 M H2 SO4 for basic stud-
ies and then in 0.5 M H2 SO4 +0.5 M CH3 OH for MOR at a sweep
rate of 0.1 V s−1 . The durability test was carried out between 0.4 V
and 1.2 V vs. RHE at a scan rate of 0.1 V s−1 in 0.5 M H2 SO4 +0.5
M CH3 OH solution up to 50 0 0 potential cycles. The Chronoam-
perometry test was recorded at 0.94 V vs RHE under similar
conditions.
From the basic CV studies, electrochemical active surface area
(ECSA) was calculated using the charge associated with hydrogen
adsorption/desorption peak observed between 0.03-0.2 V vs. RHE
by applying the following equation [31].
QHdes
ECSA = (1)
210 × m
where, QHdes is the charge of H-desorption from CV (μC cm−2 ), m is
the mass of Pt-Ru-Ir metal loading (16.92 μg cm−2 ) over the work-
ing electrode, 210 μC cm−2 is the monolayer of hydrogen desorp-
tion on a polycrystalline Pt surface [17].
3. Results and discussion
Figure 1 shows the TEM and HRTEM images of Pt-Ru-Ir cata-
lysts, which revealed a unique morphology of ordered mesoporous
nanostructures. The TEM images (Figure 1a, 1c, and 1e) of all
three different compositions of mesoporous Pt-Ru-Ir catalysts and
the average particle size was estimated using ImageJ software and
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
Fig. 3. XPS patterns of Pt0.7 Ru0.25 Ir0.05 catalyst (a) Pt 4f region, (b) Ru 3p region, (c) Ir 4f region, and (d) O1s region.
found to be ∼4.5 nm. The lattice fringes with d-spacing values of
0.24 nm for Pt (111), 0.24 nm for Ru (101), and 0.22 nm for Ir (111)
crystalline facets are well recognized from the respective HRTEM
images (Figure 1b, 1d, and 1f), which are in good accordance with
the reported literature [22,32-34]. Similarly, the low magnification
TEM images were provided in supporting information Figure S1,
which reveals that the majority of nanoparticles were formed in
ordered mesoporous nanostructure, despite the fact that the stak-
ing of mesoporous metal nanostructures and their density causes
the materials to appear agglomerated. Whereas, the FESEM images
shown in Figure S2a, S2c, S2e, and S2g display the clustered mor-
phology of all the three Pt-Ru-Ir and Pt-Ru catalysts, and the ele-
mental composition was tabulated as an insert of Figure S2b, S2d,
S2f and S2h for each of catalysts, obtained from the SEM-EDX anal-
ysis [25,35]. These values are found to be quite comparable to the
catalyst elemental composition as established during the synthesis.
Furthermore, the Pt, Ir, Ru, and O elements have been distributed
uniformly in Pt0.7 Ru0.25 Ir0.05 catalyst, and the alloy formation of Pt,
Ir, and Ru trimetallic nanoparticles was confirmed using FESEM-
EDX mapping (Figure S3a-S3e). The selected area electron diffrac-
tion (SAED) patterns were obtained to the corresponding catalysts
and showed as an insert of Figure 1b, 1d, and 1f. The lattice fringes
were observed with diffused and intense points located in SAED
rings for all three Pt-Ru-Ir catalysts, revealing the crystalline nature
and being consistent with XRD results [36]. Additionally, ICP-AES
was used to estimate the composition of Pt0.7 Ru0.25 Ir0.05 , and the
percentage of Pt, Ru, and Ir were determined to be 68.4 %, 25.5%,
5
Electrochimica Acta 394 (2021) 139148
and 6.1 %, respectively. These values are well associated with the
SEM-EDX results as shown in Figure S2.
The crystal structure and alloy formation of Pt-Ru-Ir catalysts
for various elemental compositions were investigated using pow-
der X-ray diffraction (XRD) analysis [37]. Figure 2 compares the
diffraction peaks of the respective Pt-Ru-Ir catalysts to Pt-Ru and
Pt/C (Comm.), showing that the obtained XRD patterns have pre-
dominant peaks attributing to the Pt crystalline planes with some
additional peaks at lower diffraction angles [38]. The character-
istic peaks can be assigned to the (111), (200), (220), and (311)
diffraction planes corresponding to the face-centered cubic (fcc)
structure of the Pt metal for all the three compositions of Pt-
Ru-Ir and Pt-Ru catalysts, including Pt/C (Comm.) [7,20]. When
compared to standard Pt/C (Comm.), all the three Pt-Ru-Ir dis-
play a positive shift towards the higher diffraction angle, in which
the Pt0.7 Ru0.25 Ir0.05 shows a slightly higher degree of peak shift-
ing than other two compositions. Similarly, as referred to the Pt/C
(Comm.), the Pt0.7 Ru0.3 catalyst exhibits a positive shift. The peak
shifting towards higher diffraction angles is a well-identified phe-
nomenon that endorses the formation of Pt alloys with Ru and Ir
in both Pt-Ru-Ir and Pt-Ru catalysts [36].
In addition, the oxides of Ir and Ru diffraction peaks can be ob-
served at 34.54°, 40.26˚ and 44.67˚ assigned to (101), (200), and
(120) diffraction planes respectively, with some of them appear-
ing as shoulder peaks due to overlap with the high intensity of Pt
(fcc) crystalline planes. Hence, the presence of IrO2 and RuO2 has
been substantiated by the corresponding peaks as stated in the lit-
S. Ravichandran, N. Bhuvanendran, Q. Xu et al. Electrochimica Acta 394 (2021) 139148

Table 1
Electrochemical MOR parameters for Pt0.7 Ru0.25 Ir0.05 , Pt0.7 Ru0.2 Ir0.1 , Pt0.7 Ru0.15 Ir0.15 and Pt0.7 Ru0.3 , Pt/C (Comm.) catalysts.

Catalyst ECSA (m2 /g) MA (mA mg−1 ) Onset (V vs. RHE) If /Ib % of MA loss % of ECSA loss % of CO poison

Pt0.7 Ru0.25 Ir0.05 78.35 1721 0.45 1.37 48.8/5000 19.5/5000 0.0047
Pt0.7 Ru0.2 Ir0.1 43.20 716 0.50 1.27 57.6/5000 32.2/5000 0.0056
Pt0.7 Ru0.15 Ir0.15 43.03 1371 0.48 1.35 47.7/5000 38.3/5000 0.0049
Pt0.7 Ru0.3 25.80 560 0.51 1.20 39.8/5000 45.3/5000 0.0150
Pt/C (Comm.) 77.01 165.7 0.51 1.14 58.7/5000 40.0/5000 0.0440

Fig. 4. Cyclic voltammograms recorded in N2 - saturated 0.1 M H2 SO4 electrolyte at

0.1 V s−1 scan rate for Pt0.7 Ru0.25 Ir0.05 , Pt0.7 Ru0.2 Ir0.1 , Pt0 .7 Ru0.15 Ir0.15 , and Pt0.7 Ru0.3 ,
and Pt/C (Comm.) catalysts.

erature [26,39], neither any specific peaks for metallic Ru and Ir

have been observed. Furthermore, the diffraction peak positions for
RuO2 and IrO2 tend to be very close and cannot be distinguished,
thus could be due to the similar structure and lattice parameters
[40]. The intensity of shoulder peaks observed at 40.26˚, 44.67˚
with (200) and (120) planes was found to be significant and steep
for Pt0.7 Ru0.25 Ir0.05 catalyst as compared to the other compositions
of Pt-Ru-Ir and Pt0.7 Ru0.3 catalysts, implying strong lattice contrac-
tion by intra-metallic interaction between Pt, Ru, and Ir [22]. Ac-
cording to the XRD results, the significance of RuO2 and IrO2 along
with active Pt could be attributed as an excellent booster for oxy-
gen evolution (producing OH− by dissociation of water), depicting
as more beneficial to accelerate MOR activity [22,27].
The crystallite size of the OMNs Pt-Ru-Ir, Pt-Ru, and Pt/C
(Comm.) catalysts was calculated using the Scherrer equation for
the predominant (111) crystalline plane. The crystallite size was
found to be 3.59, 3.75, 3.67, and 4.38 nm for Pt0.7 Ru0.25 Ir0.05 ,
Pt0.7 Ru0.2 Ir0.1 , Pt0.7 Ru0.15 Ir0.15 , and Pt0.7 Ru0.3 catalysts, respectively.
Fig. 5. (a) Cyclic voltammograms of methanol oxidation at 0.1 V s−1 scan rate in
Whereas, the crystallite size of Pt/C (Comm.) was about 2.92 nm. N2 saturated 0.5 M methanol + 0.5 M H2 SO4 electrolyte, (b) comparison of Mass
Similarly, the d-spacing and lattice constant (a) values for all the activity at peak potentials for Pt0.7 Ru0.25 Ir0.05 , Pt0.7 Ru0.2 Ir0.1 , Pt0 .7 Ru0.15 Ir 0.15 , and
catalysts were determined by applying the following equations, (1) Pt0.7 Ru0.3 , and Pt/C (Comm.) catalysts.
& (2):[41]
d = nλ/sinθ (2)
summarized. The d-spacing value of Pt0.7 Ru0.25 Ir0.05 was found to
  be 2.2473 Å, which is comparatively smaller than Pt0.7 Ru0.2 Ir0.1 ,
a=d× h2 + k2 + l 2 (3) Pt0.7 Ru0.15 Ir0.15 , Pt0.7 Ru0.3 (2.2576 Å), and Pt/C (Comm.) (2.2673 Å)
catalysts. Whereas, the similar trend was observed for lattice con-
where, λ is the wavelength of incident radiation (λ = 1.5418 Å), d stant values in this following order as Pt0.7 Ru0.25 Ir0.05 (3.8925 Å)
is the spacing of the crystal planes, n is an integer, θ is the X-ray <Pt0.7 Ru0.2 Ir0.1 (3.9103 Å) <Pt0.7 Ru0.15 Ir0.15 (3.9103 Å) <Pt0.7 Ru0.3
diffraction angle and h, k, l are the miller indices of the particu- (3. 9103 Å) <Pt/C (Comm.) (3.9273 Å). Based on the lattice con-
lar crystalline plane, (here, h=k=l=1). In Table S1, the structural stant values, the percentage of compressive strain was calculated
parameters of all the catalysts from XRD and TEM analysis were and about -0.886 % for Pt0.7 Ru0.25 Ir0.05 catalyst, which is nearly two

6
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
Fig. 6. Mass activity of Pt0.7 Ru0.25 Ir0.05 catalyst compared with benchmark Pt-based MOR catalysts of self-support and supported from reported literature, since 2012-2020.
times higher than all other catalysts might be due to the impact of
trace Ir content and its synergism with Pt and Ru elements.
The BET-specific surface area (SSA) and mesoporous behav-
ior of Pt0.7 Ru0.25 Ir0.05 catalyst was analyzed using N2 adsorption-
desorption isotherm as shown in Figure S4 (Supporting informa-
tion). The SSA was found to be 118.3 m² g−1 with an average di-
ameter of the pore size of about 2.65 nm, using the Barrett-Joyner-
Halenda (BJH) process and the adsorption isotherm (inset of Figure
S4) [36]. As a result, the larger SSA might well be attributed to
the unique characteristics of the ordered mesoporous morphology
of the Pt-Ru-Ir catalyst, and the obtained values are in strong ac-
cordance with the template’s wall thickness (KIT-6) and published
literature [35].
The electronic state of elements and surface composition of the
Pt0.7 Ru0.25 Ir0.05 and Pt0.7 Ru0.3 catalysts were scrutinized using X-
ray photoelectron spectroscopy (XPS). The deconvoluted XPS peaks
of Pt 4f, Ru 3p, Ir 4f, and O 1s elements for both Pt0.7 Ru0.25 Ir0.05 ,
Pt0.7 Ru0.3 catalysts are shown in Figure 3a-d and Figure S5a-c, re-
spectively. The deconvoluted Pt 4f spectra of the Pt0.7 Ru0.25 Ir0.05
catalyst (Figure 3a) represents a combination of doublets with Pt
4f5/2 and Pt 4f7/2 peaks at 73.20 eV and 70.02 eV correspond-
ing to metallic state (Pt0 ) and another set of doublets of 73.70 eV
(4f5/2 ) and 70.57 eV (4f7/2 ) corresponding to divalent state (Pt2+ ),
might be of Pt-O or Pt-OH formations [22,25,42]. As like that of
the Pt0.7 Ru0.3 catalyst (Figure S5a) exhibit a Pt 4f doublets at 73.20
eV (4f5/2 ) and 69.80 eV (4f7/2 ) corresponding to Pt4+ and Pt2+ re-
spectively, with a negative shift of 0.22 eV for Pt 4f7/2 compared to
Pt0.7 Ru0.25 Ir0.05 catalyst [20].
Figure 3b shows that the Ru 3p has asymmetric peaks with
broad tails at 483.0 eV and 461.0 eV for 3p1/2 and 3p3/2 , respec-
tively, assigned to the metallic (Ru0 ) and ionic (Ru4+ ) states [43-
45], with some satellite peaks in the higher binding energy re-
gion for the Pt0.7 Ru0.25 Ir0.05 catalyst. Similarly, the Pt0.7 Ru0.3 cat-
alyst (Figure S5b) has the respective peaks of Ru 3p at very close
binding energy values of 461.01 eV (3p3/2 ) and 482.7 eV (3p3/2 )
to the Pt0.7 Ru0.25 Ir0.05 catalyst. The XPS spectra for O 1s shows a
broad single peak with multiple deconvoluted peaks assigned to a
variety of oxygen states such as oxide (528.4 & 529.6 eV), hydrox-
ide (530.6 eV), the water molecule (532.4 eV), and vacant oxygen
(531.4 eV) as shown in Figure 3d [44,46]. Relatively similar charac-
teristics of O 1s XPS peaks were observed for the Pt0.7 Ru0.3 catalyst
and shown in Figure S5c. Furthermore, the vacant oxygen from O
1s XPS suggests potential electron transfer by the overlapping of Pt
7
Electrochimica Acta 394 (2021) 139148
and Ru, as well as a slight negative change of BE (0.22 eV) for Pt
4f compared to pristine Pt [46], revealing that there could be more
active sites for MOR.
Furthermore, the deconvoluted Ir 4f spectra (Figure 3c) showed
a doublet of Ir 4f7/2 and 4f5/2 at 61.35 eV and 64.35 eV, refer-
ring to the metallic and tetra valence states of iridium, respec-
tively [22,39]. The outer catalyst surface is likely to have intercon-
version of Ir redox states in the form of oxide/hydroxide species,
which could enable facile electron transfer at the interface of active
sites during methanol oxidation [47]. According to the bifunctional
mechanism, the involvement of hydroxide species either from Ru
and Ir may actively participate in removing the strongly adsorbed
CO species during methanol dehydrogenation. As a consequence,
combining two active oxophilic elements (such as Ru and Ir) with
Pt, in the form of oxides could enhance methanol oxidation kinet-
ics while also contributing to improved stability under durability
test conditions [48]. Based on the XPS study, the elemental com-
position (in atomic %) of Pt0.7 Ru0.25 Ir0.05 catalyst was estimated to
be 49.4 % Pt, 18.1 % Ru, 3.1 % Ir, and 29.4 % oxygen, while Pt0.7 Ru0.3
catalyst had 51.4 % Pt, 20.3 % Ru, and 28.3 % oxygen.
Using steady-state voltammetry techniques, the electrocatalytic
efficiencies of OMNs of Pt-Ru-Ir, Pt-Ru, and industrial Pt/C catalysts
have been extensively investigated for MOR. The electrochemical
characterization of the catalysts was examined by recording the CV
profiles in N2 saturated 0.5 M H2 SO4 at 0.1 V s−1 [17]. In Figure 4,
the CV profiles of all three Pt-Ru-Ir with Pt-Ru and Pt/C (Comm.)
catalysts, exhibit a typical butterfly pattern with hydrogen adsorp-
tion/desorption (Hads /Hdes ) and oxide formation/reduction peaks at
low and high potential regions, respectively [3,20]. Both Pt-Ru-Ir
compositions and Pt-Ru catalysts have a CV pattern that is close to
that of Pt/C (Comm.), which clearly indicates that surface reactions
were dominated by Pt active sites. The electrochemically active
surface area of Pt0.7 Ru0.25 Ir0.05 was estimated from the Hads/Hdes
peak area and found to be around 78.35 m2 g-1 as shown in
Table 1, which is significantly higher than other compositions of
Pt0.7 Ru0.2 Ir0.1 (43.2 m2 g-1 ) and Pt0.7 Ru0.15 Ir0.15 (43.03 m2 g-1 ) cat-
alysts [22]. The ECSA of the Pt0.7 Ru0.3 catalyst is nearly three times
lower (25.8 m2 g-1 ), and the Pt/C (Comm.) (77.01 m2 g-1 ) is nearly
equal to that of the Pt0.7 Ru0.25 Ir0.05 catalyst. The particle size dis-
tribution and elemental composition of the Pt0.7 Ru0.25 Ir0.05 catalyst
contribute to a higher ECSA.
The MOR activity of OMNs of Pt-Ru-Ir, Pt-Ru, and Pt/C
(Comm.) catalysts were determined by CV in N2 saturated 0.5 M
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
Fig. 7. (a) Chronoamperometry curves of Pt-Ru-Ir, Pt-Ru and Pt/C (Comm.) catalysts recorded at 0.65 V vs. RHE, and (b) bar chart of ECSA before and after the durability
test.
methanol + 0.5 M H2 SO4 electrolyte at a scan rate of 0.1 V s−1
(Figure 5a) [5,49]. As can be observed from the MOR-CV profiles,
the Pt0.7 Ru0.25 Ir0.05 catalyst has superior methanol oxidation per-
formance, i.e., the onset potential was around 0.45 V and the for-
ward peak current density was about 20.38 mA cm−2 at 0.94 V,
which can be ascribed to the dehydrogenation of methanol. During
the reverse potential scan, a second oxidation peak was observed
with a current density of 17.82 mA cm−2 at 0.74 V, implying that
the surface adsorbed intermediate fragmentations were further ox-
idized. Notably, all three Pt-Ru-Ir catalyst compositions have rela-
tively high MOR activity than Pt0.7 Ru0.3 and Pt/C (Comm.) catalysts,
which could be associated with the synergistic impact of Pt with
8
Electrochimica Acta 394 (2021) 139148
Ru and Ir elements. Furthermore, as described in many works of
literature, the presence of Ru-oxides and Ir-oxides plays a very im-
portant role in the oxidation reaction of methanol by restoring the
active Pt sites through a bifunctional mechanism [20,50]. As a re-
sult, it was clearly demonstrated and addressed using XRD and XPS
results for the respective Pt-Ru-Ir catalysts.
In terms of mass activity (Figure 5b), the Pt0.7 Ru0.25 Ir0.05 has a
superior magnitude of 1721 mA mg−1 compared to Pt0.7 Ru0.2 Ir0.1
(716 mA mg−1 ), Pt0.7 Ru0.15 Ir0.15 (1371 mA mg−1 ), and Pt0 .7 Ru0.3
(560 mA mg−1 ) catalysts, which is potentially competing with
other reported benchmark MOR catalysts from reported litera-
tures [3-6,8-12,15,22,31,32,34,37,38,42,45,49,51-59] as presented in
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
Fig. 8. ADT-cyclic voltammograms recorded in N2 saturated 0.5 M H2 SO4 electrolyte at 0.1 V s−1 scan rate for (a) Pt0.7 Ru0.25 Ir0.05 , (b) Pt0.7 Ru0.2 Ir0.1 , (c) Pt0 .7 Ru0.15 Ir0.15 , (d)
Pt0.7 Ru0.3 , and (e) Pt/C (Comm.) catalysts.
Figure 6. It clearly demonstrates that a trace amount of Ir might be
more optimal for improved MOR activity. According to Sawy et al.,
increasing the Ir content in the catalyst composition weakens the
bond of adsorbed CO and methanol to active Pt sites, causing the
methanol adsorption/dehydrogenation reaction to slow down and
the MOR activity to decrease even further [60].
From the respective CV profiles (Figure 5a), the order of If /Ib
value was found to be in the following order: Pt0.7 Ru0.25 Ir0.05 (1.37)
>Pt0.7 Ru0.15 Ir0.15 (1.35) >Pt0.7 Ru0.20 Ir0.10 (1.27) >Pt0.7 Ru0.3 (1.20)
>Pt/C (Comm.) (1.14). The improved CO resistance of all Pt-Ru-Ir
catalysts might be due to the synergistic effect between Pt, Ru,
and Ir, as evidenced by the higher magnitude of If /Ib values during
methanol oxidation, among other catalysts [19,56]. A Chronoam-
perometry (CA) test can also be used to assess the rate of CO poi-
soning during MOR and the catalysts’ stability at fixed potential
overtime for all catalysts. Figure 7a depicts the CA profiles of all
OMNs of Pt-Ru-Ir, Pt-Ru, and Pt/C (Comm.) catalysts recorded at
0.65 V for 3600 sec in a mixture of 0.5 M methanol + 0.5 M H2 SO4
solution [20,53,57].
The MOR oxidation currents of all catalysts were found to be
decreasing steadily up to 500s and became constant up to 3600s.
Based on the decay of oxidation current over time, the following
formula can be used to calculate the percent of CO poisoning rate
[22]:
δ = 100/ j0 ∓ (dj/dt )t>500s
Electrochimica Acta 394 (2021) 139148
where, j0 is the initial oxidation current density (mA cm−2 ),
(dj/dt)t > 500s is the slope from the linear regression of current vs.
time plot. The poisoning rate (δ ) for all three OMNs of Pt-Ru-Ir cat-
alysts was found to between 0.0047 and 0.0056 % (Table 1), which
is lower than Pt0.7 Ru0.3 (0.045%), standard Pt/C (Comm.) (0.044)
catalysts. This strongly supports the high catalytic activity of Pt-Ru-
Ir catalysts attributed to the unique morphology and bifunctional
mechanism induced by RuO2 and IrO2 .
The durability of electrocatalysts is critical in assessing their
performance over time, which is investigated using the continuous
potential cycling process, also known as the accelerated durability
test (ADT). In Figure 8a-e, the CV profiles show the characteristics
of all electrocatalysts before and after ADT, recorded at 0.1 V s−1
in N2 saturated 0.5 M H2 SO4 [41,59,61]. After 50 0 0 potential cy-
cles, Pt0.7 Ru0.25 Ir0.05 is more stable than other catalysts, retaining
nearly 80 % of its initial ECSA compared to Pt0.7 Ru0.2 Ir0.1 (68 %),
Pt0.7 Ru0.15 Ir0.15 (62 %), Pt0.7 Ru0.3 (55 %), and Pt/C (Comm.) (60 %).
The durability trend was exemplified from the bar chart of change
in ECSA after 50 0 0 cycles of durability test for all three Pt-Ru-Ir,
Pt0.7 Ru0.3 and Pt/C (Comm.) catalysts (Figure 7b). The extended sta-
bility was observed in terms of catalytic mass activity (Figure 9a-e)
loss of nearly 48 % for Pt0.7 Ru0.25 Ir0.05 after 50 0 0 potential cycles
in the evaluation of the MOR activity as performed under similar
conditions of MOR-CV. As a result, the stability of OMNs of Pt-Ru-
Ir catalysts was found to be much better than that of Pt0.7 Ru0.3
and standard Pt/C (Comm.). This may be due to the support-free
(4) morphology with a key function of trace Ir content and particle
9
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
Fig. 9. ADT-cyclic voltammograms recorded in N2 saturated 0.5 M methanol + 0.5 M H2 SO4 electrolyte at 0.1 V s−1 scan rate for (a) Pt0.7 Ru0.25 Ir0.05 , (b) Pt0.7 Ru0.2 Ir0.1 , (c)
Pt0 .7 Ru0.15 Ir0.15 , (d) Pt0.7 Ru0.3 , and (e) Pt/C (Comm.) catalysts.
size distribution, as well as a strong interaction between Pt, Ru,
and Ir, as evidenced by the % of lattice compressive strain [22,47].
Notably, the Pt0.7 Ru0.25 Ir0.05 has outperformed stability and activ-
ity to the reported benchmark Pt-based multimetallic electrocat-
alysts for MOR (Table S2) [5,38,58]. Moreover, the alloy forma-
tion of Pt with Ru and trace amount of Ir, higher specific surface
area, small crystallite and particle size of the Pt0.7 Ru0.25 Ir0.05 cat-
alyst, as well as the co-existence of two critical components, Ru-
oxides and Ir-oxides, played key roles in the enhanced MOR activ-
ity and stability compared to other catalysts. The beneficial effect
of the secondary metal Ru in Pt-Ru is attributed to a bifunctional
mechanism, the activity was decreased by dissolution. As previ-
ously stated, the Ir content played a critical role in inducing the
electronic effect with Ru by altering the electronic properties of Pt,
as evidenced by the XRD and XPS results. Sawy et al. [60] demon-
strated that the presence of oxophilic metals (Ir and Ru) with Pt
have a significant impact on the bifunctional mechanism of MOR.
According to their conclusions, increasing Ir content causes the
downshift of Pt d-band center, resulting in weak interactions be-
tween surface adsorbents (such as methanol and CO) and active
Pt sites [22,60,62,63]. More importantly, the strong electronic ef-
fect of Ir on Pt, depending on its composition, may weaken the
methanol-Pt interaction, resulting in a lack of accessibility of ac-
tive sites and sluggish methanol dehydrogenation, resulting in poor
MOR activity and stability. Furthermore, the CA results demon-
strated that the CO poisoning rate of Pt0.7 Ru0.25 Ir0.05 was relatively
lower than that of other compositions and Pt0.7 Ru0.3 , Pt/C catalysts.
This could be due to the fact that the trace amount of Ir has been
well optimized based on the bifunctional effect on MOR as de-
10
Electrochimica Acta 394 (2021) 139148
scribed above. As a result, the synergism inferred from strong elec-
tronic effects with low Ir content, and lesser CO poisoning rate has
been well evidenced in displaying the improved kinetics of MOR
on Pt0.7 Ru0.25 Ir0.05 with extended stability.
4. Conclusion
In summary, OMNs of Pt-Ru-Ir catalysts with different ele-
mental compositions were successfully prepared using the KIT-6
template-assisted chemical reduction process. TEM and XRD anal-
ysis were used to investigate the physicochemical properties of
Pt-Ru-Ir catalysts, which showed that the Pt0.7 Ru0.25 Ir0.05 cata-
lyst has an OMN morphology with a particle size distribution
of around 4.51 nm and crystalline size of 3.59 nm. The meso-
porous nature of the Pt0.7 Ru0.25 Ir0.05 catalyst, as well as the co-
existence of RuO2 and IrO2 , were exposed by BET and XPS stud-
ies, which helps in promoting the electrocatalytic activity for MOR.
As compared to Pt0.7 Ru0.3 and standard Pt/C (Comm.) catalysts,
the Pt0.7 Ru0.25 Ir0.05 catalyst has a higher mass activity (1721 mA
mg−1 ), ECSA (78.35 m2 g−1 ), and extended stability (retaining 80.5
% ECSA after 50 0 0 cycles), demonstrating the catalyst superior ef-
ficiency towards MOR. According to electrochemical studies, the
presence of two active oxophilic metals (Ru and Ir) alloying with
Pt, as well as the effect of trace Ir content, was determined and
well correlated with its physicochemical features, taking into ac-
count the improved performance of Pt-Ru-Ir catalysts. The develop-
ment of morphology-controlled trimetallic Pt-based nanostructures
with rational secondary element compositions (Ru & Ir) has suc-
cessfully demonstrated improved catalytic efficiency, and it might
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
be a promising strategy for designing potential anode materials for
DMFC.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgements
We thank the financial support from National Key Research
and Development Program of China (2018YFE0121200), National
Natural Science Foundation of China (Nos. 21676126), China Post-
doctoral Science Foundation (No. 2019M661751), Jiangsu Province
Postdoctoral Fund (No. 2019K187) and the Priority Academic Pro-
gram Development (PAPD) of Jiangsu Higher Education Institutions.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.electacta.2021.139148.
References
[1] Q. Liang, L. Zhang, M. Cai, Y. Li, K. Jiang, X. Zhang, P.K. Shen, Preparation
and charaterization of Pt/functionalized graphene and its electrocatalysis for
methanol oxidation, Electrochim. Acta 111 (2013) 275–283.
[2] X. Wang, M. Sun, S. Xiang, M. Waqas, Y. Fan, J. Zhong, K. Huang, W. Chen,
L. Liu, J. Yang, Template-free synthesis of platinum hollow-opened structures
in deep-eutectic solvents and their enhanced performance for methanol elec-
trooxidation, Electrochim. Acta 337 (2020) 135742.
[3] B. Narayanamoorthy, K.K.R. Datta, M. Eswaramoorthy, S. Balaji, Highly Active
and Stable Pt3Rh Nanoclusters as Supportless Electrocatalyst for Methanol Ox-
idation in Direct Methanol Fuel Cells, ACS Catal 4 (2014) 3621–3629.
[4] X.L. Tian, L. Wang, P. Deng, Y. Chen, B.Y. Xia, Research advances in unsupported
Pt-based catalysts for electrochemical methanol oxidation, J. Energy Chem. 26
(2017) 1067–1076.
[5] S. Lu, K. Eid, D. Ge, J. Guo, L. Wang, H. Wang, H. Gu, One-pot synthesis of PtRu
nanodendrites as efficient catalysts for methanol oxidation reaction, Nanoscale
9 (2017) 1033–1039.
[6] K. Deng, Y. Xu, D. Yang, X. Qian, Z. Dai, Z. Wang, X. Li, L. Wang, H. Wang,
Pt–Ni–P nanocages with surface porosity as efficient bifunctional electrocata-
lysts for oxygen reduction and methanol oxidation, J. Mater. Chem. A 7 (2019)
9791–9797.
[7] V. Thiagarajan, P. Karthikeyan, R. Manoharan, S. Sampath, A. Hernán-
dez-Ramírez, M.E. Sánchez-Castro, I.L. Alonso-Lemus, F.J. Rodríguez-Varela,
Pt-Ru-NiTiO3 Nanoparticles Dispersed on Vulcan as High Performance Electro-
catalysts for the Methanol Oxidation Reaction (MOR), Electrocatalysis 9 (2018)
582–592.
[8] C. Li, T. Liu, T. He, B. Ni, Q. Yuan, X. Wang, Composition-driven shape evolution
to Cu-rich PtCu octahedral alloy nanocrystals as superior bifunctional catalysts
for methanol oxidation and oxygen reduction reaction, Nanoscale 10 (2018)
4670–4674.
[9] Q. Wang, S. Chen, H. Lan, P. Li, X. Ping, S. Ibraheem, D. Long, Y. Duan, Z. Wei,
Thermally driven interfacial diffusion synthesis of nitrogen-doped carbon con-
fined trimetallic Pt3CoRu composites for the methanol oxidation reaction, J.
Mater. Chem. A 7 (2019) 18143–18149.
[10] X. Du, S. Luo, H. Du, M. Tang, X. Huang, P.K. Shen, Monodisperse and self-
-assembled Pt-Cu nanoparticles as an efficient electrocatalyst for the methanol
oxidation reaction, J. Mater. Chem. A 4 (2016) 1579–1585.
[11] S. Xue, W. Deng, F. Yang, J. Yang, I.S. Amiinu, D. He, H. Tang, S. Mu, Hexapod
PtRuCu Nanocrystalline Alloy for Highly Efficient and Stable Methanol Oxida-
tion, ACS Catal 8 (2018) 7578–7584.
[12] L. Huang, Z. Wang, W. Gong, P.K. Shen, Atomic Platinum Skin under Synergy
of Cobalt for Enhanced Methanol Oxidation Electrocatalysis, ACS Appl. Mater.
Interfaces 10 (2018) 43716–43722.
[13] A.-X. Yin, X.-Q. Min, Y.-W. Zhang, C.-H. Yan, Shape-Selective Synthesis and
Facet-Dependent Enhanced Electrocatalytic Activity and Durability of Monodis-
perse Sub-10 nm Pt−Pd Tetrahedrons and Cubes, J. Am. Chem. Soc. 133 (2011)
3816–3819.
[14] S. Sun, Q. Gao, H. Wang, J. Zhu, H. Guo, Influence of textural parameters on
the catalytic behavior for CO oxidation over ordered mesoporous Co3O4, Appl.
Catal. B 97 (2010) 284–291.
[15] B.A. Kakade, T. Tamaki, H. Ohashi, T. Yamaguchi, Highly Active Bimetallic PdPt
and CoPt Nanocrystals for Methanol Electro-oxidation, J. Phys. Chem. C 116
(2012) 7464–7470.
[16] Y. Zhang, R. Shi, J. Ren, Y. Dai, Y. Yuan, Z. Wang, PtFeCu Concave Octahedron
Nanocrystals as Electrocatalysts for the Methanol Oxidation Reaction, Langmuir
35 (2019) 16752–16760.
11
Electrochimica Acta 394 (2021) 139148
[17] S. Yin, Z. Wang, X. Qian, D. Yang, Y. Xu, X. Li, L. Wang, H. Wang, PtM (M = Co,
Ni) Mesoporous Nanotubes as Bifunctional Electrocatalysts for Oxygen Reduc-
tion and Methanol Oxidation, ACS Sustainable Chem. Eng. 7 (2019) 7960–7968.
[18] Q. Wang, S. Chen, P. Li, S. Ibraheem, J. Li, J. Deng, Z. Wei, Surface Ru enriched
structurally ordered intermetallic PtFe@PtRuFe core-shell nanostructure boosts
methanol oxidation reaction catalysis, Appl. Catal. B 252 (2019) 120–127.
[19] X. Bai, J. Geng, S. Zhao, H. Li, F. Li, Tunable Hollow Pt@Ru Dodecahedra via
Galvanic Replacement for Efficient Methanol Oxidation, ACS Appl. Mater. In-
terfaces 12 (2020) 23046–23050.
[20] M. Li, Y. Wang, J. Cai, Y. Li, Y. Liu, Y. Dong, S. Li, X. Yuan, X. Zhang, X. Dai,
Surface sites assembled-strategy on Pt–Ru nanowires for accelerated methanol
oxidation, Dalton Trans. 49 (2020) 13999–14008.
[21] E.A. Franceschini, M.M. Bruno, F.J. Williams, F.A. Viva, H.R. Corti, High-Activity
Mesoporous Pt/Ru Catalysts for Methanol Oxidation, ACS Appl. Mater. Inter-
faces 5 (2013) 10437–10444.
[22] N. Bhuvanendran, S. Ravichandran, W. Zhang, Q. Ma, Q. Xu, L. Khotseng,
H. Su, Highly efficient methanol oxidation on durable PtxIr/MWCNT catalysts
for direct methanol fuel cell applications, Int. J. Hydrogen Energy 45 (2020)
6447–6460.
[23] P. Sivakumar, V. Tricoli, Novel Pt–Ru nanoparticles formed by vapour deposi-
tion as efficient electrocatalyst for methanol oxidation: Part II. Electrocatalytic
activity, Electrochim. Acta 51 (2006) 1235–1243.
[24] S. Kwon, D.J. Ham, T. Kim, Y. Kwon, S.G. Lee, M. Cho, Active Methanol Oxi-
dation Reaction by Enhanced CO Tolerance on Bimetallic Pt/Ir Electrocatalysts
Using Electronic and Bifunctional Effects, ACS Appl. Mater. Interfaces 10 (2018)
39581–39589.
[25] H. Huang, J. Zhu, D. Li, C. Shen, M. Li, X. Zhang, Q. Jiang, J. Zhang, Y. Wu, Pt
nanoparticles grown on 3D RuO2-modified graphene architectures for highly
efficient methanol oxidation, J. Mater. Chem. A 5 (2017) 4560–4567.
[26] W. Wang, Y. Li, H. Wang, Improved methanol oxidation on a PtRu–RuO2/C
composite catalyst with close contact, Reaction Kinetics, Mechanisms and
Catalysis 108 (2013) 433–441.
[27] C. Zhou, H. Wang, J. Liang, F. Peng, H. Yu, J. Yang, Effects of RuO2 Content in
Pt/RuO2/CNTs Nanocatalyst on the Electrocatalytic Oxidation Performance of
Methanol, Chin, J. Catal. 29 (2008) 1093–1098.
[28] H. Wang, S. Liu, H. Zhang, S. Yin, Y. Xu, X. Li, Z. Wang, L. Wang, Multinary
PtPdNiP truncated octahedral mesoporous nanocages for enhanced methanol
oxidation electrocatalysis, New J. Chem. 44 (2020) 15492–15497.
[29] Z. Yan, L. Gao, C. Dai, M. Zhang, X. Lv, P.K. Shen, Metal-free mesoporous car-
bon with higher contents of active N and S codoping by template method for
superior ORR efficiency to Pt/C, Int. J. Hydrogen Energy 43 (2018) 3705–3715.
[30] Q. Wang, Y. Zhang, Y. Zhou, Z. Zhang, J. Xue, Y. Xu, C. Zhang, X. Sheng, N. Kui,
Nanocasting synthesis of an ordered mesoporous CeO2-supported Pt nanocat-
alyst with enhanced catalytic performance for the reduction of 4-nitrophenol,
RSC Adv. 6 (2016) 730–739.
[31] H. Huang, X. Hu, J. Zhang, N. Su, J. Cheng, Facile Fabrication of Platinum-Cobalt
Alloy Nanoparticles with Enhanced Electrocatalytic Activity for a Methanol Ox-
idation Reaction, Sci Rep 7 (2017) 45555.
[32] H. Huang, L. Ma, C.S. Tiwary, Q. Jiang, K. Yin, W. Zhou, P.M. Ajayan, Wor-
m-Shape Pt Nanocrystals Grown on Nitrogen-Doped Low-Defect Graphene
Sheets: Highly Efficient Electrocatalysts for Methanol Oxidation Reaction, Small
13 (2017) 1603013.
[33] R. Jiang, D.T. Tran, J. Li, D. Chu, Ru@ RuO2 Core-Shell Nanorods: A Highly Active
and Stable Bifunctional Catalyst for Oxygen Evolution and Hydrogen Evolution
Reactions, Energy & Environmental Materials 2 (2019) 201–208.
[34] N. Zhang, L. Bu, S. Guo, J. Guo, X. Huang, Screw Thread-Like Platinum–Copper
Nanowires Bounded with High-Index Facets for Efficient Electrocatalysis, Nano
Lett 16 (2016) 5037–5043.
[35] H. Wang, H.Y. Jeong, M. Imura, L. Wang, L. Radhakrishnan, N. Fujita, T. Cas-
tle, O. Terasaki, Y. Yamauchi, Shape-and size-controlled synthesis in hard tem-
plates: sophisticated chemical reduction for mesoporous monocrystalline plat-
inum nanoparticles, J. Am. Chem. Soc. 133 (2011) 14526–14529.
[36] P. Karthika, H. Ataee-Esfahani, H. Wang, M.A. Francis, H. Abe, N. Rajalakshmi,
K.S. Dhathathreyan, D. Arivuoli, Y. Yamauchi, Synthesis of Mesoporous Pt–Ru
Alloy Particles with Uniform Sizes by Sophisticated Hard-Templating Method,
Chemistry–An Asian Journal 8 (2013) 902–907.
[37] H. Li, Y. Pan, D. Zhang, Y. Han, Z. Wang, Y. Qin, S. Lin, X. Wu, H. Zhao, J. Lai,
B. Huang, L. Wang, Surface oxygen-mediated ultrathin PtRuM (Ni, Fe, and Co)
nanowires boosting methanol oxidation reaction, J. Mater. Chem. A 8 (2020)
2323–2330.
[38] L. Huang, M. Wei, N. Hu, P. Tsiakaras, P.Kang Shen, Molybdenum-modified and
vertex-reinforced quaternary hexapod nano-skeletons as efficient electrocata-
lysts for methanol oxidation and oxygen reduction reaction, Appl. Catal. B 258
(2019) 117974.
[39] T. Audichon, T.W. Napporn, C. Canaff, C.u. Morais, C.m. Comminges, K.B. Kokoh,
IrO2 coated on RuO2 as efficient and stable electroactive nanocatalysts for
electrochemical water splitting, J. Phys. Chem. C 120 (2016) 2562–2573.
[40] Y. Lee, J. Suntivich, K.J. May, E.E. Perry, Y. Shao-Horn, Synthesis and activities
of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline
solutions, J. Phys. Chem. Lett. 3 (2012) 399–404.
[41] K. Peng, N. Bhuvanendran, S. Ravichandran, W. Zhang, Q. Ma, Q. Xu, L. Xing,
L. Khotseng, H. Su, Bimetallic Pt3Mn nanowire network structures with en-
hanced electrocatalytic performance for methanol oxidation, Int. J. Hydrogen
Energy 45 (2020) 30455–30462.
[42] Y. Qin, M. Luo, Y. Sun, C. Li, B. Huang, Y. Yang, Y. Li, L. Wang, S. Guo, In-
termetallic hcp-PtBi/fcc-Pt Core/Shell Nanoplates Enable Efficient Bifunctional
S. Ravichandran, N. Bhuvanendran, Q. Xu et al.
Oxygen Reduction and Methanol Oxidation Electrocatalysis, ACS Catal 8 (2018)
5581–5590.
[43] Q. Wang, S. Chen, J. Jiang, J. Liu, J. Deng, X. Ping, Z. Wei, Manipulating the
surface composition of Pt–Ru bimetallic nanoparticles to control the methanol
oxidation reaction pathway, Chem. Commun. 56 (2020) 2419–2422.
[44] R. Bavand, A. Korinek, G.A. Botton, A. Yelon, E. Sacher, PtRu Alloy Nanoparticles
I. Physicochemical Characterizations of Structures Formed as a Function of the
Type of Deposition and Their Evolutions on Annealing, J. Phys. Chem. C 121
(2017) 23104–23119.
[45] J. Xie, Q. Zhang, L. Gu, S. Xu, P. Wang, J. Liu, Y. Ding, Y.F. Yao, C. Nan, M. Zhao,
Y. You, Z. Zou, Ruthenium–platinum core–shell nanocatalysts with substan-
tially enhanced activity and durability towards methanol oxidation, Nano En-
ergy 21 (2016) 247–257.
[46] J. Yi, W.H. Lee, C.H. Choi, Y. Lee, K.S. Park, B.K. Min, Y.J. Hwang, H.-S. Oh, Effect
of Pt introduced on Ru-based electrocatalyst for oxygen evolution activity and
stability, Electrochem. Commun. 104 (2019) 106469.
[47] V. Baglio, R.S. Amin, K.M. El-Khatib, S. Siracusano, C. D’Urso, A.S. Aricò,
IrO2 as a promoter of Pt–Ru for methanol electro-oxidation, PCCP 16 (2014)
10414–10418.
[48] D. Geng, D. Matsuki, J. Wang, T. Kawaguchi, W. Sugimoto, Y. Takasu, Activ-
ity and Durability of Ternary PtRuIrࢧC for Methanol Electro-oxidation, J. Elec-
trochem. Soc. 156 (2009) B397.
[49] J. Park, H.J. Kim, A. Oh, T. Kwon, H. Baik, S.-I. Choi, K. Lee, RuOx-decorated
multimetallic hetero-nanocages as highly efficient electrocatalysts toward the
methanol oxidation reaction, Nanoscale 10 (2018) 21178–21185.
[50] L. Huang, X. Zhang, Q. Wang, Y. Han, Y. Fang, S. Dong, Shape-Control of Pt–Ru
Nanocrystals: Tuning Surface Structure for Enhanced Electrocatalytic Methanol
Oxidation, J. Am. Chem. Soc. 140 (2018) 1142–1147.
[51] G. Chen, X. Yang, Z. Xie, F. Zhao, Z. Zhou, Q. Yuan, Hollow PtCu octahedral
nanoalloys: Efficient bifunctional electrocatalysts towards oxygen reduction re-
action and methanol oxidation reaction by regulating near-surface composi-
tion, J. Colloid Interface Sci. 562 (2020) 244–251.
[52] S. Lu, K. Eid, M. Lin, L. Wang, H. Wang, H. Gu, Hydrogen gas-assisted synthe-
sis of worm-like PtMo wavy nanowires as efficient catalysts for the methanol
oxidation reaction, J. Mater. Chem. A 4 (2016) 10508–10513.
[53] M. Li, Q. Jiang, M. Yan, Y. Wei, J. Zong, J. Zhang, Y. Wu, H. Huang, Three-dimen-
sional boron-and nitrogen-codoped graphene aerogel-supported Pt nanoparti-
cles as highly active electrocatalysts for methanol oxidation reaction, ACS Sus-
tainable Chem. Eng. 6 (2018) 6644–6653.
12
Electrochimica Acta 394 (2021) 139148
[54] C. Yang, Q. Jiang, W. Li, H. He, L. Yang, Z. Lu, H. Huang, Ultrafine Pt Nanopar-
ticle-Decorated 3D Hybrid Architectures Built from Reduced Graphene Ox-
ide and MXene Nanosheets for Methanol Oxidation, Chem. Mater. 31 (2019)
9277–9287.
[55] M.S. Khalifeh-Soltani, E. Shams, E. Sharifi, Pt–Ru nanoparticles anchored on
poly(brilliant cresyl blue) as a new polymeric support: Application as an ef-
ficient electrocatalyst in methanol oxidation reaction, Int. J. Hydrogen Energy
45 (2020) 849–860.
[56] C. Li, Y. Qu, L. Du, G. Chen, S. Lou, Y. Gao, G. Yin, Synthesis of Well-Defined
Pt-Based Catalysts for Methanol Oxidation Reaction Based on Electron–Hole
Separation Effects, ACS Sustainable Chem. Eng. 7 (2019) 8597–8603.
[57] Q.-X. Chen, C.-X. Yu, H.-H. Li, Z. He, J.-W. Liu, Composition Modulation
of Pt-Based Nanowire Electrocatalysts Enhances Methanol Oxidation Perfor-
mance, Inorg. Chem. 59 (2020) 1376–1382.
[58] W. Chen, Z. Lei, T. Zeng, L. Wang, N. Cheng, Y. Tan, S. Mu, Structurally ordered
PtSn intermetallic nanoparticles supported on ATO for efficient methanol oxi-
dation reaction, Nanoscale 11 (2019) 19895–19902.
[59] W. Xiong, B.A.T. Mehrabadi, S.G. Karakolos, R.D. White, A. Shakouri, P. Kasak,
S.J. Zaidi, J.W. Weidner, J.R. Regalbuto, H. Colon-Mercado, J.R. Monnier, En-
hanced Performance of Oxygen-Functionalized Multiwalled Carbon Nanotubes
as Support for Pt and Pt–Ru Bimetallic Catalysts for Methanol Electrooxidation,
ACS Appl. Energy Mater. 3 (2020) 5487–5496.
[60] E.N. El Sawy, V.I. Birss, Understanding the role of Ir during methanol oxidation
at PtxIry alloy nanoparticles, J. Electrochem. Soc. 164 (2017) F1572.
[61] Z. Bai, J. Luo, D. Ming, C. Wang, H. Xu, W. Ye, High active and durable N-doped
carbon spheres-supported flowerlike PtPd nanoparticles for electrochemical
oxidation of liquid alcohols, Electrochim. Acta 356 (2020) 136794.
[62] K. Eguiluz, G. Salazar-Banda, D. Miwa, S. Machado, L. Avaca, Effect of the cata-
lyst composition in the Ptx (Ru–Ir) 1− x/C system on the electro-oxidation of
methanol in acid media, J. Power Sources 179 (2008) 42–49.
[63] N. Bhuvanendran, S. Ravichandran, S.S. Jayaseelan, Q. Xu, L. Khotseng, H. Su,
Improved bi-functional oxygen electrocatalytic performance of Pt–Ir alloy
nanoparticles embedded on MWCNT with Pt-enriched surfaces, Energy 211
(2020) 118695.
Another random document with
no related content on Scribd:
 THE WESTMANNA ISLANDS—
REYKJAVIK.

Tuesday morning, July 26. Open sea and not a sail visible, although we carefully
scan “the round ocean.”
Tremendous rolling all night; everything turning topsy-turvy and being
knocked about—my portmanteau, which was standing on the cabin floor,
capsized. Only by dint of careful adjustment and jambing in the form of the
letter z could we prevent ourselves from being shot out of our berths.
To-day we have the heaviest rolling I ever experienced. It is impossible even to
sit on the hurricane deck without holding on by a rope, and not easy even with
such assistance. Deck at an angle of 40 to 45°. The boat fastened aloft
aggravates matters. A very little more, or the slightest shifting of the cargo,
would throw us on our beam ends. The boat getting loose from its fastenings
when we are on the larboard roll would break off the funnel. The Captain has
hatchets ready, at once to send it overboard or break it up if requisite for our
safety. The bell tolling with the roll of the ship, first on the one side, and then
on the other; generally four or five times in succession. A series of large rollers
alternate with lesser waves; the bell indicates the former. Waves without wind
roll in from the N. and N.W., both on the starboard and port bow.
In the afternoon saw a piece of wreck—mast and cordage—floating past,
most likely a record of woe; involving waiting weary hearts that will not die.
Not a speck on the whole horizon line; a feeling of intense loneliness would at
times momentarily creep over us. Birds overhead flying south brought to mind
Bryant’s beautiful poem addressed to “The Waterfowl,” which he describes as
floating along darkly painted on the crimson sky:
“There is a Power whose care
Teaches thy way along that pathless coast,—
The desert and illimitable air
Lone wandering but not lost.
 Thou’rt gone, the abyss of heaven
Hath swallowed up thy form; yet, on my heart,
Deeply hath sunk the lesson thou hast given,
And shall not soon depart.

He, who from zone to zone

Guides through the boundless sky thy certain flight,
In the long way that I must tread alone
Will lead my steps aright.”

The heavy rolling still continues. Hope the cargo will keep right, or we shall
come to grief. Thought of the virtues of my friends. However, maugre a dash
of danger, a group of us on the hurricane deck really enjoyed the scene as if we
had been veritable Mother Carey’s chickens. One sang Barry Cornwall’s song
“The Sea;” another by way of contrast gave us “Annie Laurie” and “Scots wha
hae wi’ Wallace bled;” and towards evening we all joined in singing “York;”
that grand old psalm tune harmonizing well with the place and time—
“The setting sun, and music at the close!”

The gulf-stream and the rollers meeting make a wild jumble. Barometer very
low—2810; low enough for a hurricane in the tropics. Stormy rocking in our
sea-cradle all day and all night.

Wednesday, July 27.—Vessel still rolling as much as ever. Saw a skua—a black
active rapacious bird, a sort of winged pirate—chasing a gull which tried hard
to evade it by flying, wavering backwards and forwards, zig-zagging, doubling,
now rising and now falling, till at last, wearied out and finding escape
impossible, it disgorged and dropt a fish which the skua pounced upon,
picking it up before it could reach the surface of the sea. The fish alone had
been the object of the skua’s pursuit. The skua is at best but a poor fisher and
takes this method of supplying its wants at second hand. Subsequently we
often observed skuas following this their nefarious calling; unrelentingly
chasing and attacking the gulls until they gave up their newly caught fish, when
they were at once left unmolested and allowed to go in peace; but whether the
sense of wrong or joy at escape predominated, or with what sort of feelings
and in what light the poor gulls viewed the transaction, a man would require to
be a bird in order to form an adequate idea.
We cannot now be far from Iceland, but clouds above and low thick mists
around preclude the possibility of taking observations or seeing far before us.
In clear weather we are told that the high mountains are visible from a distance
of 100 or 150 miles at sea.
At half-past Three o’clock P.M., peering hard through the mist, we discover, less
than a mile ahead, a white fringe of surf breaking on a low sandy shore for
which we are running right stem on. It is the south of Iceland; dim heights
loom through the haze; the vessel’s head is turned more to the west and we
make for sailing, in a westerly direction with a little north in it, along the shore
up the western side of the island which in shape somewhat resembles a heart.

NEEDLE ROCKS—OFF PORTLAND HUK.

The mist partially clears off and on our right we sight Portland Huk, the most
southern point of Iceland. Here rocks of a reddish brown colour run out into
the sea rising in singular isolated forms like castellated buildings; one mass
from a particular point of view exactly resembles the ruins of Iona, even to the
square tower; other peaks are like spires. Strange fantastic needle-like rocks or
drongs shoot up into the air—the Witches’ fingers (Trollkonefinger) of the
Northmen. The headland exhibits a great arched opening through which, we
were told, at certain states of the tide, the steamer could sail if her masts were
lowered. It is called Dyrhólaey—the hill door—and from it the farm or village
close by is named Dyrhólar. Behind these curious rocks appeared a range of
greenish hills mottled with snow-patches, their white summits hid in the
rolling clouds.
There are numerous waterfalls; glaciers—the ice of a pale whity-green colour
—fill the ravines and creep down the valleys from the Jökuls to the very edge
of the water. Their progressive motion here is the same as in Switzerland, and
large blocks of lava are brought down imbedded in their moraine. I perceived
what I thought to be curved lines on the surface like the markings on mother-
of-pearl, indicating that the downward motion of a glacier is greater in the
centre than where impeded by friction at the sides.
On the shoulders of the range of heights along the coast, snow, brown-
coloured patches and green-spots were all intermingled; while the upper
mountain regions of perpetual snow were meanwhile for the most part hid in
clouds which turban-like swathed their brows in fleecy “folds voluminous and
vast.”
The steamer is running, at nine knots, straight for the Westmanna Islands,
where a mail is to be landed. They lie off the coast nearly half way between
Portland Huk, the south point, and Cape Reykjanes the south-west point of
Iceland.
How gracefully the sea-birds skim the brine, taking the long wave-valleys,
disappearing and reappearing amongst the great heaving billows. We note
many waterfalls leaping from the mountain sides to the shore, and at times
right into the sea itself, from heights apparently varying from two to four
hundred feet.
We now approach the Westmanna Islands, so called from ten Irish slaves—
westmen—who in the year A.D. 875 took refuge here after killing Thorleif their
master. They are a group of strange fantastically shaped islets of brown lava-
rock; only three or four however have any appearance of grass upon them, and
but one island, Heimaey—the home isle, is inhabited. The precipitous rock-
cliffs are honeycombed with holes and caves which are haunted by millions of
birds. These thickly dot the crevices with masses of living white; hover like
clouds in the air, and swarm the waters around like a fringe—resting,
fluttering, or diving, by turns.
Westmannshavn, the harbour of the islands, is a bay on the north-west of
Heimaey where a green vale slopes down to the sea. It is sheltered by the
islands of Heimaklettur on the North, and Bjarnarey on the East. We observed
a flag flying, and a few huts scattered irregularly and sparsely on the slope.
This place is called Kaupstadr—or head town—but there is no other town in
the group. The roofs of the huts were covered with green sod and scarcely to
be distinguished from the grass of the slope on which they stood save by the
light blue smoke which rose curling above them from turf fires.
A row-boat came off for the mail, which, we were told, had never before been
landed here from a steamer; the usual mode is to get it from Reykjavik in a
sailing vessel. For those accustomed to at least half a dozen deliveries of letters
every day, it was strange to think that here there were fewer posts in a whole
year. These Islands have, on account of their excellent fisheries, from very
remote periods been much frequented by foreign vessels. Before the discovery
of Newfoundland, British merchants resorted hither, and also to ports on the
west coast of Iceland, to exchange commodities and procure dried stock-fish.
Icelandic ships also visited English ports. This intercommunication can be
distinctly traced back to the time of Henry III.; but by the beginning of the
fifteenth century it had become regular and had risen to importance. It was
matter of treaty between Norway and England; but, with or without special
licenses, or in spite of prohibitions—sometimes with the connivance and
permission of the local authorities, and at other times notwithstanding the
active opposition of one or both governments—the trade being mutually
profitable to those engaged in it continued to be prosecuted. English tapestry
and linen are mentioned in old Icelandic writings, and subsequently we learn
that English strong ale was held in high estimation by the Northmen.
Edward III. granted certain privileges and exemptions to the fishermen of
Blacknie and Lyne in Norfolk on account of their Icelandic commerce. In
favourable weather the distance could be run in about a fortnight.
From Icelandic records we learn that in the year A.D. 1412, “30 ships engaged
in fishing were seen off the coast at one time.” “In A.D. 1415 there were no
fewer than 6 English merchant ships in the harbour of Hafna Fiord alone.”
Notwithstanding the proclamations and prohibitions both of Eric and Henry
V. the traffic still continued to increase; and we incidentally learn that in the
year A.D. 1419 “Twenty-five English ships were wrecked on this coast in a
dreadful snow-storm.” Goods supplied to the natives then, as in later times,
were both cheaper and better than could be obtained from the Danish
monopolists. It will be remembered by the reader that when Columbus visited
Iceland he sailed in a bark from the port of Bristol.
Gazing on this singular group of rocky Islands, on the coast of Iceland, so
lone and quiet, and reverting to the early part of the thirteenth century, it was
strange to realize that into this very bay had then sailed and cast anchor the
ships of our enterprising countrymen—quaint old-fashioned ships, such as we
may still see represented in illuminated MSS. of the period; and that their latest
news to such English merchants or fishermen as had wintered or perhaps been
stationed for some time at Westmannshavn—supposing modern facilities for
the transmission of news—would not have been the peace of Villafranca but
the confirmation of Magna Charta;—instead of the formation of volunteer
corps, nobles hastening to join the fifth Crusade;—not the treading out of a
Sepoy revolt, but Mongolian hordes overrunning the Steppes of Russia;—and
instead of some important law-decision, celebrated trial, or case in Chancery,
they might hear of an acquaintance who had perished in single combat, or who
had indignantly and satisfactorily proved his or her innocence by submitting to
trial by ordeal. These were the old times of Friar Bacon—the days of alchemy
and witchcraft. Haco had not yet been crowned King of Norway; Snorre
Sturleson was yet a young man meditating the “Heimskringla.” The chisel of
Nicolo Pisano and the pencil of Cimabue were at work in Italy. Neither Dante
nor Beatrice as yet existed; nor had the factions of Guelph and Ghibeline
sprung into being. Chaucer was not born till the following century. Aladdin
reigned; Alphonzo the Wise, King of Leon and Castile, had not promulgated
his code of laws. Not a single Lombard moneylender had arrived to settle in
London; and the present structure of Westminster Abbey had not then been
reared.

BJARNAREY.

On leaving Westmannshavn, sailing north between the islands of Heimaklettur

and Bjarnarey, we saw two men rowing a boat deeply laden to the gunwale
with sea-fowls, probably the result of their day’s work. The cliffs everywhere
alive with birds, and the smooth sea beneath them, in the glorious light of the
evening sun, dotted black as if peppered with puffins and eider-ducks.
Nine P.M. Sketched various aspects of the islands and several of the strange
outlying skerries.

WESTMANNA SKERRIES.

When the Westmanna Islands are reckoned at fourteen, that number does not
include innumerable little rocky stacks and islets of all fantastic shapes alone or
in groups; some like Druidical stones or old ruins, others of them far out and
exactly like ships in full sail, producing a strange effect on the horizon.
The island nearest the coast of Iceland on the east of Heimaey is called
Erlendsey; that furthest north-west is Drángr; and the furthest west
Einarsdrángr. On the south-west is an islet called Alsey; we have also an Ailsa
in the frith of Clyde: both names probably signifying fire-isle. The islet furthest
south is called Geirfuglasker. These names are necessarily altogether omitted
on common small maps.
We witness a glorious sunset on the sea,—the horizon streaked with burning
gold:
“Now ’gan the golden Phœbus for to steepe
His fiery face in billows of the west,
And his faint steedes watered in ocean deepe
Whiles from his journall labours he did rest.”

Although the surface of the sea is quite smooth, a heavy ground swell keeps
rolling along. A bank of violet cloud lies to the left of the sun, while dense
masses of leaden and purple-coloured clouds are piled above it. An opening
glows like a furnace seven times heated, darting rays from its central fire
athwart the sky, and opening up a burning cone-shaped pathway of light on
the smooth heaving billows, the apex of which reaches our prow.
Such the scene, as we sail north-west between the northernmost out-lying
skerries of the Westmanna group and the south-west coast of Iceland and
silently watch the gorgeous hues of sunset. Strangely at such times “hope and
memory sweep the chords by turns,” till the past, fused down into the present,
becomes a magic mirror for the future.
The air is mild and warm; time by Greenwich twenty-minutes to eleven. The
sun is not yet quite down, and—by the ship’s compass, without making any
allowance for deviation—is setting due north. At a quarter-past 12 A.M. when
we leave the deck, it is still quite light.

CAPE REYKJANES LOOKING SOUTH.

COAST NEAR REYKJAVIK.

Thursday Morning, July 28. Rose early—we are sailing along the Krisuvik coast in
the direction of Cape Reykjanes—smoky cape—which runs out from the
south-west of Iceland. The low lying coast is of black lava; behind it rise
serrated hill-ranges, and isolated conical mountains; some of a deep violet
colour, others covered with snow and ice, the dazzling whiteness of which is
heightened by contrast with the low dark fire-scathed foreground. White fleecy
clouds are rolling among the peaks, now dense and clearly defined against the
bright blue sunny sky—now hazy, ethereal, and evanescent. We observe steam
rising from a hot sulphur spring on the coast. These are numerous in this
neighbourhood, which contains the principal sulphur mines of the island.
Here, where we sail, volcanic islands have at different times arisen and
disappeared; flames too have sometimes been seen to issue from submarine
craters; this latter phenomenon the natives describe as “the sea” being “on
fire.”

ELDEY.

On our left we pass Eldey—or the Fire Isle—a curious isolated basaltic rock
resembling the Bass, but much smaller. It rose from the deep in historic times.
The top slopes somewhat, and is white; this latter appearance has originated its
Danish name “Maelsek,” which is pronounced precisely in the same way as
“meal-sack” would be in the Scottish dialect;—in fact the words are the same.
Many solan geese flying about; whales gamboling and spouting close to the
vessel.
Nine A.M., Greenwich time. Got first glimpse of Snæfells Jökul—the fifth
highest mountain in Iceland—height 4577 feet—lying nearly in a north-west
direction, far away across the blue waters of the Faxa Fiord. A pyramid
covered with perpetual snow and ice, gleaming in the sun, its outline is now
traced against a sky of deeper blue than any of us ever beheld in Switzerland
or Italy.
The Faxa Fiord, situated on the south-west, is the largest in the island, and
might be described as a magnificent bay, forming a semicircle which extends
fifty-six miles from horn to horn; while its shores are deeply and irregularly
indented by arms of the sea, or Fiords proper, which have names of their own,
such as Hafnafiord, Hvalfiord, or Borgarfiord. Snæfell, on the north side of it,
rises from the extremity of the long narrow strip of steep mountain
promontory that runs out into the sea, separating the Faxa from the Breida
Fiord—another large bay;—while on the south the Guldbringu Syssel,
terminating with Cape Reykjanes, is a bare low-lying black contorted lava field.
The Faxa Fiord, then, sweeping in a semicircle from Snæfell to Reykjanes,
contains several minor Fiords, and is crowded with lofty mountain-peaks,
sharp, steep, and bare. The intense clearness of the northern atmosphere
through which these appear, together with the fine contrast of their colours—
reds, purples, golden hues, and pale lilacs; rosy-tinted snow or silvery-glittering
ice—all sharply relieved against the blue sky, as if by magic confound southern
ideas of distance, so that a mountain which at first glance appears to be only
ten or fifteen miles distant, may in reality be forty or fifty, and perhaps
considerably more.
The capital of Iceland lies in the south-east of this great bay. We have been
sailing due north from Cape Reykjanes to the point of Skagi, and, rounding it,
we sail east by north right into the Faxa Fiord, cutting off the southern
segment of the bay, and are making straight for Reykjavik.
Several low-lying islands shelter the port and make the anchorage secure; one
of these is Videy on which some of the government offices formerly stood,
but it is now noted as a favourite resort of eider ducks which are here
protected by law in order to obtain the down with which their nests are lined.
Solitary fishermen are making for the shore in their skiff-like boats. A French
frigate and brig, a Danish war schooner and several merchant sloops are seen
lying at anchor, shut in by the islands and a low lava promontory. All are gaily
decked with colours. On rounding the point, Reykjavik the capital of Iceland
lies fairly before us. It is situated on a gentle greenish slope rising from the
black volcanic sand of that “Plutonian shore.” There are grassy heights at
either side of the town and a fresh water lake like a large pond behind it. The
cathedral in the centre, built of brick plastered brown stone colour, and the
windmill on the height to the left, are the two most prominent objects. The
front street consists of a single row of dark-coloured Danish looking wooden
houses facing the sea. These we are told are mostly merchants’ stores. Several
of them have flag-staffs from which the Danish colours now flutter. All our
glasses are in requisition. Numerous wooden jetties lead from the sea up to the
road in front of the warehouses, and, on these, females like the fish-women of
Calais, “withered, grotesque, wrinkled,” and seeming “immeasurably old,” with
others younger and better looking, are busily engaged in carrying dried fish
between the boats and the stores. Young and old alike wear the graceful
Icelandic female head-dress—viz. a little black cloth scull-cap, jauntily fastened
with a hair pin on the back part of the head. From the crown of this cap hangs
a silver tube ornament, out of which flows a long thick black silk tassel falling
on the shoulder.
Two streets run inland from the front street, and at right angles to it. That on
the left contains the Governor’s house, and the residences of several officials.
It leads to the house where the Althing or Icelandic Parliament now assembles,
and where, in another part of the same building, Rector Jonson teaches in the
one academy of the island. The other street on the right contains several
shops, merchants’ dwelling houses, the residence of Jón Gudmundsson,
president of the Althing, advocate, and editor of a newspaper. It leads to the
hotel, and to the residence of Dr. Hjaltalin, a distinguished antiquarian and the
chief physician of the island. In the same direction, a little higher up, is the
lonely churchyard.
Between these two streets, houses stand at irregular intervals, and nearly all
have little garden-plots attached to them.
On the outskirts, flanking the town, which in appearance is more Danish than
Icelandic, are a few fishermen’s huts, roofed over with green sod; and these, we
afterwards found, were more like the style of buildings commonly to be met
with throughout the island.
As we cast anchor, the morning sunshine is gloriously bright and clear, sea and
sky intensely blue, and the atmosphere more transparent than that of
Switzerland or Italy. Beyond Reykjavik, wild bare heights rise all round the bay;
here—mountains of a ruddy brown colour, deeply scarred and distinctly
showing every crevice; there—snow-patches gleaming on dark purple hills;
here—lofty pyramids of glittering ice; there—cones of black volcanic rock;
while white fleecy clouds in horizontal layers streak the distant peaks, and keep
rolling down the shoulders of the nearer Essian range.
The arrival of the steamer is quite an event to the Icelanders. A boat came off
from the shore, and another from the French brig, to get the mail-bags. We
brought tidings of the peace of Villafranca, and heard the cheering of the
French sailors when the news was announced to them. Dr. Mackinlay, who
had remained, exploring various parts of the island, since the previous voyage
of the Arcturus, and for whom we had letters and papers, kindly volunteered
to give us information about the Geyser expedition. From his habits of keen
observation, patient research, and kind-heartedness, he was well qualified to do
so.
He recommended Geir Zöga, who had accompanied him on board, as a good
trustworthy guide. We wished to start at once, so as to make the most of our
time, but the undertaking was a more serious affair than we had anticipated.
Ultimately, before landing, we arranged to start next morning at eight o’clock,
as the very best we could do.
The distance to be got over is 72 miles, literally without roads or shelter; and
mostly over wild rough stony wastes, in comparison with which the bed of a
mountain water-course would be a good macadamized road. Provisions, traps,
and everything we require have to be taken along with us.
We are a party of six; the guide has two assistants; nine riders in all, each
requires a relay horse, so that eighteen ponies for the riders, and six for the
baggage are requisite for our expedition. These have to be bargained for and
collected together by Zöga from the farms around Reykjavik; and as the
ponies now run almost wild over the wastes in pursuit of scant herbage, and
neither receive grooming, stabling, nor feeding, this is a work of time, and will
occupy, Dr. Mackinlay tells us, not only the whole afternoon but the greater
part of the night.
No one had brought provisions north but myself, so arrangements are made
with the steward of the steamer for supplying them, and mine thrown in with
the rest pro bono publico. Having fixed that Zöga should call in the evening at
the hotel and report progress, at half-past 11 o’clock A.M. we got into the
Captain’s boat to land, where, long ago, Ingolf the first colonist had drawn his
ship on shore. As the remainder of the day is at our disposal, curiosity is on
edge to explore Reykjavik, the general plan and appearance of which has
already been described—partly by anticipation.
The sun-glare is oppressively hot. As we approach the jetty we observe groups
of men and women standing on the beach to see the passengers land. Some of
the younger women are good-looking, and become the picturesque costume of
the country;—those curious little black caps with silver ornaments and long
black silk tassels already described; jackets faced with silver lace or rows of
metal buttons; belts similarly ornamented; long flowing dark wadmal skirts of
home manufacture; and primitive shoes made of one bit of cow-skin or any
kind of hide, prepared so as in colour to resemble parchment or the skin one
sometimes sees stretched like a drum-head over the mouth of a jar of honey.
A few other ladies are in morning dress, with shawls or handkerchiefs thrown
gracefully over their heads, and nothing peculiar or different in their costume
from what we are accustomed to see at home.
Mr. Haycock had received a letter of introduction to Mr. Simson, and I had
one to Mr. Sievertsen; the latter is a retired merchant, and the former carries
on a large business of a very miscellaneous kind—such being the character of
all the stores or factories here. As the houses of these gentlemen both lay in
the same direction, we set out together in order to obtain advice as to what
was to be seen in Reykjavik and its neighbourhood. In passing along the front
street, the stores—mostly belonging to Danish merchants—presented quite a
bustling business aspect; while the dwelling houses, with lattice windows, white
curtains and flower-pots of blooming roses and geraniums, exhibited an air of
cleanliness, comfort and refinement. From the absence of roads, carts are
useless; one wheel barrow which we saw, belonging to an enterprising
storekeeper, we were told, was the only wheeled vehicle in the island.
Mr. Sigurdur Sievertsen received us most cordially. This intelligent old
gentleman conducted Sir George Mackenzie, who was his father’s guest, to the
Geysers; and he is alluded to by Sir George, in his travels, as “young Mr.
Sievertsen.” Time works changes! or, as Archbishop Whately would more
accurately put it, changes are wrought, not by, but “in time.” However, Mr.
Sievertsen is hale and hearty, and many summers may he yet see! On the wall
we saw the portrait of his gifted and much lamented son, who several years
ago died in Paris. He had been taken there by Louis Philip to receive a free
education, as a graceful acknowledgment to the Icelanders for kindness shewn
to the crew of a French vessel wrecked on their coast.
 L Men’sshoes. G Girls’ shoes. S Snuffbox made of walrus tusk. H Female-head-
dress with flowing silk tassel (see p. 49). D Distaff. M Two-thumbed mits.]

Our host has visited Britain, and both speaks and writes English fluently.
Neither he nor his amiable wife spared any pains in trying to be of service to
us. They gave us all manner of information, and kindly assisted us in procuring
specimens of native manufacture, such as—silver trinkets of beautiful
workmanship; fine knitted gloves soft as Angola wool; fishermen’s mits with
no divisions for the fingers but each made with two thumbs, so that when the
fishing line wears through one side the other can be turned; caps; men and
women’s shoes; quaint snuff boxes made of walrus tusk, or horn; and sundry
other souvenirs which we wished to take south with us.
In Mr. Simson’s store we saw everything from a needle to an anchor; from the
coarsest packsheet to French ribbons. At Mr. Smith’s, whose son had come
north with us on his way from Copenhagen, we invested in seal-skins and
eider-down—the latter for pillows and coverlets. This down, the eider-duck
plucks from its breast to line its nest; it and the eggs are taken away. Again the
nest is lined, and again robbed. The third time, the drake repairs it, supplying
the down; and if this be also taken away the nest is altogether deserted by the
ill-used pair. One nest yields about two and a half ounces of the finest clean
down, or about half a pound in all if removed three times. What is plucked
from the dead bird, it is said, possesses none of that wonderful elasticity which
constitutes the value of the other. We should think, however, that this would
depend on the state of the plumage at the time. Many thousand pounds weight
of it are annually exported for quilts, pillows, cushions, &c. It sells in Iceland at
from 10/6 to 17/6 per ℔. From three to four ℔s. are sufficient for a coverlet,
which, to be enjoyed in perfection, ought to be used unquilted and loose like a
feather bed. Quilting is only useful where a small quantity of down is required
to go a long way; but, with three or four pounds at command, there is no
comparison in point of comfort between loose and quilted—we have tried
both. The eider coverlet combines lightness and warmth in a degree which
cannot be otherwise obtained. With a single sheet and blanket, it is sufficient
for the coldest wintry night. Its elasticity is proverbial; hence the Icelandic
conundrum we had propounded to us by our good friend Mr. Jacobson,
“What is it that is higher when the head is taken off it?” Answer—“An eider-
down pillow!”
In walking along we saw some young ladies, in elegant Parisian costume, out
sunning themselves like butterflies. The thermometer stood at 72°, so, light
coloured fancy parasols were in requisition and enjoyed no sinecure to-day,
even in Iceland. Single days here are sometimes very bright and warm, though
rarely without showers; for the weather is very changeable, and summer short
at best. Less rain falls in the northern part of the island than in the southern;
because the mountains in the south first catch and empty the rain clouds
floating from the south-west over the course of the gulf-stream. For this
reason there is more sunshine in the north, crops too are heavier and earlier;
for, notwithstanding the 3° higher latitude, the summer temperature is nearly
the same as that of the south. In winter, however, it is colder, from the
presence of Spitzbergen icebergs and Greenland ice-floes stranded on the
shore, while the sea to the north and east is filled with them. Last winter was
very severe: the south and west were also filled. My friend Dr. Mackinlay has
treated this subject—the climate of Iceland—so admirably, that I cannot
refrain from quoting his MS. notes:
“The number and size of the rivers” says he, “cannot fail to strike the attention
of every visitor who sees much of the country especially along the coasts. The
main cause of this is, of course, the abundant rain-fall which is out of all
proportion to the latitude of Iceland.
“This excess is owing to two causes—The mountainous nature of the country;
and its geographical position. Iceland lies in the direct course of one of the
branches of the gulf-stream. No land intervenes between it and the Bermudas.
The rain-charged clouds from the south-west are therefore ready to part with
their moisture as soon as they touch the shores of Iceland. As they move
northwards, to the back-bone of the island, their temperature diminishes so
rapidly that the whole of their moisture becomes precipitated. Winds from the
S.W., S., and S.E., drench the southern part of the Island, but bring fair
weather to the north.
“As the southernly winds are the most frequent, the north side enjoys the
greatest number of sunny days in summer; and hence vegetation is more
luxuriant there, even though the latitude is 3° higher, and the southernly winds
are chilled in passing over the great mountain chain. The mean summer
temperature of the north is almost as high as that of the south; but the mean
temperature of the year is 14° lower. In the south this is 47°, but in the north it
is 33°. The climate of the south is insular in its character, while that of the
north is continental. Severe continuous frosts are rare about Reykjavik; while
along the north coast the winters are very severe. The severity of the winters is
mainly caused by the presence of ice in the adjoining seas. The cold Arctic
current from Spitzbergen, which impinges on the north coast, comes freighted
in winter with an occasional iceberg; while the westerly winds and the west
Icelandic branch of the gulf-stream combine to fill the seas to the north and
east of the island with ice floes from Greenland. In ordinary winters, the seas
to the south and east are open; but in extraordinary winters they also are filled.
Such a winter was that of 1858-9. The corresponding winter in Britain was
very mild, and owed its mildness to the same cause which produced the hard
winter of Iceland—the unusual prevalence of westerly winds.
“In the first months of 1859, the sea between Greenland and Iceland—200
miles wide—was packed with ice floes; and upon these several bears made
their way across to Iceland. Floating ice surrounded the island; but along the
north coast the sea itself was frozen so far out that the people of Grimsey,
twenty miles or so from the nearest point of Iceland, actually rode across to
the mainland. At Akur Eyri in the beginning of April, Reaumur’s thermometer
registered 26° of cold—a temperature equal to 26½° of Fahrenheit. So late as
June, seven French fishing boats were lost in the ice on the north coast, and a
French ship of war nearly met with the same fate. Speaking of northern ice,
Captain Launay, of the French man-of-war referred to, told me that its
approach could be foreseen at the distance of twenty-five to thirty miles by a
peculiar reflection of the sky. As the distance diminishes, the sky gets overcast,
the temperature falls rapidly, and fish and sea-fowl disappear. The Greenland
ice is much more dangerous than the Spitzbergen. The latter is 120 to 150 feet
high, massive and wall-sided, but of no great extent. The former is in immense
floes, often forming bays in which ships are caught as in a snare. It seldom
exceeds 40 feet in height; but is jagged and peaked. Sometimes drift-timber
gets nipped between the floes, and is set fire to by the violent friction it
sustains. The sound of the crushing ice was described by Captain Launay as
most horrible.”
Thus much of the climate.
Dr. Mackinlay took Mr. Haycock and me to call for the Governor, the Count
Von Trampe, who is a Dane, and well known for his urbanity to strangers. He
kindly introduced us to his family. The house itself resembles, and at once
suggests pictures we have seen of missionaries’ houses in Madagascar. Within
doors, however, all is tasteful and elegant. One peculiarity is worth noting, viz.:
that the walls of his suite of apartments are covered with French portraits,
paintings, engravings, and lithographs, nearly all presentations. In the public
room, I only observed one that was not French. Judging from the walls, we
might have been in the residence of a French Consul. French frigates are put
on this station, year after year, ostensibly to look after the fisheries. Great
court is paid to the leading islanders, and France would fain be in the
ascendant here as elsewhere. Iceland, meanwhile, costs Denmark an outlay of
several thousands a year; because, say some of the Icelanders, more is not
invested in improvements of various kinds in order to make it pay. This state
of matters would render negotiations easy on the part of Denmark, were the
acquisition of the island an object to France. It would be an easy method of
paying for assistance rendered in any Holstein difficulty or other cunningly laid
European mine that may yet explode; when the cause of justice and right, as it
ever is, being declared all on the side of France, she will disinterestedly go
forward with her eagles for freedom and glory.
Such contingencies may arise, although the Danes are our natural allies and
our Scandinavian brethren. It may be asked, what would the French do with
the island? It would be chiefly useful to them for forming and training hardy
seamen for the navy, as they already do to some extent both here and on the
Newfoundland coast where the fisheries are maintained and subsidized for
that very purpose. It would furnish a station in the North Sea, from which to
descend and menace our North American traffic; and it contains extensive
sulphur mines, which, in the event of Sicily being shut against us, are available
for munitions of war in our gunpowder manufactories; in another point of
view, it is invaluable, as the great salmon-preserve of Europe.
Intelligent Icelanders who cherish the memory of their ancient freedom, to my
certain knowledge, regard all such French tendencies and contingencies with
decided aversion. But in the event of a transfer being mooted, would the
Icelanders be consulted in the matter? I fear not, and that it would only be
announced to them in the French fashion, as fait accompli: may such however,
never be the fate of this interesting island!
These remarks, although suggested here by the pictures in the Governor’s
drawing-room, have no reference, it is right to state, to the Count Von
Trampe’s views on this subject, which I do not happen to know; nor on the
other hand, to the officers’ of the vessels stationed here, who all seem to be
gentlemanly kind-hearted fellows. A variety of facts and observations,
however, all tended to confirm me in this impression; besides, it is the policy
which the French are pursuing elsewhere.
From the Governor’s, we proceed to call for Mr. Randröp, the states
apothecary, and receive a most hospitable, true, northern welcome. We meet
several French officers and see the usual quantum of French prints on the
walls. But he is the French consul or agent. Coffee, cakes, and wine, are
handed round to us by the ladies, this being the custom of the country, and in
drinking to us, the form is always, “Welcome to Iceland.” Mr. Randröp speaks
a little English, and the two young ladies, his step-daughters, are acquiring it.
Here, as in Germany, the class book in common use is “The Vicar of
Wakefield.” Madame Randröp, who speaks French and German and plays on
the piano-forte, shewed us several beautiful silver trinkets, bracelets, pins, &c.,
of Icelandic manufacture; the style an open mediaeval looking fretwork, that
might satisfy the most fastidious artistic taste.
The Governor’s house and Mr. Randröp’s are the two centres of Reykjavik
society, and at one or other of them, of an evening, any stranger visiting these
parts is almost certain to be found. One is expected to make quite a round of
visits if he be authenticated, or have any sort of introduction to any one of the
circle; an omission would even be regarded as a slight. Hence Dr. Mackinlay
took us to call for a considerable number of people, all of whom were cordial
and glad to see us.
Our next visit was to the Rev. Olaf Pálsson, Dean and Rector of the Cathedral.
Learned, intelligent, communicative and obliging, he at once, in the kindest
manner possible, placed himself at our service and offered us every assistance
in his power. In his library I observed many standard works of reference in
various languages, and opened several volumes that seemed to recognize me as
a friend whom they had met before: “Lord Dufferin’s Letters from High
Latitudes”—a presentation copy—“Caird’s Sermons;” “Life of the Rev.
Ebenezer Henderson”—the Icelandic traveller; “Stanley’s Sinai and Palestine,”
&c. The worthy pastor both speaks and writes English fluently, and has
translated a number of Icelandic stories and fairy tales.[4]
The Pastor’s honest ruddy face, light flaxen hair, and unassuming manner; his
rosy cheeked children, the monthly roses in the window-sill, and the library—
all go to form a pleasing picture in the Walhalla of memory. He afterwards
accompanied us to call for Rector Jonson. The Rector is a good specimen of
the genus homo; tall and burly, while his active mind is vigorous, inquisitive,
and accomplished. He showed us over various rooms, where the different
branches are taught, some of them containing cabinets of geological and
zoological specimens. The school is supported by government; and about sixty
select young men intended for the church and other learned professions here
receive a free education; a few of them only go to Copenhagen yet further to
complete their studies.
Although the island contains 64,603 inhabitants, this, as we have said, is the
only Academy or College; and there is not a single juvenile school.
The population is so widely scattered that schools would be quite
impracticable; for the six thousand farms which the island contains, on the
habitable coast belt which surrounds the central deserts, are often separated
from each other by many dreary miles of lava wastes and rapid rivers
dangerous to ford.
Parents, however, all teach their children to read and write by the fireside on
the long winter evenings, as they themselves were taught; and the people are
thus home educated from generation to generation, and trained to habits of
intellectual activity from their youth. Thus, as a mass, the Icelanders are
without doubt the best educated people in the world.
For six centuries the Icelanders have evidenced their love of literature by
writing and preserving old Sagas and Eddas;—by producing original works on
mythology, law, topography, archaeology, &c.—several of these at once the
earliest and best of their kind in Europe; and by executing many admirable
translations from the classics.
Such literary labours have often been carried on by priests in remote districts,
who subsist on a miserable pittance, and dwell in what we would consider
mere hovels,—men who are obliged to work, at outdoor manual labour, the
same as any of their neighbour peasants and parishoners, in order to keep the
wolf from the door. Henderson found Thorláksson, the translator of “Paradise
Lost,” busy making hay. His living only yielded him £7 per annum, and the one
room in which he slept and wrote was only eight feet long by six broad. This
translation was not printed till after his death. Verily good work lovingly done
is its own reward. These men had little else to cheer them on.
We next visited the Cathedral, which stands in the back part of the town, with
an open square space in front of it, and a little fresh water lake—inland—to
the left. It is a modern edifice, built of brick, plastered. At the entrance we
were joined by our friend Professor Chadbourne. The interior is very neatly
fitted up with pews, has galleries, organ, &c.; and can accommodate three or
four hundred people.
An oil painting above the communion table represents the resurrection; but
the only object of artistic interest is a white marble baptismal font, carved and
presented to the Cathedral by Thorwaldsen, whose father was an Icelander. It
is a low square obelisk. The basin on the top is surrounded with a symbolical
wreath of passion-flowers and roses, delicately carved in high relief out of the
white marble. On the front is represented, also in relief, the baptism of our
Saviour by St. John; on the left side, the Madonna and Child, with John the
Baptist as an infant standing at her knee; on the right, Christ blessing little
children; while at the back, next the altar, are three cherubs, and underneath
them is inscribed the following legend: “Opus haec Romae fecit, et Islandiae,
terrae sibi gentiliacae, pietatis causâ, donavit Albertus Thorvaldsen, anno
MDCCCXXVII.” It is a chaste and beautiful work of art.

In the vestry the Rev. Olaf Pálsson opened several large chests, and shewed us
numerous vestments belonging to the bishop and priests; one of these with
gorgeous embroideries had been sent here to the bishop by Pope Julius II. in
the beginning of the sixteenth century. The cloth was purple velvet,
embroidered and stiff with brocade of gold.
Above the church, immediately under the sloping roof, an apartment runs the
whole length of the building. In it is deposited the free public library of
Reykjavik, which consists of more than 6000 volumes in Icelandic, Danish,
Latin, French, English, German, and various other languages. A copy of every
book published at Copenhagen is sent here by government, and from time to