Ultrasound-assisted fabrication of

Ti3C2Tx MXene toward enhanced

energy storage performance Xinyue
Zhang
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 Ultrasonics Sonochemistry 86 (2022) 106024

Contents lists available at ScienceDirect

Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Ultrasound-assisted fabrication of Ti3C2Tx MXene toward enhanced energy

storage performance
Xinyue Zhang, Wu Zhang *, Haitao Zhao
School of Materials Science and Engineering, Shenyang Ligong University, Shenyang, Liaoning 110159, PR China

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

Keywords: Ti3C2Tx MXenes are normally fabricated by removal of main group element from the corresponding transition
Ti3C2Tx MXene metal carbides, and they have been actively studied due to their superior energy storage performance. However,
Ultrasound the low efficiency in removal of main group element (named as chemical etching) has significantly limited the
Energy Storage performance
application of MXene or MXene-related materials. Herein, we demonstrated an ultrasound-assisted approach to
synthesize Ti3C2Tx MXene material by using Ti3AlC2 as the precursor. The experimental results indicate that the
efficiency of chemical etching of Ti3AlC2 was dramatically promoted by ultrasound. The etching time was greatly
shortened to 8 h while typically 24 h is sufficient in dilute hydrofluoric acid. Particularly, the high etching ef­
ficiency was achieved by using 2% hydrofluoric acid under the aid of ultrasound, which is lower in concentration
than those reported in the previous literature. The specific capacitance of the 8 h sonicated sample is 155F/g,
which is much higher than that of the un-sonicated sample prepared under the same experimental conditions.
Additionally, the specific capacitance retention of the prepared 8 h sonicated sample was 97.5% after 20,000
cycles of charging/discharging, exhibiting an outstanding energy storage stability compared with the materials
reported in previous literatures. It was proposed that removal of AlF3 from the surface of the etched particles was
significantly promoted and the hydrogen bonds between the terminations of two different adjacent layers were
broken by the acoustic cavitation effect of ultrasound.

1. Introduction
MXenes are normally fabricated by removal of main group element
from the corresponding transition metal carbides. MXene and MXene-
based materials find their application in a variety of fields, including
energy storage, catalysis, sensors, nanogenerator, desalination, and
microwave shielding [1,2]. For example, self-assembled MXene nano­
structures possess superior catalytic performances for water treatment
and hydrogen production [3,4,5]. MXene or MXene-based materials are
commonly prepared from their corresponding MAX precursors, which
exhibit 3D crystal structure but consist of the bonding and stacking of 2D
layered structures. In the structure of MAX, the “M” represents early
transition metals. e.g., V, Ti and Mo. “A” consists of main group ele­
ments, typically those elements from groups 13 and 14, such as Al, Si,
Zn, and Ga. Regarding the “X” element in the MAX structure, a prime
example is C [6]. As an alternative, N is also considered as a suitable
candidate for “X” component. A characteristic of MAX materials is the
octahedral layered structure, which planarly extends by an edge-sharing
configuration and thereby forms an “M− X” layer structure. The “A”
atoms are located intermediately between two different “M− X” layers
[6]. Consequently, rearrangement of the MAX to prepare its corre­
sponding MXene structures could be achieved by selective removal of
“A” atoms while keeping the MX layers in the original structure, which is
known as etching of MAX precursors. The resultants of etching of MAX
materials normally exhibit accordion-like structures. A more appealing
characteristic of the as-prepared MXenes is that the stacked accordion-
like MXenes could be delaminated into monolayered or few-layer
nanosheets, which shows superior properties, such as high specific
surface area, good hydrophilicity, and rich surface chemistry, compared
with their original accordion-like counterparts.
To date, various methods and etchants have been developed. Among
the abundant etching etchants, hydrofluoric acid (HF) is the first and
mostly reported etchant to obtain MXenes from their corresponding
MAX precursors. Naguib et al. [7] employed 50% HF as the etchant to
remove Al components in the MAX phase, and accordion-like Ti3C2Tx
MXene powder with van der Waals force and hydrogen bonds between
each layer was obtained, the resulting Ti3C2Tx MXene powder was
consistent with the corresponding Ti3AlC2 MAX phase in stoichiometry

* Corresponding author.
E-mail address: neusmmzhangwu@163.com (W. Zhang).

https://doi.org/10.1016/j.ultsonch.2022.106024
Received 5 February 2022; Received in revised form 29 April 2022; Accepted 30 April 2022
Available online 5 May 2022
1350-4177/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
X. Zhang et al.
and crystal structure, excepting that the Al atomic layer was removed.
Although the feasibility of high concentration hydrofluoric acid for MAX
phase etching has been experimentally proved, the harsh etching re­
actions and the dissolved oxygen gas in aqueous etchants induce extra
structural defects to the resulting MXenes and promote their degrada­
tion into TiO2. Fluorine-containing salts, such as KHF2, NaHF2, and
NH4HF2, have been developed to perform the etching of MAXs, the
etching time is usually more than 24 h, which leads to a low efficiency
for preparation of MXene [8]. Recently, electrochemical etching ap­
proaches emerged to get desired materials with high efficiency [9,10]. A
prime example is that CuCl2 molten salt has been employed to etch MAX
powders [9]. Apparently, a high temperature (approximately 750 ◦ C is
needed in the etching process, which sets an obstacle to the practical
production and application of the molten salt method. Aqueous solu­
tions have also been considered as suitable baths for electrochemical
etching of MAX precursors, it was found that a significant anodic effect
and the resulting emission of toxic gas make it an undesirable route for
etching of the MAX phase.
Ultrasound has been widely employed in extraction [11], food pro­
cessing [12], emulsification [13], and other fields. Additionally, it is
currently gaining popularity as a promising technique for material
synthesis due to its green, innovative, and cost-effective characteristics.
Various materials such as nanostructured materials [14], conducting
polymers [15], and photocatalysts [16], have been successfully pre­
pared by ultrasound-assisted approaches. Introduction of ultrasound can
provide extra energy to the as-used solution, allowing better mass
transfer than those for the un-sonicated solutions in mixing, drying, and
extraction processes. In this regard, ultrasound is a suitable candidate
for improving the efficiency of etching Ti3AlC2 during preparation of
MXenes.
As mentioned above, MXenes have attracted great attention as next-
generation capacitive energy-storage materials. In this regard, although
MXenes show promising application prospects in energy storage, the
practical electrochemical performance of few- and mono-layered
MXenes falls short of expectations, and no commercialized MXenes are
available to date. This results from the blocking effect of surface anion
and excessive accumulation of layers. As an alternative, accordion-like
MXenes, which are physically more stable and possess higher cycling
stability than the few- and mono-layered ones, are attracting more and
more attention as promising energy storage materials.
Inspired by the advantage of MXenes in the field of energy storage,
Ti3C2Tx was synthesized by using Ti3AlC2 in the present work. As
described previously, the most challenging issues for preparation of
MXenes can be summarized as: (1) low etching efficiency while chemical
reagents were used except for high concentration hydrofluoric acid; (2)
When concentrated hydrofluoric acid is used as the etchant, the harsh
reactions induce extra structural defects; (3) The high temperature or
significant anodic effects limits the application of electrochemical ap­
proaches for etching of MAX phase. To address the above challenges,
dilute hydrofluoric acid (2 wt%) was used as the etchant to ease the
experimental conditions and prevent the formation of TiO2, of particular
to this work is the introduction of ultrasound, which is a highly energy-
efficient method for material synthesis, thereby achieving efficient
etching of Ti3AlC2 precursor.
2. Experimentation
2.1. Materials and instrumentation
In the present work, All the chemical reagents were purchased from
Shanghai Macklin Biochemical Co., Ltd and were used without further
purification. Powdery Ti3AlC2 (purity: 98 %, average particle size: 74
μm) and hydrofluoric acid were used as a precursor and the etchant,
respectively. 1 M H2SO4 solution serves as the electrolyte to test the
electrochemical properties of the synthesized materials. Deionized
water (DI water) was used throughout the experiments for any washing
2
Ultrasonics Sonochemistry 86 (2022) 106024
purpose or preparation of desired solutions. Acetylene black, poly­
vinylidene fluoride (PVDF), as well as N-methylpyrrolidone (NMP),
were used to prepare the electrode. Carbon paper (purchased from Toray
Industries, Inc. Japan.) was used as the collector to prepare the working
electrode.
X-ray diffractometer (XRD, MPDDY2094, Netherlands) with Cu Ka
radiation (λ = 0.15406 nm) was operated at a scan range of 5◦ ~90◦ to
study phase composition of the as-prepared samples. Scanning electron
microscope (SEM, Tescan Vega II, Czech Republic), equipped with En­
ergy Dispersive Spectrometer (iXRF Systems, 550i) was used to study the
morphology of the samples. XPS experiments were carried out using an
ESCALAB 250Xi (Thermo Fischer) X-ray photoelectron spectrometer
with a basic chamber pressure of 4 × l0-9 mbar. Al anode was used as the
X-ray source (x-ray radiation of 1486.6 eV) in the XPS characterization
with a working voltage at 14.6 kV. An ICP-OES (Thermo Scientific, icap
pro) was used to perform analyzing of the Al content in the samples.
All the electrochemical tests, including cyclic voltammetry (CV),
galvanostatic charge/discharge (GCD) measurements, and electro­
chemical impedance spectroscopy (EIS), were performed using a CHI
760E (purchased from Shanghai CH Instrument Co., Ltd) electro­
chemical workstation. A sonicator (Model: KQ 2200DE, purchased from
Kunshan Ultrasonic Instruments, Co. Ltd.) was employed to generate
ultrasound during the etching experiments. A 50 ml Teflon autoclave
with a 2 mm diameter open pore on the gap to emit the generated gas
served as the container to perform etching experiments. A centrifuge
(Model: TG16-WS, Shanghai Luxiang Centrifuge Instrument Co., Ltd)
was used for centrifugal experiments.
2.2. Experimental procedure
2.2.1. Preparation of the Ti3C2Tx MXene powders
According to the information from previous literatures, all the
etching experiments were performed at 50℃ throughout the work.
Briefly, 2 g Ti3AlC2 was added at a rate of 0.2 g/min into 2 wt% hy­
drofluoric acid solution in 10 mins to avoid intense boiling. The solution
was heated in a water bath in the sonicator. The sonication assisted wet-
chemical etching of the Ti3AlC2 powders as the temperature was
increased to 50℃. The acquired slurry was repeatedly centrifuged for 15
cycles at 5000 rpm/min for 3mins for each cycle of operation until the
pH of the supernatant was close to 6.5. Subsequently, the mixture was
filtered by using a vacuum suction pump. The filter cake was dried in the
vacuum oven at 50℃ for 12 h. The hydrofluoric acid etching treatment
can be represented by: [17].
Ti3AlC2 + 3HF = Ti3C2 + AlF3 + 3/2H2 (1)
Ti3C2 + 2H2O = Ti3C2(OH)2 + H2 (2)
Ti3C2 + 2HF = Ti3C2F2 + H2 (3)
2.2.2. Fabrication of the electrode
Regarding fabrication of the electrode, the as-prepared Ti3C2Tx
MXene powders were mixed with acetylene black and polyvinylidene
fluoride (PVDF) at a mass ratio of 8:1:1, among which the acetylene
black and PVDF serve as the conductor and binder, respectively. Typi­
cally, 10 mg acetylene black and 10 mg PVDF were consecutively added
into 80 mg MXene powder, the mixture was then mixed with 0.5 ml NMP
in a 20 ml Teflon container and then was magnetically stirred for 3 h at
room temperature to achieve sufficient mixing of the slurry. Subse­
quently, the acquired slurry was then uniformly coated on a 1 × 2 cm
carbon paper with an active area of 1 × 1 cm. The newly prepared
electrode was dried in a vacuum oven for 12 h to perform electro­
chemical tests.
X. Zhang et al.
2.2.3. Electrochemical tests
Prior to the electrochemical tests, the prepared electrodes were
soaked in the electrolyte for 12 h to make the electrolyte fully adsorbed
on the active materials. Cyclic voltammetric (CV) experiments were
performed at a scan range of 10 ~ 100 mV/s with an interval of 20 mV/s.
Galvanostatic charge–discharge (GCD) tests were performed within the
selected potential range of CV from 1A/g to 5A/g. Electrochemical
impedance spectroscopy (EIS) measurements were conducted from 100
kHz to 0.01 Hz with an amplitude of 5 mV starting from open circuit
potential (OCP). Galvanostatic cycling experiments were performed at a
current density of 1 A/g. The specific capacitance can be calculated by
using the acquired CV and GCD curves, the corresponding equations are
shown as follows [18]:
∫ using 50 wt% hydrofluoric acid at 50 ◦ C for 2 h, which is not in agree­
IdU
C= (1)
mvΔU
IΔt
C= (2)
mΔU
where C (F/g) represents specific capacitance, F/g; m stands for the mass
of active material in the working electrode, (g); v is the scan rate of CV in
unit mV/s; ΔU (V) is the potential window in the CV or GCD curve in
unit V; I is the generated current, A; Δt is the discharge time, s.
3. Results and discussion
3.1. Material characterization
3.1.1. XRD patterns of the samples
Fig. 1(a) depicts the XRD patterns of the pristine Ti3Al2C2 powder
and the etched samples in absence and in presence of sonication. It is
vividly shown that the etched samples hold the same crystal structure as
the corresponding Ti3Al2C2. Naguib and coworkers [19] etched the
Ti3Al2C2 by using 50% hydrofluoric acid, it was reported that the stoi­
chiometry and crystal structure of the resultant Ti3C2Tx powder was
consistent with the pristine Ti3AlC2 MAX phase except for the Al atomic
layer, which is in good agreement with the results in the present work.
As shown in Fig. 1(a), the characteristic (0 0 2) peaks of as-prepared
MXene shifted from 9.6◦ in the Ti3AlC2 powder to a lower 2θ angle of
9.5◦ after 8 h of etching treatment in absence of ultrasound, and it
further shifts to 9.4◦ when the ultrasound is present. According to the
Bragg’s law [20], this is an indication of an increase in interlayer spacing
due to the removal of Al and introduction of surface terminations
(represented as Tx) in Ti3C2Tx (e.g., -F, -O, –OH) in the wet-chemical
etching of Ti3AlC2. Additionally, the intensity of decrease with
Fig. 1. (a): XRD patterns of the pristine Ti3AlC2 and the etched samples in presence of and in absence of ultrasound; (b): variation of XRD patterns with sonication
time (from 1 h to 8 h).
3
Ultrasonics Sonochemistry 86 (2022) 106024
proceeding of etching, and the peaks of the samples with sonication was
further decreased compared with that of the non-sonicated sample,
which demonstrates that the etching process was promoted by sonicat­
ion. Fig. 1 (b) shows the XRD patterns of the samples with different
timescale of sonication (from 1 h to 8 h). The peaks of (0 0 2) shifted to
the lower angle as the time increased from 1 h to 8 h and, the width of
(0 0 2) peak become larger with the increasing of sonication time, this
indicates a gradually enlarged interlayer spacing of (0 0 2) plane.
Notably, the peak at ca. 20◦ in Fig. 1(a) and (b), corresponding to (0 0 4)
plane of the Ti3AlC2 structure, lose intensity in the 8 h-sonicated sample,
which is ascribed to the successful removal of Al for the pristine Ti3AlC2.
It was reported that the characteristic peaks at around 39◦ completely
disappeared when the mono-or few-layered MXene was synthesized by
ment with the results in the present work[21]. Additionally, it is note­
worthy that all the etched (sonicated and un-sonicated) samples show
pronounced diffraction peaks throughout the whole scan range of XRD
in Fig. 1, which is a distinct difference from those of few- or mono-
layered MXenes [21]. The above findings suggest that the no appre­
ciable few- or mono-layered MXenes are generated throughout the
etching treatment in the present work, and this will be further discussed
in the present work.
3.1.2. SEM observation
SEM images of the samples in absence of and in presence of ultra­
sound are shown in Fig. 2(a) to (f). It is observed that the etching trails
emerged in the first hour of etching in presence of ultrasound. With the
increasing of etching time, more pronounced etching trails are observed.
Typical accordion-like morphology is shown in Fig. 2(c) and (f), the
sample with 8 h of sonication. Fig. 2(a) and (d) show the morphology of
the etched sample for a treatment of 8 h in absence of ultrasound.
Compared with the samples shown in Fig. 2(c) and (f), no well-defined
etching trails are observed in the un-sonicated sample shown in Fig. 2 (a)
and (d), indicating that the etching process is effectively promoted by
the ultrasound. Additionally, the surface of the samples in absence of
ultrasound is covered by nodular structures, likely the AlF3 by-product
according to Eqn. (1) in the present work, which prohibits an efficient
etching of the Ti3AlC2. The 8 h sonicated sample was tested by elemental
mapping; the results are shown in Fig. 2(g) to (j). Compared with the
other three elements, only a small amount of Al components is detected
in the 8 h sonicated sample. In addition, the distribution of F signifi­
cantly differs from that of the Al element, indicating that AlF3 is not
present on the surface of the 8 h sonicated sample.
The variation of Al content based on the ICP-OES determination re­
sults are shown in Fig. 3, i.e., the removal rate of Al for the cases in
X. Zhang et al. Ultrasonics Sonochemistry 86 (2022) 106024

Fig. 2. SEM images of the samples in absence of and in presence of ultrasound (a and d: un-sonicated sample for 8 h etching; b and e: sonicated sample for 1 h
etching; c and f: sonicated sample for 8 h etching; g to j: elemental mapping of Ti(g), C(h), F(i) and Al(j) in the 8 h etched sample in presence of ultrasound.

aluminum extraction from Ti3AlC2 in 50% hydrofluoric acid, it was

found that at least 15 h were needed to complete removal of Al from
Ti3AlC2. In-situ HF forming systems for Ti3AlC2, such as high concen­
tration of LiF/HCl and NH4HF2, which inherently use HF as the active
reagent for etching of Ti3AlC2, even showed lower efficiency in removal
of Al than fluohydric acid. The etching efficiency has been significantly
improved in the present work. Additionally, the lowest concentration of
fluohydric acid to prepare Ti3C2Tx MXene is 5% to date, the concen­
tration of fluohydric acid is further decreased to 2% in this study, while
better performance of the products is achieved, thanks to the applied
ultrasound.

3.1.3. XPS characterization

X-ray Photoelectron Spectroscopy (XPS) spectra of the prepared
samples are shown in Fig. 4. Fig. 4(a) depicts the full spectra of sonicated
samples with the sonication time of 1 h, 2 h, 4 h, and 8 h. In Fig. 4(a), the
peak at 284.8 ev is the characteristic peak of C1s, and the four peaks at
33.04, 57.9, 453.9, and 560.1 ev correspond to Ti 3p, Ti 3 s, Ti 2p, and Ti
2 s. In addition to the Ti and C-related peaks, the characteristic peaks of
F1s and O1s at 688.3 and 529.5 ev, which are absent from the pristine
Fig. 3. Variation of Al content in the etched samples.
Ti3AlC2, are detected. Additionally, similar trails of the four XPS curves
is observed. This suggests that the Ti3AlC2 precursor is continuously
presence of and in absence of ultrasound. It is clearly shown that the
etched throughout the 8 h and oxidation of Ti and C in the precursor is
removal rate of Al is much faster than that of the un-sonicated case.
present. To further confirm this information, high-resolution XPS
In particular, only ca.3% Al is left in the Ti3AlC2 structure for the first
spectra were conducted by using the 1 h and 8 h sonicated samples. The
two hours of etching in presence of ultrasound, while the corresponding
high-resolution C 1 s spectrum of 1 h exhibit the peaks at 284.8, 285.75,
value for the case of without ultrasound is 10.05%, indicating a much
287.72, and 288.54 eV, which belong to C–C, C-O, C = O, CF3-C = O
faster removal rate of Al for the ultrasound aided case than those of
chemical bonds, respectively [24], and this demonstrates that the C
without ultrasound. Notably, the Al contents in the etched sample are
element in the sample is continuously oxidized and fluoridized. Inter­
close to a constant value (1.71% and 5.72% for the sonicated and un-
estingly, the CF3-C = O chemical bond transferred to C6F6 chemical bond
sonicated cases, respectively) after the etching treatment. Alhabeb and
[25], which corresponds to the peak at 289.42 eV in Fig. 4(c), and this is
coworkers have done some profound work on preparation of Ti3C2Tx
a strong indication for further fluoridized of the etched samples.
MXenes [22]. They employed 5 wt% and 10 wt% fluohydric acid as the
The behavior of fluoride is barely discussed in the previous litera­
etchant to prepare accordion-like Ti3C2Tx MXenes, which were further
tures. Here the high-resolution F 1 s spectrum is conducted by using 1 h
delaminated into monolayered ones, the required etching time is 24 h
and 8 h sonicated samples. In the high-resolution F 1 s spectrum of 1 h
and 18 h, respectively [22]. Mashtalir et al. [23] studied the kinetics of
sonicated sample (Fig. 4(d)), the peak corresponding to (–CH2-CF2-) n at

4
X. Zhang et al.
Fig. 4. (a) XPS survey of the samples with the sonication time of 1 h, 2 h, 4 h, and 8 h; (b) to (g): high-resolution spectrum of C 1 s(b) and (c), F 1 s(d) and (e), Ti (g)
and (h) for the 1 h and 8 h sonicated samples.
689.68 ev is observed, indicating that the Al atoms are partially
substituted by hydrogen and fluoride atoms. Another peak at 688.07 ev
is observed, which is a characteristic of (-CF2-CF2-) n chemical bonds. i.
e., the hydrogen atoms are removed and replaced by fluorine atoms in
the precursor. With the proceeding of the etching, a new peak at 690.8
ev is detected, which is a diagnostic criterion of C6F6 group, indicating
that the Ti atoms locating at the edge of the MAX phase are substituted
by fluoride, which is not reported in the previous literature. The high-
resolution Ti spectrum of 1 h and 8 h sonicated samples are presented
in Fig. 4(f) and (g), six peaks with respectively similar binding energy
are observed in both graphs, suggesting that the chemical and electronic
environment of Ti atom are not altered with the timescale of etching.
The peaks in Fig. 4(f) and (g) at 457.64, 458.55, 459.95, 461.54.1,
463.77 and 465.07 eV correspond to Ti-C 2p3/2, Ti2+/Ti3+ 2p3/2, Ti-O
2p3/2, Ti-C 2p1/2, Ti2+/Ti3+ 2p1/2 and Ti-O 2p1/2, respectively. The
high-resolution Ti spectrum in Fig. 4(f) and (g) proves the oxidation of Ti
atoms into TiO2 in the precursor, which has been found in the previous
literature. [26].
3.2. Electrochemical performance of the samples
Prior to testing the electrochemical performance of the samples,
stability of the samples is an issue to be considered. To determine the
stability of the samples, duplicate experiments were performed, no
appreciable decomposition of the sample was found, i.e., the prepared
samples are thermally and electrochemically stable under the tested
conditions. To evaluate the electrochemical performance of the Ti3C2Tx
MXene, cyclic voltammetric (CV) experiments were performed in a
three-electrode configuration. The performed potential range of CV was
5
Ultrasonics Sonochemistry 86 (2022) 106024
selected within the decomposing potential of the electrolyte. Fig. 5 de­
picts the CVs of different samples at different scan rates from 10 mV/s to
100 mV/s.
It is vividly shown that the electrochemical properties of sonicated
samples improved significantly with increasing of the timescale of
sonication. Regarding the CV of the sample in absence of ultrasound, no
well-defined trails for typical behaviors of the energy storage materials
were observed, and the specific capacitance of the 8 h un-sonicated
sample (Fig. 5(a)) at 10 mV/s was calculated to be only 3.4F/g, while
the corresponding specific capacitance for the sonicated sample (Fig. 5
(d)) with the same timescale of treatment is 155F/g, which is a signifi­
cant improvement in specific capacitance compared with the un-
sonicated sample. Wu et al. [20] synthesized organ-like Ti3C2Tx
MXene by using hydrofluoric acid for 24 h, they reported a specific
capacitance of ca. 100F/g at the same scan rate (10 mV/s). Additionally,
the specific capacitances of the sonicated samples are 4.3, 6.9, 100, and
155F/g with the sonication time of 1 h, 2 h, 4 h, and 8 h, which
experimentally proves that prolonging of sonication time favors the
electrochemical performance of the acquired MXenes. This is in good
agreement with our SEM observation in the present work.
The capacitive behavior of the as-prepared 8 h etched samples with
and without ultrasound was studied through galvanostatic char­
ge–discharge (GCD) measurements in the range from 1A/g to 5 A/g
(Fig. 6(a) and (b)). It is observed that the GCD curves of the sonicated
sample show better symmetrical triangles than those of the un-sonicated
sample. As expected by the results in CV tests, the sonicated sample with
8 h of treatment exhibits better capacitive behavior than the un-
sonicated MXene, better reversibility of the electrochemical perfor­
mance. The specific capacitances of the 8 h sonicated sample are 180,
X. Zhang et al.
Fig. 5. Cyclic voltammograms (CV) of the prepared samples with scan rate from 10 to 100 mV/s; (a) 8 h-unsonicated; (b) 2 h-sonicated; (c): 4 h-sonicated; (d) 8
h-sonicated.
124.8, 111.8, 103.3, and 91F/g as the current density increase from 1 to
5 A/g. The GCD curve of the 8 h sonicated sample retains a superior rate
capability of ca 50% at 5 A/g, indicating an outstanding quick char­
ge–discharge performance of the electrode prepared by the 8 h sonicated
sample. Electrochemical impedance spectroscopy (EIS) was further
performed to study the charge transfer resistance (Rct) and ion transport
in the tested electrode [27,28], Nyquist plots of all samples showed
negligible semicircles and a relatively low Rct, suggesting that removal
of Al did not significantly affect the electronic conductivity of Ti3C2Tx.
In the low-frequency range, interpretation of Nyquist plots for all the
four tested electrodes suggests a good ionic conductivity of the elec­
trodes, i.e., at low frequencies, the slope of the plot for 8 h-unsonicated
sample shows lower diffusion resistance compared to the sonicated
samples. This is ascribed to the lower concentration of surface terminal
groups caused by the AlF3 byproduct, which is discussed in the SEM
observation in the present work. The real axis intercept at high fre­
quency corresponds to the uncompensated resistance of the bulk elec­
trolyte solution (Rs), as observed in Fig. 6(d), here the Rs values for the
sonicated samples are found to be smaller than that of the un-sonicated
sample. Variation of specific capacitance with the scan rate of CV was
listed in Table 1, it is shown that the specific capacitance decreases with
the increase of scan rate for all the four samples, this could be assigned to
the contribution of diffusion of ions in the electrolyte. At large scan
rates, for example, 100 mV/s, the ions do not have enough time to
diffuse into the surface of the active material, thereby decreasing the
specific capacitance of the as-prepared MXenes.
Apart from specific capacitance, cycling stability is attractive merit
of electrochemical capacitors, it is a key factor to determine the poten­
tial of the electrode material for practical applications. Herein, GCD
experiments were performed for 20,000 cycles at 5 A/g to determine the
cycling stability of the MXene, the results are shown in Fig. 7, inset of
Fig. 7 shows the profile of the first and the last cycles of GCD curves. The
6
Ultrasonics Sonochemistry 86 (2022) 106024
capacitance retention of the electrode is 97.5% after 20,000 cycles of
test, which is overwhelming stability compared with the previously re­
ported MXene or MXene-based materials. Fig. 8 shows the comparison of
the capacity retention of the as-prepared 8 h-sonicated sample with
previously reported MXene or MXene-based materials
[20,29,30,31,32,33,34].
3.3. Proposed consequence of ultrasound on synthesis of Ti3C2Tx MXene
To visualize the effect of ultrasound on synthesis of accordion-like
Ti3C2Tx MXene and compare the etching mechanism in absence of
and in presence of ultrasound, a schematic was drawn and shown in
Fig. 9. In the initial stage of etching, the Al atoms at the edge of Ti3AlC2
were removed by HF, and thereby the Ti3AlC2 surface was covered by
the resulting AlF3 and the Al atoms were replaced by surface termina­
tions, such as -F, –OH, and -O, which is likely to form hydrogen bonds
between two adjacent layers and impede removal of Al from the pristine
Ti3AlC2. The as-formed AlF3 and hydrogen bond could significantly
prohibit further extraction of Al from Ti3AlC2 precursor and lead to low
efficiency of chemical etching. In the case in presence of ultrasound, the
above-mentioned AlF3 byproducts are effectively removed from the
surface of the etched Ti3AlC2, and more opportunities are created for the
HF etchant to attack the inside Al atoms due to the acoustic cavitation
effect of ultrasound. Additionally, the acoustic cavitation effect created
by ultrasound can prevent/break the above-mentioned possible
hydrogen bond between two adjacent layers and thereby dramatically
promote the etching efficiency. Consequently, it is also reasonable to
conclude that ultrasound can be also employed in other electrochemical
processes, e.g., electrochemical reduction of CO2. It was found that CO
plays a unique and vital role during the electrochemical reduction of
CO2 [35], and according to our analysis, the introduction of ultrasound
can boost the selectivity of CO in CO2 electrochemical reduction, which
X. Zhang et al. Ultrasonics Sonochemistry 86 (2022) 106024

Fig. 6. GCD curves of the prepared samples with current density from 1 to 5 A/g; (a) 8 h-unsonicated; (b) 8 h-sonicated; (c) Nyquist plots of 8 h-unsonicated, 2 h-
sonicated, 4 h-sonicated, and 8 h-sonicated electrodes, (d): the magnified section in the low frequency of Fig. 6(c).

is analogous to the effect of ultrasound in the present work.

Table 1
Variation of specific capacitance with different sonication time at different scan
4. Conclusion
rates.
San rate (mV/ Specific Capacitance of the sample(F/g)
In the present work, we demonstrated a highly efficient approach for
s)
8 h- 2 h- 4 h- 8 h- the chemical etching of Ti3AlC2 to prepare Ti3C2Tx MXene with superior
unsonicated sonicated sonicated sonicated energy storage performance. The as-prepared Ti3C2Tx MXene for 8 h
10 3.4 6.9 100.2 155.0
sonication showed a well-defined accordion-like structure, especially for
20 3.2 6.5 85.2 138.3 the 8 h sonicated sample. XRD patterns show that the (0 0 2) planes of
40 2.9 6.2 73.9 121.7 the etched samples shifted to a lower angle due to the broadening of the
60 2.8 5.9 66.1 110.5 space between different layers. Furthermore, a more pronounced shift of
80 2.8 5.5 59.4 102.4
(0 0 2) plane was observed when the ultrasound was present. SEM
100 2.7 5.0 48.0 89.5
observation showed that well-defined accordion-like morphology is
observed after 8 h treatment with ultrasound. The removal of the Al
layer in the precursor was promoted significantly, only 1.63 wt% of Al is

Fig. 7. Cycling stability of 8 h-sonicated sample at 5A/g; inset of Fig. 6: the GCD curves of the first cycle and the last cycle of cycling stability test.

7
X. Zhang et al.
Fig. 8. Comparison of the capacity retention of the as-prepared 8 h-sonicated sample with previously reported MXene or MXene-based materials.
Fig. 9. Schematic of the consequence of ultrasound on the synthesis of accordion-like Ti3C2Tx MXene.
left in the etched sample with 8 h of sonication, while the corresponding
percentage is 7.88 wt% in the counterparts without sonication. Oxida­
tion of C and Ti in the chemical etching process was proved by XPS
characterization. The specific capacitance was calculated by using CV
and GCD curves, it is shown that the specific capacitance of the 8 h-
sonicated sample is 155F/g, which is approximately 45-fold of the un-
sonicated sample prepared with the same experimental condition.
Additionally, the specific capacitance retention of the prepared 8 h
sonicated sample was 97.5% after 20,000 cycles of charging/discharg­
ing, exhibiting an outstanding energy storage stability compared with
the previously reported MXene or MXene-based materials.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors gratefully acknowledge the financial support from the
Department of Science and Technology of Liaoning Province, China
(2019-ZD-0261).
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Another random document with
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 We had canyaos, or bonfires with “head-dances,” and all the
strange varieties of entertainment provided by the village headmen.
The musical instrument of the Igorrote is called a ganza, which is a
round brass gong with a handle made of a human jaw-bone, upon
which the “musician” beats a rhythmical measure with a soft, padded
mallet as he whirls and twists in his fantastic dance. These ganzas—
some of them very old,—are tribal rather than individual property
and it is very difficult to induce their owners to part with them. Their
value is computed in carabaos instead of in rice, or in dollars and
cents. If you should ask an Igorrote how much he would take for his
ganza, especially if it were one associated with tribal history, he
would very likely look smilingly solemn and say: “One hundred
carabao,” or any other prohibitive number that might happen to
occur to him. This is a form of racial pride and deserves respect.
We went from Bontoc back through Sagada to Cervantes, and then
started down the long, narrow trail straight through the mountains
to Baguio. At Cervantes we received our first messages from Manila
and, among other things, was an order to Major Stevens to report for
duty. His going gave us an opportunity to send letters down and
report ourselves alive and not at all anxious to get home, but we
didn’t like losing the Major. We had, by this time, become a very well
acquainted, well-disciplined and congenial party and we disliked
seeing the beginning of the end of our expedition. General Bell
directed everything and joined in our sports and foolishness
whenever he could do so without endangering the dignity of the
“corps,” but, while he was kindness itself, he was so strict with the
young officers that we had sometimes to steal our opportunities for
relaxation.
A few hours’ riding south from Cervantes are some famous copper
mines which were owned by a Spanish syndicate. We turned off in
their direction and came into a most extraordinary country. The
whole face of the landscape looks like corroded copper, and the great,
scarred gulches where the ore has been taken out make one think of
chaos, or dreams of an inferno. I don’t know how to express an idea
of bigness in a mere touch of description as I pass on through the
story of this trip, but I want to convey an impression of
overwhelming size in everything. It is a great, wild world where one
sees miles in every direction and where nature seems to have done
everything on a gigantic scale.
A mile or so beyond the copper mines we came upon a veritable
mountain paradise,—from our point of view, at least. It was the home
of Don José Mills, a Spaniard who, for some unknown reason, had
banished himself to this out-of-the-world spot and, with what labour
and pains can only be imagined, had made for himself a civilised
abode. I was shown to a room all by myself, which had in it a real bed
with springs and a mattress. It was the first one I had seen for I don’t
know how long. I regarded it with great curiosity at first, then I sat
down on it most respectfully. I lay down and stretched myself out;
then I pulled up a soft blanket and, though it was only midday,
nothing short of the gravest emergency could have induced me to
move. The emergency presented itself, finally, in the form of
luncheon and I discovered that Don José had returned hurriedly
from Candon in order to entertain us and that he had brought with
him everything in the form of food and liquid refreshments that he
could find. The result was a triumph, and we decided that we should
like to remain under his hospitable roof indefinitely.
That night, amid much merriment, we initiated our host into the
mysteries and secrets of a little society we had formed and which we
called the Earring Club. Our insignia was a big, brass Igorrote
earring, and we had signs and pass-words, to say nothing of a song
which nobody but ourselves could sing. We appropriated the Cavalry
tune of “For Seven Long Years I’ve Courted Nancy,” but the words
were our own and it was not difficult to supply a new verse to fit each
incident or occasion as it came along. The song began:
Bureau of Science,
Manila.

IGORROTE CHIEF PROUDLY

DISPLAYING HIS HOUSE
DECORATIONS OF HUMAN SKULLS
AND CARABAO HORNS
 Bureau of Science,
Manila.

BONTOC IGORROTES WITH

GANZAS, SHOWING HANDLES
MADE OF HUMAN JAW BONES

For twelve long days we’ve hiked through mountains,

Heigh ho! Cross roaring rivers!
For twelve long days we’ve hiked through mountains,
Ha! Ha! While on our way through wild Lepanto!

Up at Sagada we came upon the only bed of mint that any of us

had ever seen in the Philippines, and as General Bell had almost an
inspired knowledge as to what mint was originally intended for, this
gave us material for three new verses:
One rainy day we reached Sagada,
Heigh ho! Among the rice fields!
One rainy day we reached Sagada,
Ha! Ha! As we toiled along o’er the hills of Bontoc!
 A place most sweet with fragrant mint-beds,
Heigh ho! How did it get there?
A place most sweet with fragrant mint-beds,
Ha! Ha! ‘Way high up in the hills of Bontoc!

We didn’t do a thing but make a julep,

Heigh ho! Without the cracked ice!
We didn’t do a thing but make a julep,
Ha! Ha! With the mint we found in the hills of Bontoc!

It was a free-for-all composition contest; anybody was likely to

produce a new verse, or even a whole new song with a different tune,
at any moment, and we shortened many a long mile with such
nonsense.
At Don José’s we not only sang all our songs for the benefit of our
host, but one of our number produced a harmonica, on which he
played very well indeed, and we had an impromptu baile. Then we
“dropped the handkerchief,” “followed the leader,” gave some
original renderings of German Grand Opera, played Puss-in-the-
corner, and finished the evening with our feet on a fender before a
great, open fire, recounting, with much appreciated embellishments,
our interesting experiences.
We knew we should not find any place as delightful as Don José’s
again,—not even in Manila, because Manila would be hot,—so it was
with great reluctance that we obeyed orders to be ready to leave the
next morning at six. This meant getting out of our comfortable,
civilised beds at five o’clock, while the stars would still be out, and
when the ashes of our evening’s fire would be cold and grey on the
hearth. It was a cheerless thought, but we had to “get to Loo” said
General Bell.
It was raining—of course—and there was not much scenery visible
except when the clouds would float upward, now and then, like veils
lifted off grand panoramas, but by this time we had ceased to
consider the weather. When we got to Loo we found the “town”
consisted of just two empty log huts, one with a plaited reed floor,
the other with no floor at all, and neither of them with any sort of
partition. We stretched a rope across the middle of the better one,
hung Igorrote blankets on it by way of a screen, and prepared to
make ourselves comfortable on the, fortunately flexible, floor; ladies
on one side, gentlemen on the other. But along late in the afternoon a
pack train of mules and Igorrotes and orderlies arrived from the
south bringing us the astonishing news that the Commissioners were
only a few miles behind and expected to camp that night at Loo!
The rain had settled down into a dreary, soaking patter; it was
cold; we were all wet; there was no place for a fire; and, altogether,
we were fairly uncomfortable.
The Commissioners, Mr. Worcester and Mr. Moses, with their
private secretaries and a doctor—five in all—came along about an
hour behind their pack train. They straggled in one by one, very
grumpy, and we decided right away that they had not been taught, as
we had been, to make the best of everything and to cultivate
sociability on the trail. They had had a much more difficult day’s
riding than we because the trail up is much harder than the trail
down, but we were pretty certain, on the whole, that we were much
the better managed party.
With more Igorrote blankets we arranged another partition in the
hut to make room for them, then we gave them a good hot dinner—
cooked in the tent which had been put up for kitchen purposes—and
immediately a social thaw set in. We got all the news from Manila
that we were so anxious for, and all the latest gossip. The news was
disquieting. A cablegram had come announcing that the Supreme
Court had decided there should be no duties in Porto Rico against
United States imports, and instructing the Commission to suspend
all legislation in the Philippine Islands until further notice. This
might mean anything, but whatever else it meant it certainly meant
renewed uncertainty and the possibility that no change in the
government would be made until after Congress met.
The politics of the situation were extremely complicated and
seemed to revolve around a question which, because of a rather
pugnacious manner of expressing it, had become a popular clamour.
The question was: “Does the Constitution follow the Flag?” In other
words, really, could duties be collected on imports from one
American port to another? In any case, the question in respect to us
was one for Congress to answer and it seemed to me we were facing
another long period of uneasiness and delay.
We knew the entire Commission had expected to make a trip in
June for the purpose of organising the Christian provinces in the far
north beyond the Mountain Province, but they were halted by the
order to suspend definite activities, and Commissioners Worcester
and Moses had taken advantage of the “breathing spell” to run up
into the mountains and inspect proposed routes for roads and
railways. That is how we happened to encounter them at Loo. We
shared their opinion that one of the greatest things that could be
done for the country was to make the mountains of central Luzon,
with their glorious climate, easily accessible. The trails as we found
them were mere paths worn by the feet of Igorrotes and, besides
being very narrow, were at such grades as to make them in many
places all but impassable. The party, highly representative of
American authority in the Islands, as it was, sat around on the
bamboo floor, huddled up in blankets, and talked long into the night
about hopes and fears and governmental problems of great difficulty
and importance.
We left Loo at six o’clock in the morning and after eight straight
hours of the hardest work we had yet been called upon to do, we
arrived at Cabayan. According to my own diary: “I was completely
tired. The greater part of the way we rode through beautiful pine
forests, but up and down hills as steep as the side of a house; across
rivers, and up a waterfall.” This sounds like pretty heavy going, but
my account of it written at the time was, I am sure, only slightly
exaggerated. I remember distinctly that from Loo to Baguio, five full
days, we walked a great part of the way; and not only did we walk,
but we rendered necessary assistance to our horses which, giving out
one by one, had to be dragged up the steep grades and “eased” down
the opposite sides in a way that would have been highly ludicrous
had we been engaged in anything but a very serious business. Only
the steady old mules plodded along “without a word,” and found
their own way in safety around the dangerous turns.
 Bureau of Science, Manila.

THE BENGUET ROAD BEFORE AND AFTER COMPLETION.

NOT THE MOST THRILLING CURVE ON THIS SPECTACULAR
HIGHWAY

After leaving Bontoc we travelled down through Nueva Viscaya

and into Benguet, the southermost division of the Mountain
province. At Cabayan we had for camping quarters a large
presidencia and schoolhouse combined, while a tent was put up and
rudely equipped for bathing purposes. This was luxury indeed, and
we began to think that we had left all hardship behind us; but the
next night, after a seven hours’ “hike” over a terrible trail, we found
shelter in a miserable hut with only one room which we all had to
occupy, with Igorrote blankets for partitions.
The Igorrotes grew less and less interesting as we went along and
displayed few evidences of the industry and thrift which characterise
the more northern tribes. The mountains are higher and the scenes
are broader and more wonderful at the southern end of the range,
but the only cultivation we came upon was in the villages and along
the banks of the little rushing streams. It was evident that we were
approaching “civilisation.” Here and there we went through small
groves of coffee trees, beautiful in a wealth of snow-white blossoms,
but evidently deserted, and wretchedly ragged and unkempt.
 Baguio, now the summer capital of the Philippine Islands, the
“Philippine Simla,” as it is so often called, lies at the top of what has
become justly celebrated as “the magnificent Benguet Road,” the
building of which has been the subject of more controversy than
almost any other one thing that American authority and enterprise
has accomplished in the Islands. The Benguet Road when I first saw
it was known as “Mead’s Trail,” so named in honour of the engineer
who made the original survey for it, and in some places it was
nothing more than a thin line drawn against perpendicular cliffs to
indicate where cutting was to be done.
Let somebody else argue the question as to whether or not this
road has justified the faith of the men who built it. My husband and
his colleagues were responsible for the beginning of it and Mr. Taft
authorised the payment of the large sums of money which went into
it, but he does not in the least object to honest criticism of the
project. His only question is: “How else could we have accomplished
what we did?” For which there is no satisfactory answer. I have
ridden over it since it was completed and, in common with a majority
of those who have enjoyed this privilege, I am strongly prejudiced in
its favour. There are few, if any roads in the world more spectacular,
or which represent a greater triumph of engineering skill. Fairly
hewn out of the almost solid, but too crumbling, walls of the Bued
River Canyon, it winds for about seventeen miles through constantly
changing scenes of extraordinary grandeur, then it strikes the
foothills of the mountains and rises in a succession of splendid
upward sweeps to an altitude of more than five thousand feet in less
than six miles.
The Benguet Road was originally a railway project and was to have
been built by the British company which owns the Manila and
Dagupan Railway. But this syndicate wanted a perpetual grant and a
guarantee from the government which could not then be given. It
was necessary, in any case, to build a wagon-road before railway
construction could be started and Captain Mead, who was sent out at
the head of a surveying party, reported that such a road would cost at
least $50,000, or $75,000. The Commission appropriated the
$50,000 and issued orders to have the work begun, fully expecting to
have to add another $25,000 before the road was finished. Nobody
knows what character of road Captain Mead had in mind when he
made his estimate, but it transpired that nothing short of first-class
construction would last through even one heavy rain. Besides, the
Bued River Canyon had to be spanned six or eight times with
tremendous suspension bridges, and before the project was
completed an unwilling government had spent something like
$2,500,000 on it. This was spread over a period of years, of course,
and much of it went for necessary improvements or for the
replacement of storm-wrecked bridges and graded sections, but its
enemies like to refer to it as our two and a half million dollar road.
The Manila and Dagupan Railway company extended its road up
to the point where the Benguet Road begins and thus a way was
opened into the only region in the Philippines where one may find
really invigorating air. And while the road was building Baguio
development began. A United States Army Camp was established on
a ridge overlooking a wide range of pine-covered hills, and a hospital
was erected for the accommodation of invalid soldiers who, before
these facilities for taking care of them were provided, had always, at
great expense to the government, to be sent back to the United
States. A civil hospital and tuberculosis camp were opened; good
hotels under private ownership soon took the place of field tents and
rough board shacks; markets and stores were started, bringing in
supplies in wholesale lots, and fair-sized buildings soon began to go
up in a substantial business section; people began to build houses as
rapidly as builders could be found to do the work; churches and
schools began to appear where nothing was before; a summer camp
for the recuperation of thousands of public school teachers was
started in a high valley carpeted with pine-needles, and lecture
courses for vacation instruction were instituted; a country club was
organised with golf links, a baseball diamond, polo grounds, tennis
courts and everything that goes to make a country club successful.
The plan of the city was drawn by Architect Burnham of Chicago,
who visited Benguet for the purpose, and a great central plaza was
provided with artistic, but inexpensive buildings for the
accommodation of the two branches of the government. Cottages in
rows went up almost overnight; rich Filipinos and a few Americans
built fine homes; beautifully metalled drives began to wind in and
out and over and around the hills, and a high-class government
automobile ‘bus line was put on the Benguet Road which is the
delight of every American or other foreigner in the Islands, as well as
of many hundreds of Filipinos who annually take advantage of this
wholly novel opportunity to reach a salubrious climate in their own
land, and by a route which in any European country would attract
scores of thrill-seeking tourists.
And so the Philippine Simla was begun. Its friends, or, in other
words, most people have dreams of a great future for it when it shall
be a thriving, prosperous city and a health resort for everybody “east
of Suez” who needs to seek near by a temperate and invigorating
climate.
It is six years since I saw Baguio, for I visited it the last time in
1907, but even then I could not believe that it was built on the
ground that I had ridden over and found practically uninhabited only
six years before. At that time a provincial government had been
organised, and an American, Mr. Phelps Whitmarsh, who was a
writer and had lived among the Igorrotes a long time, was appointed
governor. But he was governor of a wild-tribe province which did not
then boast any greater signs of civilisation than winding foot trails
and a few groups of low-thatched huts which were known as towns.
We rode in from Trinidad, not many miles from Baguio, on the
morning of the 23rd of June and went straight to the governor’s
“mansion.” We were welcomed by Mrs. Whitmarsh into a nipa-
roofed, suali house which, though it was quite large, had no
partitions except such as were made of bamboo screens and hangings
of bright-coloured Igorrote cloths. But it had a big, open fireplace
and a fine blaze from odorous pine boughs was crackling up the
chimney. This seemed particularly cosy and delightful to us because
we had just been camping in native huts in which the only place for a
fire was a square of earth in the middle of the floor and we were not
only quite frozen but we were thoroughly smoked.
 THE ZIGZAG. HOW THE BENGUET ROAD CLIMBS TO AN
ALTITUDE OF OVER 5,000 FEET IN SIX MILES

At Baguio we got letters and telegrams from Manila and one of the
telegrams announced my husband’s appointment as Governor of the
Islands, so I knew that an adjustment of state affairs had been made
and that I should reach Manila to begin a new era in my Philippine
experience. Mr. Taft wrote me that the plans for his inauguration
were practically complete and that he was issuing cards for a big
reception in honour of General MacArthur at our house on the
evening of the Fourth of July. This filled me with something like
panic, because I didn’t expect to reach Manila until after the first of
July and I didn’t see how I could get ready on such short notice to
entertain hundreds of people. However, it was not for me to enter a
protest on such a score, so it was decided that we would go down as
soon as we possibly could.
We spent two days enjoying the delightful hospitality of our
friends in Baguio and in exploring the country round about, and I,
after listening to builders’ dreams of what was to be and now is,
proceeded to select a site for my own future summer home.
 We sat around a roaring fire of an evening and sang all our songs,
rather ruefully; we recounted our many adventures, and expressed
our sincere regret that our holiday was over; then on the morning of
the 25th of June, at the dreary hour of half past four, we mounted
our refreshed and rested horses and started down the long Naguilian
trail to the coast. I wish only to add that the heat in the lowlands,
after our long breath of white man’s air in the mountains, was almost
more than we could stand, and I made the fatal mistake of leaving
Baguio in a heavy flannel riding shirt and with no thin blouse handy
to take its place.
 CHAPTER X
GOVERNOR TAFT

There is no denying that the arrangements made, during my

absence in the north, for my participation in the events attending my
husband’s induction into the office of Governor of the Philippines
were enough to fill me with dismay.
Mr. Taft had issued two thousand invitations for the reception at
our house in honour of General MacArthur, and on my way down
from Baguio I had been spending my time wondering how I should
take care of the three or four hundred I imagined had been asked. I
had received no information more definite than the simple statement
that invitations had been sent out, and it was not until I reached
Manila that I learned the startling number. I thought my husband
knew something about the limitations of our house, but I found that
he had not taken this important matter into consideration at all.
Fortunately we had a large garden in fairly good condition by this
time, so I immediately went to work and had it decorated with long
lines and festoons of Japanese lanterns; I ordered a large
refreshment tent put up in the middle of the wide lawn; then I sat
down and prayed for fair weather. It was the rainy season and I knew
that only a specially importuned Providence could keep the
afternoon of the Fourth of July clear.
The inauguration of the first American Governor was an occasion
of great dignity and interest. The ceremony took place on a platform
erected at one end of a large square in the Walled City which is
enclosed on one side by the Ayuntamiento, or Insular Capitol, and on
another by the Cathedral. The foundations of the Inaugural stand
were of historic interest in that they were originally intended to
support a magnificent residence for Spanish Governors-General and
were on the site of the ancient gubernatorial mansion which was
destroyed by an earthquake in 1863. The rebuilding had never
progressed beyond the laying of the massive granite base, and this
still stands as a mute reminder to progressive Americans of the
dilatory and otherwise questionable methods which once obtained in
the Philippine government.
The Cathedral Plaza—since renamed Plaza McKinley—presented a
memorable scene that Fourth of July morning. The architectural
grace and time-mellowed colours of the old Spanish buildings
blended with the rich luxuriance of many-hued tropic plants and the
green of spreading acacias. American flags covered the canopied
platforms and floated from every possible point of vantage.
Americans and Filipinos, all in gala attire, were pressed close
together in the spectators’ stands which extended on either side of
the central pavilion; the plaza below was thronged with Filipinos of
every rank and condition, in all manner of bright jusis and calicoes;
while above the crowd towered many American soldiers and sailors
in spic-and-span khaki or white duck.
The programme was much like other programmes. General
MacArthur and his staff occupied the centre of the platform. A well
trained and finely conducted Filipino band played several numbers;
there was a prayer and an invocation; then my husband, looking
larger even than his natural size in his crisp white linen suit, stepped
to the front of the platform and stood gravely looking down upon the
stocky little Chief Justice of the Archipelago, Señor Arellano, who
administered the oath of office. Afterward Mr. Taft and Mr.
Fergusson stood together and delivered, in English and Spanish,
paragraph by paragraph in translation, the Inaugural address.
I think only one unfortunate incident occurred to mar the
complete harmony of the occasion, and that was furnished by a
United States Congressman of the Military Committee of the House,
who was visiting Manila at the time.
Tickets of admission to the central pavilion had been sent to him,
but he had forgotten to bring them with him. However, when he
arrived at the plaza he started, with several ladies who were with
him, to mount the steps of the Inaugural platform on which no ladies
were allowed. He was stopped, naturally, and a guard offered to
conduct his guests to seats on a side pavilion, telling him at the time
that the central stand had been reserved for government officials and
representatives, among whom he, of course, was included. This
separate seating of the ladies seemed to annoy him for some reason,
and he announced his intention of remaining with his party. He was
then shown to the best available seats and the incident seemed to be
closed. But he was by no means satisfied with his position, especially
when he found that the wives of some of the Commissioners had
seats in front of him. I think the heat must have been affecting him
for he called the Naval Lieutenant, who was in charge as usher, and
made audible protest against “those wives of clerks” being put before
him and his wife. The young naval officer was polite, but quite firm
in his refusal to take any steps to remedy matters.
“You don’t seem to know who I am!” he exclaimed, with manifest
indignation.
“No, sir, I do not,” mildly replied the Lieutenant.
“Well,” said the angry man, “I’m a member of the Military
Committee of the House of Representatives. I helped to make this
Army out here and I’ve come out to see what kind of work I did. I
don’t like it, and I’m going home and unmake it. This treatment of
me here is of a piece with the treatment I’ve received ever since I’ve
been in these islands.”
This didn’t sound quite fair. He had been treated with marked
courtesy by everybody and had accepted rather lavish hospitality
from both Army officers and civil officials. In fact, he had received
every possible attention in a most unusually hospitable community.
The young Lieutenant bristled up and said:
 MR. TAFT TAKING THE OATH OF OFFICE AS THE FIRST
AMERICAN GOVERNOR OF THE PHILIPPINE ISLANDS

“Sorry, sir, but I’m obeying orders; and I’d just like to tell you that
I consider your remarks exceedingly impolite.”
Upon which the gentleman from Washington left the pavilion and
went down to stand in a place which the guards had been ordered to
keep clear.
The rest of the story I heard afterward. It seems that both General
Barry and General Davis saw him and took pains to go down and ask
him up into the central pavilion, but he refused to go. Then one of
the guards came up and politely informed him: “Orders, sir, you’ll
have to stand back.” By this time he was infuriated and he turned on
the guard and, after identifying himself, repeated his remarks about
having made the Army and being determined to go back to
Washington and unmake it.
“Well,” said the guard, “I guess you can’t unmake me. I’ve just
been mustered out of the United States Army and am a plain
American citizen. I don’t understand that Congress can do much
about unmaking American citizens.” Which all goes to show that it
doesn’t do much good to lose one’s temper. The gentleman took his
party and stalked out of the plaza.
 My hopes for the evening were blasted. About five o’clock the
heavens opened and such a sheet of water descended upon my
refreshment tent and my strings of gay paper lanterns as one never
sees in the Temperate Zone. It was raining in torrents when our
guests began to arrive, and if many of those invited had not been
kept at home by the weather I don’t know what I should have done
with the crowd. I had a wide hall, a small reception room, a dining-
room and the verandah, but two thousand people are a good many,
and I’m sure a large majority of them came in spite of the weather. It
was a “crush,” and a warm, moist crush, but it was a gala occasion,
everybody was in good humour and the evening passed much more
pleasantly than I had any reason to expect. This was the first
entertainment of such proportions that I had undertaken in Manila,
and I saw at once that, as the Governor’s wife, I should need all the
spaciousness of Malacañan Palace.
I think General MacArthur was pleased with our farewell
hospitality to him; he seemed to be; and I think his feelings toward
Mr. Taft, when he left the Islands the next day, were exceedingly
friendly. But we heard later that letters had come from companions
of his on the ship which said that he very keenly resented the fact
that the new Governor had not seen fit to mention him with praise in
his Inaugural address. Mr. Taft said he was very sorry, but, in view of
the relations which were known to exist between the Military
government and the Commission, he thought it would have been
very difficult to find the tactful words which would have satisfied the
General, and in uttering which he would not have stultified himself.
I am quite sure that General MacArthur never disliked my
husband personally. His resentment was against the Commissioners
in their official capacity, whereby his own authority was diminished.
In later years, as Secretary of War, Mr. Taft met him very often and
their relations were always perfectly cordial. After his death there
was considerable newspaper comment to the effect that he had been
very badly treated. There was no refutation of the charges, but
everybody familiar with the facts knew they had no foundation.
When Mr. Taft was Secretary of War, on his recommendation
General MacArthur was given the highest rank in the United States
Army, that of Lieutenant-General, and at his own request was sent by
Mr. Taft on a mission to travel through China with his son, an Army
officer, as his aide, and to make a military report upon the country.
On his return, at his own request, he was not assigned to specific
command, but was ordered to his home at Milwaukee to prepare the
report on China, and there he remained by his own choice until his
retirement.
On the morning of July 5, we moved to Malacañan, and General
Chaffee, who succeeded General MacArthur, took our house on the
Bay. There was a great deal of contention with regard to this
exchange of houses. Mr. Taft knew that to the mind of the Filipinos
the office of Governor, without the accustomed “setting” and general
aspects of the position, would lose a large part of its dignity and
effectiveness. He also knew that a Civil Government, unless it were
quartered in the Ayuntamiento, the recognised seat of government,
would inspire but little confidence or respect. The outward
semblance is all-important to the Filipino mind, yet knowing this the
Military authorities clung with dogged tenacity to every visible
evidence of supremacy, and it took an order from Washington to get
them to vacate the Ayuntamiento in which they had, in the
beginning, refused the Commission adequate office room. An official
order also turned the Governor’s residence over to the new Governor
and, at the same time, relieved Mr. Taft of the necessity for deciding
what to do with our house in Malate. It was the best available house
in the city and every man on the Commission wanted it, so if the War
Department had not taken it for the Commanding General
somebody’s feelings surely would have suffered. Mr. Taft had about
decided to toss a coin in the presence of them all to see which one of
his colleagues should have it.
In some ways we regretted that the move was necessary, for we
were very comfortable in our “chalet,” as Señor Juan de Juan had
editorially called it, and invigorating dips in the high breakers of the
Bay had become one of our pleasantest pastimes. But we knew that
no amount of executive orders could turn our homely and unpalatial
abode into a gubernatorial mansion, so we needs must move for the
effect on the native mind, if for nothing else. Not until we did, would
the Filipinos be convinced that Civil Government was actually
established.
Not that I wasn’t well pleased with the idea of living in a palace,
however unlike the popular conception of a palace it might be. I had
not been brought up with any such destiny in view and I confess that
it appealed to my imagination.
Malacañan is old and rather damp and, in my time, some of it had
not been furnished or finished according to modern ideas, but in size
and dignity it leaves nothing to be desired, and it has historic
associations which give it an atmosphere that I found to be quite
thrilling. It contains many fine, old-world Spanish portraits, and
there is one large canvas of especial interest which hangs at the head
of the main stairway. It depicts the ceremony through which
Magellan made peace with the natives of Cebu when he landed on
that island in April, 1521. This consisted of drawing blood from the
breasts of the principal parties to the contract, the one drinking that
of the other. The Spaniards called it the Pacto de Sangre, or the
Blood Pact, and so the picture is named. In our own day the
Katipunan League, the strongest and most sinister of all the
insurrectionary secret societies, are said to have adopted this
ceremony in their rites of initiation, and members of the League
could be identified by a peculiar scar on the breast.
The grounds at Malacañan contain, perhaps, twenty acres, and in
those days there were fields and swamps in the enclosure as well as
lawns and fountains, flower-beds and kitchen gardens. There were
five or six good-sized houses in the grounds for the use of secretaries
and aides, and the stables were very large.
I would not care to hazard a guess as to the number of parientes
we sheltered in the quarters of our employés. Mr. Taft called these
quarters our “Filipino tenement” and “Calle Pariente,” but screened
with shrubbery and spreading down the sides of a twenty-acre lot the
colony did not seem as conspicuous as our huddled tribe had been in
Malate.
The Palace is architecturally Spanish, yet it lacks the large patio,
having two small courts instead. The lower floor, on a level with the
ground, is really nothing more than a basement and has no usable
spaces in it except some raised offices and cloak rooms. Frequently
during bad typhoons I have seen water two and three feet deep in the
entrance hall, but it always receded very rapidly and seldom gave us
any inconvenience. The entrance, which is paved with marble, is very
broad, and there is a wide and imposing staircase of polished
hardwood leading to the reception hall above. The great living-rooms