Covalent Organic Framework

Decorated TiO2 Nanotube Arrays for

Photoelectrochemical Cathodic
Protection of Steel Chunli Wang & Wei
Gao & Nazhen Liu & Yu Xin & Xinyu Liu
& Xiutong Wang & Yong Tian & Xuwei
Chen & Baorong Hou
Visit to download the full and correct content document:
https://ebookmass.com/product/covalent-organic-framework-decorated-tio2-nanotube
-arrays-for-photoelectrochemical-cathodic-protection-of-steel-chunli-wang-wei-gao-na
zhen-liu-yu-xin-xinyu-liu-xiutong-wang-yong-tian-xuw/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Elsevier Weekblad - Week 26 - 2022 Gebruiker

https://ebookmass.com/product/elsevier-weekblad-
week-26-2022-gebruiker/

Jock Seeks Geek: The Holidates Series Book #26 Jill

Brashear

https://ebookmass.com/product/jock-seeks-geek-the-holidates-
series-book-26-jill-brashear/

The New York Review of Books – N. 09, May 26 2022

Various Authors

https://ebookmass.com/product/the-new-york-review-of-
books-n-09-may-26-2022-various-authors/

Calculate with Confidence, 8e (Oct 26,

2021)_(0323696953)_(Elsevier) 8th Edition Morris Rn
Bsn Ma Lnc

https://ebookmass.com/product/calculate-with-
confidence-8e-oct-26-2021_0323696953_elsevier-8th-edition-morris-
rn-bsn-ma-lnc/
A novel TiO2 nanotube arrays/MgTixOy multiphase-
heterojunction film with high efficiency for
photoelectrochemical cathodic protection Chang Feng &
Zhuoyuan Chen & Jiangping Jing & Mengmeng Sun & Guiying
Lu & Jing Tian & Jian Hou
https://ebookmass.com/product/a-novel-tio2-nanotube-arrays-
mgtixoy-multiphase-heterojunction-film-with-high-efficiency-for-
photoelectrochemical-cathodic-protection-chang-feng-zhuoyuan-
chen-jiangping-jing-mengmeng-sun-guiyi/

1 st International Congress and Exhibition on

Sustainability in Music, Art, Textile and Fashion
(ICESMATF 2023) January, 26-27 Madrid, Spain Exhibition
Book 1st Edition Tatiana Lissa
https://ebookmass.com/product/1-st-international-congress-and-
exhibition-on-sustainability-in-music-art-textile-and-fashion-
icesmatf-2023-january-26-27-madrid-spain-exhibition-book-1st-
edition-tatiana-lissa/

Fabrication of heterostructured β-Bi2O3-TiO2 nanotube

array composite film for photoelectrochemical cathodic
protection applications Zi-Chao Guan & Hai-Peng Wang &
Xia Wang & Juan Hu & Rong-Gui Du
https://ebookmass.com/product/fabrication-of-
heterostructured-%ce%b2-bi2o3-tio2-nanotube-array-composite-film-
for-photoelectrochemical-cathodic-protection-applications-zi-
chao-guan-hai-peng-wang-xia-wang-juan-hu-rong-gui-d/

Carbon quantum dots (CQDs) modified TiO2 nanorods

photoelectrode for enhanced photocathodic protection of
Q235 carbon steel Min Feng & Ying Liu & Sainan Zhang &
Yupeng Liu & Ning Luo & Daoai Wang
https://ebookmass.com/product/carbon-quantum-dots-cqds-modified-
tio2-nanorods-photoelectrode-for-enhanced-photocathodic-
protection-of-q235-carbon-steel-min-feng-ying-liu-sainan-zhang-
yupeng-liu-ning-luo-daoai-wang/

Morphology controlled synthesis of Co(OH)2/TiO2 p-n

heterojunction photoelectrodes for efficient
photocathodic protection of 304 stainless steel Xiayu
Lu & Li Liu & Jianwen Ge & Yu Cui & Fuhui Wang
https://ebookmass.com/product/morphology-controlled-synthesis-of-
cooh2-tio2-p-n-heterojunction-photoelectrodes-for-efficient-
photocathodic-protection-of-304-stainless-steel-xiayu-lu-li-liu-
 Corrosion Science 176 (2020) 108920

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Covalent Organic Framework Decorated TiO2 Nanotube Arrays for T

Photoelectrochemical Cathodic Protection of Steel
Chunli Wanga,b,c,1, Wei Gaob,1, Nazhen Liua,c,*, Yu Xina,c, Xinyu Liua,b,c, Xiutong Wanga,c,
Yong Tiand, Xuwei Chenb,*, Baorong Houa,c
a
Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao, 266071, China
b
Research Center for Analytical Sciences, Department of Chemistry, College of Sciences, Northeastern University, Box 332, Shenyang, 110819, China
c
Open Studio for Marine Corrosion and Protection, Pilot National Laboratory for Marine Science and Technology (Qingdao), 1 Wenhai Road, Qingdao 266237, China
d
School of Environmental and Municipal Engineering, Qingdao University of Technology, 11 Fushun Road, Qingdao 266033, China

A R T I C LE I N FO A B S T R A C T

Keywords: For the first time, a covalent organic framework TpBD was grown in situ on TiO2 nanotube arrays (NTAs), and
A. Steel the performance of the composite was investigated for the application of photoelectrochemical (PEC) cathodic
A. Polymer protection. The synthesized TpBD/TiO2 NTA composite exhibited enhanced PEC cathodic protection perfor-
B. SEM mance under visible light. Coupled with the TpBD/TiO2 NTA photoanode, the photoinduced potential drop
B. XPS
values for 304 stainless steel and Q235 carbon steel in 3.5 wt% NaCl solution were 910 and 370 mV, respec-
C. Cathodic protection
tively. It was proposed that the enhanced PEC performance was due to the formation of a Z-scheme hetero-
junction between TpBD and TiO2.

1. Introduction
Structural steel materials, e.g., stainless steel (SS) and carbon steel
(CS), are widely used in various industries due to their low costs and
excellent mechanical properties. However, these properties can be
compromised upon the corrosion of steel; a process that results in en-
vironmental pollution, energy waste, and serious engineering safety
incidents [1–5]. Thus, it is advantageous to protect steel against cor-
rosion. Compared with the traditional corrosion protection methods
(e.g., coating, impressed current, and sacrificial cathodic protection
[6–8]), photoelectrochemical (PEC) cathodic protection is an energy-
saving and economical anticorrosion technology [9]. The key feature of
this technology is the semiconductor photoanode, which produces
electrons under light irradiation. The photoelectrons produced then
transfer to the metal, with the potential difference as the driving force.
As a result, the potential of the metal shifts negatively, achieving
thermodynamic stability. In 1995, Yuan and Tsujikawa successfully
applied a TiO2 electrode as a suitable photoanode to protect copper
from corrosion under UV light [10]. Since then, the application of TiO2
for photocathodic protection has provoked widespread interest due to
its long-term chemical stability, low cost, relative nontoxicity, and fa-
cile synthesis [11–16]. However, the wide band gap (3.2 eV) of TiO2
limits its application to the UV light region, which accounts for only 5%
of the total solar spectrum [17]. Additionally, its high defect density
leads to an unfavorable combination of photoexcited carriers [18].
However, in recent years developments have been made that address
such limitations, including metal and nonmetal element doping [19,20]
and co-sensitization with some narrow band gap organic and inorganic
semiconductors [21,22].
Covalent organic frameworks (COFs), an emerging category of
porous materials, are constructed via self-assembly of pure organic
molecules [23]. With their chemical stability, tunable band gaps, long-
range order structures, and high surface area, COFs have been applied
extensively in gas storage, biosensing, degradation, catalysis, and bat-
tery applications [24–29]. Recent studies have demonstrated the ex-
cellent photocatalytic properties of COFs [30–33]. Thus the use of COFs
as semiconductors, which are capable of structure control and function
design, show great promise in the application of PEC cathodic protec-
tion.
Herein, for the first time, a highly stable COF (TpBD, Scheme 1) was
grown in situ on TiO2 NTAs via a simple hydrothermal step, and its
application in PEC cathodic protection was investigated. Since PEC
cathodic protection requires the absorption of light and the production
of photoelectrons, the TpBD/TiO2 NTA composite was expected to
improve protection performance compared to pure TiO2 NTAs, possibly
due to the following reasons: (1) the π-conjugated structure causes a

⁎
Corresponding authors.
E-mail addresses: liunazhen@qdio.ac.cn (N. Liu), chenxuwei@mail.neu.edu.cn (X. Chen).
1
Authors contributed equally to this work.

https://doi.org/10.1016/j.corsci.2020.108920
Received 2 January 2020; Received in revised form 14 July 2020; Accepted 31 July 2020
Available online 06 August 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
C. Wang, et al.
Scheme 1. Condensation reaction and chemical structure of TpBD.
decrease in the electron transfer resistance; (2) the absorption of visible
light is enhanced due to the low band gap of TpBD; (3) the reserved
pore structure of a TpBD/TiO2 NTA composite hinders the recombina-
tion of carriers by offering a complete reaction between the holes and
the trapping agent (Na2S in this case); and (4) the formation of a het-
erojunction between TpBD and TiO2 would improve the separation of
the photoelectrons from the holes.
2. Experimental
2.1. Materials
Ti foils (> 99% purity) were purchased from Baoji Group Co., Ltd.
(Baoji, China). Ammonium fluoride (NH4F), hydrogen peroxide (H2O2),
nitric acid (HNO3), sodium sulfide (Na2S·9H2O), glycol, ethanol, acetic
acid, 1,4-dioxane, acetone, and 1,3,5-trimethylbenzene were purchased
from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China).
Benzidine (BD) was provided by Aladdin Bio-Chem Technology Co.,
Ltd. (Shanghai, China). 1,3,5-Triformylphloroglucinol (Tp) was pur-
chased from Tongchuangyuan Pharmaceutical Technology Co., Ltd.
(Chengdu, China). Nafion solution was purchased from Sigma-Aldrich
Co., (St. Louis, MO, USA). All the aqueous solutions were prepared
using deionized (DI) water (18.2 MΩ cm) purified using a SMART ultra-
pure water system. All of the reagents used were analytical grade
without further purification.
2.2. Preparation of TiO2 NTAs
Among the three crystalline phases, the anatase TiO2, which is
generally obtained by potentiostatic anodization, is more favorable in
the field of photocatalysis [34]. Ti foils (40 mm × 10 mm × 1 mm)
were ultrasonically degreased in deionized water and ethanol for
15 min each. Then, the Ti sheets were polished in a solution containing
NH4F (4.5 g), H2O (25 mL), H2O2 (30 wt%, 60 mL), and HNO3 (68 wt%,
60 mL) to remove surface oxides. The electrochemical cell composed of
a two-electrode system with Pt foil and a Ti sheet as the counter elec-
trode and working electrode, respectively. A DC voltage of 20 V was
Scheme 2. Schematic illustration of the TpBD/TiO2 NTA composite’s fabrication.
2
Corrosion Science 176 (2020) 108920
applied between the two electrodes for 1.5 h in an electrolyte comprised
of 80.0 mL ethylene glycol, 8.0 mL DI water, and 0.45 g NH4F. After
anodization, the samples were cleaned using DI water and ethanol
several times to remove any residual electrolyte. The as-prepared
samples were annealed at 450 °C for 2 h in air at a heating rate of
5 °C min−1 and naturally cooled afterward to obtain the TiO2 NTAs in
the anatase phase.
2.3. Fabrication of the TpBD/TiO2 NTA composite
1,3,5-triformylphloroglucinol (Tp 6.3 mg, 0.03 mmol) and benzi-
dine (BD 8.3 mg, 0.045 mmol) were dissolved in a mixture of mesity-
lene/1,4-dioxane (30 mL, 1:1). Subsequently, aqueous acetic acid (6 M,
0.5 mL) was added dropwise to the above mixture in a Teflon liner. The
resulting solution was sonicated for 10 min to obtain a homogeneous
dispersion; then, a piece of TiO2 foil was placed aslant into the solution
in the Teflon liner, which was loaded into a stainless steel autoclave and
heated at 120 °C for 72 h. After cooling to room temperature, a dark red
precipitate (TpBD) and a TpBD/TiO2 NTA composite on a Ti matrix
were obtained after extraction with acetone for 24 h (Soxhlet extrac-
tion), the samples were then dried at 60 °C for 6 h under vacuum. The
fabrication process of the TpBD/TiO2 NTA composite is shown in
Scheme 2. The 10-TpBD/TiO2 NTA composite was synthesized using
the same procedure with increased amounts of Tp (63 mg, 0.3 mmol)
and BD (83 mg, 0.45 mmol).
2.4. Characterization
The X-ray diffraction (XRD) patterns were recorded on a Bruker D8
Advance (Bruker, Germany) diffractometer using Cu Kα radiation (λ
=1.5406 Å). The attenuated total reflection infrared spectroscopy
(ATR-IR) was performed on a Nicolet 5700 Spectrometer (Thermo
Nicolet, USA). The field emission scanning electron microscope (FE-
SEM) images were recorded with a Hitachi SU8220 (Hitachi, Japan).
The transmission electron microscopy (TEM) and high resolution
transmission electron microscopy (HRTEM) analyses were carried out
on a JEOL JEM-2100 (Tokyo, Japan) with an accelerating voltage of
200 kV. The X-ray photoelectron spectroscopy (XPS) was recorded on a
Thermo Escalab 250Xi (Thermo Fisher Scientific, USA) with an Al Kα X-
ray source. The UV-vis diffuse reflectance spectra (DRS) were recorded
on a U-3900H spectrophotometer (Hitachi, Japan). The Electron Spin
Resonance (ESR) spectra were measured by the JES-FA200 (JEOL,
Japan).
2.5. Electrochemical measurements
The electrochemical measurements were made using a CHI760E
electrochemical workstation (Shanghai Chenhua Instrument Co. Ltd.,
China). The open circuit potential (OCP-t) and photoinduced current
density (i-t) curves were recorded in an electrochemical cell, as shown
in Scheme 3. In the corrosion cell containing 3.5 wt% NaCl, a saturated
calomel electrode (SCE) served as the reference electrode (RE) and a
steel sample served as the working electrode (WE). The fabricated
photoanode was placed in the photoanode cell containing 0.1 M Na2S
and 0.2 M NaOH, which were used as sacrificial agents for promoting
C. Wang, et al.
Scheme 3. Schematic diagram of the electrochemical test for measuring (a) photoinduced open circuit potential and (b) photoinduced current density.
Fig. 1. SEM images of (a) TiO2 NTAs, (b) TpBD/TiO2 NTAs, (c) 10-TpBD/TiO2 NTAs, and (d) TpBD, respectively. Insets are the cross-sectional image of (a) and (b).
the separation of the photoelectrons and holes. The photoanode cell and
the corrosion cell were separated by a Nafion membrane. The OCP-t
and i-t curves were measured under intermittent illumination. A 300 W
Xenon lamp (PLS-SXE 300 C, Beijing Perfect light Company, China)
with a 420 nm cut-off filter was used to generate visible light with an
energy density of 100 mW cm−2. During the OCP-t measurement, the
steel sample and the fabricated photoanode were electrically coupled
and connected to the working electrode. For the i-t test, the photoanode
and the steel sample were connected to the working electrode and
ground wire, so that the photogenerated electrons could flow from the
photoanode to the steel. In addition, the counter electrode (CE) and RE
interfaces were linked by a short circuit to remove the influence of
polarization.
The photoinduced i-V test was conducted in a three-electrode cell
containing 0.1 M Na2SO4, where the prepared photoanode served as the
WE, and the SCE and Pt foil served as the RE and CE, respectively. The i-
V curve was recorded from −1.0 to 1.0 V at a scan rate of 0.02 V s−1,
where the light was switched on and off every 5 s.
The electrochemical impedance spectroscopy (EIS) was conducted
in a three-electrode cell containing 0.1 M Na2S and 0.2 M NaOH, using a
GAMRY Interface 1000. The prepared photoanode was served as the
WE, and the SCE and Pt foil served as the RE and CE, respectively. The
EIS test was carried out at OCP and spectra were recorded over a fre-
quency range of 105 to 10−2 Hz with an AC voltage magnitude of 5 mV.
3
Corrosion Science 176 (2020) 108920
The results were analyzed using Princeton ZSimpWin version 3.60
software.
The Mott-Schottky (MS) curve was measured in the potential range
of −0.6 V to 1.0 V with an AC potential frequency of 1000 Hz under
dark conditions. The working electrode was prepared as follows: 5.0 mg
of TpBD, 1.0 mL of ethanol and 10 μL of Nafion solution (5 wt%) were
mixed under sonication, and 200 μL of the above suspension was spread
onto the surface of an FTO (fluorine-doped tin oxide) glass substrate
with an area of 10 mm × 10 mm and then dried at room temperature.
3. Results and discussion
3.1. Characterization of the fabricated material
The surface morphologies of the TiO2 NTAs, TpBD, and TpBD/TiO2
NTAs are shown in Fig. 1. The well-ordered and compact TiO2 NTAs
grown on the Ti foil had inner diameters in the range of 30 - 60 nm and
an average length of ∼1000 nm (Fig. 1a). The top view of the TpBD/
TiO2 NTAs showed nanotubes with inner diameters in the range of 20 -
40 nm, which was due to the deposition of TpBD (Fig. 1b). Fig. 1d
showed that the synthesized free TpBD particles were spherical, with an
average diameter of ∼1 μm; however, the TpBD grown in situ on the
TiO2 NTAs was quite different (Fig. 1b and 1c); the significant change of
the TpBD morphology on the TiO2 NTAs was caused by the preferred
C. Wang, et al.
Fig. 2. TEM images of (a) TiO2 NTAs, (b) TpBD/TiO2 NTAs and (c) HRTEM
image of the TpBD/TiO2 NTAs.
growth of TpBD along the edges of the pore opening on TiO2 NTAs [18].
The retained channel structure of the TpBD/TiO2 NTA composite with a
large specific surface area, had the potential to provide sufficient con-
tact between the fabricated material and the surrounding solution,
which could hinder the recombination of carriers by offering a com-
plete reaction between the holes and its trapping agent (Na2S, in this
case). Meanwhile, it is worth mentioning that although the pore
structure was retained in the 10-TpBD/TiO2 NTA composite, the PEC
cathodic protection performance between the TpBD/TiO2 NTAs and 10-
TpBD/TiO2 NTA composites showed minor differences (not shown).
The microstructures of the TiO2 NTAs and TpBD/TiO2 NTAs were
further investigated by TEM and HRTEM (Fig. 2). Fig. 2a showed a
batch of TiO2 nanotubes with inner diameters of ∼50 nm and the for-
mation of ordered NTAs. Fig. 2b showed the microstructure of the
TpBD/TiO2 NTA composite. Compared with the TiO2 NTAs, the basic
outlines of the nanotubes in the TpBD/TiO2 NTA composite were vague
and unclear, likely due to the deposition of the TpBD. The interplanar
spacing of the (101) plane of the anatase TiO2 (0.351 nm) and the (100)
4
Corrosion Science 176 (2020) 108920
plane of the TpBD (0.325 nm) can be observed from the HRTEM image
(Fig. 2c) [35]. The results suggest that TpBD was successfully grown on
the TiO2 NTAs.
The XRD experiments were performed to determine the crystalline
structures of the synthesized materials (Fig. 3). The obtained TpBD
particles displayed moderate crystallinity, likely due to the fact that
rapid growth of the COFs via precipitation limited the formation of
highly crystalline structures [36]. The reflection peaks at 2θ = 3.6º,
6.0º, 7.1º, 9.3º and 26.7º were consistent with the simulated diffraction
data. While the diffraction peaks of Ti and TiO2 could be observed in
the TpBD/TiO2 NTAs sample, the characteristic peaks of TpBD were not
observed. Possible reasons for this are the fact that: a very small
quantity of TpBD was loaded on the TiO2 NTAs and the lack of crys-
tallinity of the TpBD grown in situ on the TiO2 NTAs. In Fig. 1, the
morphologies of the free TpBD particles (Fig. 1d) and the TpBD grown
in situ on the TiO2 NTAs (Fig. 1b and 1c) were quite different, thus
suggesting the morphology of the TpBD varied with the growth con-
ditions, which may influence the crystallinity of the TpBD. The HRTEM
and XRD results indicated contradictory information regarding the
crystallinity of the TpBD grown on the TiO2 NTAs. This may be due to
the different sample preparation methods for the XRD and TEM ana-
lyses. In the TEM analysis, the sample was super thin, thus enabling
local crystallinity of the TpBD to be detected.
The chemical composition of the TpBD/TiO2 NTA composite was
further studied by XPS analysis (Fig. 4). The result showed no obvious
Ti peaks in the full scan spectrum (Fig. 4a), because the detection limit
for the XPS analysis was only a few nanometers and the TiO2 NTAs was
covered with an appreciable amount of TpBD (Fig. 1) [37–39]. The full
scan spectrum of the TpBD/TiO2 NTA composite confirmed the pre-
sence of C 1s (285 eV), N 1s (400 eV), and O 1s (531 eV). Deconvolution
of the C 1s high resolution XPS spectrum (Fig. 4b) into four distinct
peaks allowed for the assignment of the C = C (284.8 eV), C-N
(286.2 eV), C-C (287.0 eV) and C = O (288.4 eV) bonds [22,32]. In the
N 1s spectrum (Fig. 4c), the peaks with binding energies of 398.8 and
399.9 eV were assigned to the C-N-C and N-H bonds, respectively
[27,40]. In the O 1s spectrum (Fig. 4d), two peaks located at 531.7 and
535.0 eV were assigned to the lattice oxygen in the TpBD structure
through C = O bonding [40] and chemically adsorbed water molecules
[41]. The XPS results indicated that TpBD was successfully loaded on
the TiO2 NTAs.
ATR-FTIR spectra of the TiO2 NTAs, TpBD, and TpBD/TiO2 NTAs
are shown in Fig. 5. In the case of the TiO2 NTAs, a wide absorption
peak at 530 cm−1 corresponded to the stretching and bending vibra-
tions of the Ti-O-Ti bond [42]. For TpBD, absorption peaks at
1618 cm−1 (carbonyl C = O stretching), 1571 cm−1 (C = C stretching),
1450 cm−1 (aromatic C = C ring stretching) and 1282 cm−1 (C-N
stretching) were observed [43,44]. The peaks above could also be ob-
served in the spectrum of the TpBD/TiO2 NTAs, thus demonstrating the
successful loading of TpBD.
The optical property of the fabricated materials was investigated by
UV-vis DRS spectra. In Fig. 6, the pure TiO2 NTAs exhibited a narrow
absorption of light in the UV light region (200 - 380 nm), while the
TpBD showed a wider and stronger absorbance. After loading the TpBD,
the TpBD/TiO2 NTAs exhibited an enhanced absorption in the visible
light range. The band gap energy (Eg) of the semiconductor photo-
catalysts can be calculated by the Kubelka-Munk equation [11,45],
αhv = A (hv − Eg )n (1)
where α is the absorption coefficient, h is Plank constant, ν is the light
frequency, and A is a constant. Among them, n, depends on the char-
acteristics of the transition of the semiconductor, e.g., direct transition
(n = 1/2) or indirect transition (n = 2). Both TiO2 and TpBD belong to
indirect transitions (n = 2) [11,30]. Hence, the Eg values of TiO2,
TpBD/TiO2, and TpBD were calculated to be 3.37, 2.40, and 2.20 eV,
respectively. The decrease of the band gap energy indicates an im-
proved absorption of visible light by the fabricated photoanode.
C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 3. XRD patterns for the TiO2 NTAs, TpBD, and TpBD/TiO2 NTA composite.

Fig. 4. (a) Survey, (b) C 1s, (c) N 1s, and (d) O 1s XPS spectrums for the TpBD/TiO2 NTA composite.

3.2. PEC cathodic performance of the fabricated material
Corrosion is the oxidation of metals; forming protective oxides or
dissolving cations depending on the condition of the environment (e.g.,
redox condition, acidity, temperature, etc.). Thermodynamically
speaking, a metal is stable and immune to corrosion below its equili-
brium potential, while metal oxidation/corrosion is favored above the
equilibrium potential. In Fig. 7, the photoinduced potential drop of 304
SS coupled with TiO2 NTAs was 290 mV, and a corresponding photo-
induced current density of 0.015 mA cm−2 was measured (Fig. 7a, c).
The PEC cathodic protection performance of the TpBD/TiO2 NTAs
showed significant improvement with a photoinduced potential drop of
910 mV and a photoinduced current density of 0.12 mA cm−2 (Fig. 7a,
c). In Fig. 7a, the onset potential of the 304SS after being coupled with
TiO2 was slightly higher than the corrosion potential of the 304SS
(black curve vs. blue curve). This observed phenomenon was incon-
sistent with previously reported studies [11,39,46,47] and was caused
by inevitable errors in the OCP measurements. In Fig. 7a, after the light
was turned off, the potential of the 304 SS coupled with TpBD/TiO2 did
not reach the original value in 300 s. The stability study (discussed later

5
C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 5. FTIR-ATR spectrums of the TiO2 NTAs, TpBD, and TpBD/TiO2 NTAs.

Fig. 6. UV-vis DRS spectra of the TiO2 NTAs, TpBD, and TpBD/TiO2 NTAs.

in Fig. 10) showed that after the light was turned off, the coupled po-
tential stabilized at a value that was slightly lower than the corrosion
potential of 304 SS in ∼1000s, indicating that time was a key factor for
the recovery of the potential. When the light was off, no photoelectrons
were transferred from the photoanode to the 304 SS; the potential of the
304 SS was governed by the kinetics of its surface anodic and cathodic
reactions, which was influenced by its surface state. In Fig. 7a, the
photoinduced potential drop of the 304 SS coupled with TpBD/TiO2
was 910 mV, indicating a highly reduced surface state of 304 SS com-
pared to that of its original surface; thus, the recovery of the surface
state was more time consuming. In comparison, the photoinduced po-
tential drop of the 304 SS coupled with TiO2 was 290 mV; thus, it took
less time for the recovery of the surface state.
Compared to the 304SS, the cathodic protection of the Q235 CS is
more challenging, because the Q235 CS has a more negative corrosion
potential of −0.72 V (Fig. 7b), and one of the requirements for a suc-
cessful PEC cathodic protection is that the conduction band potential of
the semiconductor must be more negative than the corrosion potential
of the protected metal [9]. The potential of the Q235 CS did not shift
negatively by coupling to the TiO2 photoanode under light irradiation
(Fig. 7b). In fact, the photoinduced current of the TiO2-CS was negative
(Fig. 7c), indicating the flow of electrons from CS to TiO2. The corrosion
of the CS was accelerated slightly, and a small positive potential shift of
the CS was observed. Compared with the TiO2 NTAs, the TpBD/TiO2
NTA composite showed favorable PEC cathodic protection for the Q235
CS. Under illumination, the photoinduced potential drop was 370 mV
and the photoinduced current density was 0.16 mA cm−2 (Fig. 7b and
7c). After three cycles, the coupled potential of the Q235 CS and 304 SS

6
C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 7. OCP-t curves of (a) 304 SS and (b) Q235 CS, and (c) i-t curves of 304 SS and Q235 CS connected with the TiO2 NTAs and TpBD/TiO2 NTAs photoanodes under
intermittent visible light irradiation.

7
C. Wang, et al.
Fig. 8. The photoinduced i-V curves of TiO2 NTAs and TpBD/TiO2 NTAs photoanodes under intermittent visible light illumination.
maintained a relatively steady value, demonstrating the fast and stable
response of the TpBD/TiO2 NTA composite to light.
The enhanced PEC performance of the TpBD/TiO2 NTA composite
was also confirmed by the i-V curves of the photoanodes under inter-
mittent visible light illumination (Fig. 8). The onset potential for
semiconductors to produce photoinduced current density under light
irradiation is approximately equal to the Fermi level of the corre-
sponding semiconductor, which was −0.62 V for the TiO2 and −0.92 V
for the TpBD/TiO2 NTA composite [48]. The 0.3 V negative shift of the
threshold potential indicated the enhanced reducing capacity of elec-
trons in the TpBD/TiO2 NTA composite. Additionally, the enhanced
8
Corrosion Science 176 (2020) 108920
Fig. 9. (a) Nyquist plots, (b) Bode plots of log
|Z| vs. frequency, (c) phase angle vs. frequency
of the TpBD/TiO2 NTA composite under dark
and illuminated conditions, and the equivalent
circuits established to fit the EIS results of the
TpBD/TiO2 NTA composite under (d) dark and
(e) illuminated conditions.
PEC cathodic performance of the TpBD/TiO2 composite is further
confirmed by the larger photoinduced current density compared to that
of the TiO2.
To study the interfacial properties of the TpBD/TiO2 NTA compo-
site, electrochemical impedance spectroscopy (EIS) tests were carried
out under dark and illuminated conditions, as shown in Fig. 9. In
Fig. 9a, under dark, the Nyquist plot of the TpBD/TiO2 NTA composite
was composed of a big and incomplete semicircle; under illumination,
the Nyquist diagram was featured of a much smaller and incomplete
semicircle. In Fig. 9b, the impedance modulus value of the TpBD/TiO2
NTAs under illumination was two orders of magnitude lower than that
C. Wang, et al. Corrosion Science 176 (2020) 108920

Fig. 10. The long-term potential variation of the 304 SS electrode coupled with the TpBD/TiO2 NTAs photoanode under intermittent visible light illumination.

Table 1
The electrochemical impedance parameters for the TpBD/TiO2 NTA composite under dark and illuminated conditions.
Conditions Rs Qf Rp Qdl Rct
(Ω cm2) (Ω cm2) (Ω cm2)
Y0 n Y0 n
(Ω−1 cm−2 sn) (Ω−1 cm−2 sn)

Under dark 4.24 4.65 × 10−4 0.61 17.54 5.98 × 10−5 0.93 1.30 × 105
Under illumination 3.45 1.45 × 10−3 0.59 9.46 6.35 × 10−4 1 2.23 × 103

Fig. 11. The Mott-Schottky plot of TpBD.

under the dark condition. According to the Bode plots (Fig. 9c), two
time constants corresponding to the double layer capacitance at the
electrode/electrolyte interface and a film capacitance were observed.
The impedance data was modeled by the equivalent circuits shown in
Fig. 9d (under dark) and 9e (under illumination), where Rs is the so-
lution resistance, Qf is the capacitance of the surface film; due to the
porous surface of the TpBD/TiO2 NTAs shown in Fig. 2b, Rp represents
the electrolyte resistance in the pore. In addition, Rct and Qdl represent
the charge transfer resistance and double layer capacitance, respec-
tively. The constant phase element (CPE) is used to replace the capa-
citance with a non-ideal capacitive response, and is calculated by,

9
C. Wang, et al.
Fig. 12. The valence band spectrum of XPS for TpBD.
Q=
1 intercept [45] and was −1.23 V by extrapolation [13]. It is known that
Y0 (j ω) n (2)
where Y0 represents the admittance modulus (Ω−1 sn cm−2), ω is the
angular frequency, and n is a constant with a value between 0 and 1.
CPE is converted to a pure resistor (n = 0) or a pure capacitor (n = 1).
For a CPE with n ≠ 1, its capacitance, C, can be calculated by,
1
1 −n n
C= R n Y0 (3)
where R is the resistance of the resistor paralleled with the CPE [49].
The electrochemical parameters obtained from the fitting results are
summarized in Table 1. According to equation (3), the double layer
capacitance under dark is calculated to be 6.98 × 10−5 F cm−2, which
is one magnitude lower than that under illuminated condition
(6.35 × 10−4 F cm−2), this is likely due to the production and storage
of photo-generated electrons under illumination. The Rct value is an
important parameter to evaluate the photocathodic protection perfor-
mance of the prepared photoanode [49,50]. In Table 1, the Rct values of
the TpBD/TiO2 NTAs were 1.30 × 105 Ω cm2 under dark, and
2.23 × 103 Ω cm2 under illumination, suggesting a rapid transfer of
photogenerated electrons under illuminated condition. Therefore, the
above results were consistent with the good photocathodic protection
performance of the TpBD/TiO2 NTAs composite.
Another requirement for successful PEC cathodic protection is the
stability of the photoanode, which cannot be corroded by the sur-
rounding medium during the protection process. Fig. 10 showed the
long-term variation of potential of 304 SS coupled with the TpBD/TiO2
NTAs photoanode under intermittent visible light illumination. The
coupled potential of the 304 SS was stabilized at −0.9 V after a con-
tinuous light illumination of 3 h. When the light was turned off, the
potential switched back immediately and stabilized at −0.34 V
(slightly lower than the corrosion potential of the 304 SS). After several
cycles, the TpBD/TiO2 NTA composite still exhibited good performance
during the protection process.
3.3. Proposed mechanism
The Mott-Schottky plot was measured to study the band structure of
the TpBD (Fig. 11). The positive slope revealed that the TpBD was an n-
type semiconductor, and its Efb could be obtained from the horizontal
10
Corrosion Science 176 (2020) 108920
the conduction band potential (ECB) for an n-type semiconductor is
0.2 V more negative than the Efb value [51,52]. Thus, the ECB for the
TpBD was calculated to be −1.43 V, which was −1.19 V (vs. NHE)
[30]. The calculated valance band potential (EVB) for the TpBD was
1.01 V (vs. NHE) according to the formula of EVB = ECB + Eg [53]. This
is consistent with the calculated valance band potential based on the VB
XPS spectrum of the TpBD in Fig. 12, which was 0.87 eV by extra-
polating the leading edge of the spectra to the baseline [54].
The ESR result (Fig. 13a) further verified the band structure of the
TpBD, in which the photoelectrons can reduce the adsorbed O2 mole-
cules to produce •O2− radicals (O2/•O2− = −0.3 V vs. NHE), and the
holes cannot oxidize the OH− to produce •OH (OH−/•OH = +2.68 V
vs. NHE).
According to previous reports [54,55], the ECB and EVB values of the
TiO2 were −0.29 and +2.91 V, respectively. Possible band structure
alignments for the TiO2 and TpBD were shown in Fig. 14. Fig. 14a
showed a conventional type-II heterojunction electron transfer path, in
which the photoelectrons in the CB of the TpBD transfer to that of the
TiO2, while the holes localized at the VB of the TiO2 transfer to that of
the TpBD. However, the above mechanism could not explain the fol-
lowing results: (1) according to the ESR results, the accumulated holes
in the VB of the TpBD cannot oxidize the OH− to produce •OH
(Fig. 13a), indicating the accumulation of holes at the VB of the TiO2;
(2) the Q235 CS can be protected from corrosion by the photogenerated
electrons in the TpBD/TiO2 (Fig. 7b,c), indicating the accumulation of
photoelectrons at the CB of the TpBD (more negative than the corrosion
potential of the Q235 CS, which is −0.51 V (vs. NHE)). Thus, a direct Z-
scheme mechanism [56–58] was proposed for the TpBD/TiO2 NTA
composite system (Fig. 14b) in which the electrons in the TiO2 and
holes in the TpBD could recombine directly, thus leading to an efficient
separation of photoelectrons at the CB of the TpBD and holes at the VB
of the TiO2. The remarkable improvement of the PEC cathodic protec-
tion performance of the TpBD/TiO2 NTA composite was also attributed
to the enhanced reducing capacity of the photoelectrons.
4. Conclusions
In summary, COF-TpBD modified TiO2 NTAs (TpBD/TiO2 NTAs)
were successfully fabricated. The TpBD/TiO2 NTA composite showed
C. Wang, et al.
Fig. 13. ESR spectra of radical adducts trapped by DMPO for (a) TpBD and (b) TpBD/TiO2 NTAs under visible light for 5 min.
significantly enhanced PEC cathodic protection performance for 304 SS
and Q235 CS under visible light irradiation. Additionally, the ESR and
PEC analyses indicated that a direct Z-scheme heterojunction was
formed between the TpBD and TiO2, by which an enhanced reduction
capacity of photoelectrons was reserved and an efficient separation of
charge carriers was achieved. This work demonstrates that COF mate-
rials, as semiconductors which are capable of structure control and
functional design, show promise for applications in the field of PEC
cathodic protection.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
11
Corrosion Science 176 (2020) 108920
CRediT authorship contribution statement
Chunli Wang: Investigation, Writing - original draft. Wei Gao:
Validation, Resources. Nazhen Liu: Conceptualization, Writing - re-
view & editing, Supervision, Project administration. Yu Xin: Resources.
Xinyu Liu: Resources. Xiutong Wang: Writing - review & editing.
Yong Tian: Writing - review & editing. Xuwei Chen: Project admin-
istration. Baorong Hou: Funding acquisition.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This research work was financially supported by the National
Natural Science Foundation of China (No. 51901222, 41827805) and
C. Wang, et al.
Fig. 14. Proposed mechanism for the enhanced PEC cathodic protection performance of the TpBD/TiO2 NTAs on steel under illumination.
the CAS Pioneer Hundred Talents Program. I would like to express my
gratitude to Dr. Taylor Martino (CanmetMATERIALS, Canada) for lan-
guage editing, and Dr. Zack Qin for EIS discussion.
References
[1] M.P. Ryan, D.E. Williams, R.J. Chater, B.M. Hutton, D.S. McPhail, Why stainless
steel corrodes, Nature 415 (2002) 770, https://doi.org/10.1038/415770a.
[2] U.R. Evans, Electrochemical mechanism of atomospheric rusting, Nature 206
(1965) 980–982, https://doi.org/10.1038/206980a0.
[3] B.R. Hou, X.G. Li, X.M. Ma, C.W. Du, D.W. Zhang, M. Zheng, W.C. Xu, D.Z. Lu,
F.B. Ma, The cost of corrosion in China, Npj Mater. Degrad. 1 (2017) 1–10, https://
doi.org/10.1038/s41529-017-0005-2.
[4] X.G. Li, D.W. Zhang, Z.Y. Liu, Z. Li, C.W. Du, C.F. Dong, Materials science: Share
corrosion data, Nature 527 (2015) 441–442, https://doi.org/10.1038/527441a.
[5] B. Zhang, J. Wang, B. Wu, X.W. Guo, Y.J. Wang, D. Chen, Y.C. Zhang, K. Du,
E.E. Oguzie, X.L. Ma, Unmasking chloride attack on the passive film of metals,
Nature Commun. 9 (2018) 1–9, https://doi.org/10.1038/s41467-018-04942-x.
[6] A.I. Abdulagatov, Y. Yan, J.R. Cooper, Y. Zhang, Z.M. Gibbs, A.S. Cavanagh,
R.G. Yang, Y.C. Lee, S.M. George, Al2O3 and TiO2 atomic layer deposition on copper
for water corrosion resistance, ACS Appl. Mater. Interfaces 3 (2011) 4593–4601,
https://doi.org/10.1021/am2009579.
[7] C. Christodoulou, G. Glass, J. Webb, S. Austin, C. Goodier, Assessing the long term
benefits of impressed current cathodic protection, Corros. Sci. 52 (2010)
2671–2679, https://doi.org/10.1016/j.corsci.2010.04.018.
[8] C.F. Glover, T.W. Cain, J.R. Scully, Performance of Mg-Sn surface alloys for the
sacrificial cathodic protection of Mg alloy AZ31B-H24, Corros. Sci. 149 (2019)
195–206, https://doi.org/10.1016/j.corsci.2019.01.015.
[9] Y.Y. Bu, J.P. Ao, A review on photoelectrochemical cathodic protection semi-
conductor thin films for metals, Green Energy & Environment. 2 (2017) 331–362,
https://doi.org/10.1016/j.gee.2017.02.003.
[10] J.N. Yuan, S. Tsujikawa, Characterization of sol-gel-derived TiO2 coatingsand their
photoeffects on copper substrates, J. Electrochem. Soc. 142 (1995) 3444, https://
doi.org/10.1149/1.2050002.
[11] H. Li, X.T. Wang, Y. Liu, B.R. Hou, Ag and SnO2 co-sensitized TiO2 photoanodes for
protection of 304SS under visible light, Corros. Sci. 82 (2014) 145–153, https://doi.
org/10.1016/j.corsci.2014.01.009.
[12] H. Li, Y.H. Li, T.X. Wang, B.R. Hou, 3D ZnIn2S4 nanosheets/TiO2 nanotubes as
photoanodes for photocathodic protection of Q235 CS with high efficiency under
visible light, J. Alloys. Compd. 771 (2019) 892–899, https://doi.org/10.1016/j.
jallcom.2018.09.027.
[13] J.P. Jing, Z.Y. Chen, Y.Y. Bu, M.M. Sun, W.Q. Zheng, W.B. Li, Significantly en-
hanced photoelectrochemical cathodic protection performance of hydrogen treated
Cr-doped SrTiO3 by Cr6+ reduction and oxygen vacancy modification, Electrochim.
Acta 304 (2019) 386–395, https://doi.org/10.1016/j.electacta.2019.03.020.
[14] X.Y. Lu, L. Liu, X. Xie, Y. Cui, E.E. Oguzie, F.H. Wang, Synergetic effect of graphene
and Co(OH)2 as cocatalysts of TiO2 nanotubes for enhanced photogenerated
cathodic protection, J. Mater. Sci. Technol. 37 (2019) 55–63, https://doi.org/10.
1016/j.jmst.2019.07.034.
[15] S. Ozkan, A. Mazare, P. Schmuki, Critical parameters and factors in the formation of
spaced TiO2 nanotubes by self-organizing anodization, Electrochim. Acta 268
(2018) 435–447, https://doi.org/10.1016/j.electacta.2018.02.120.
[16] G. Liu, H.G. Yang, J. Pan, Y.Q. Yang, G.Q. Lu, H.M. Cheng, Titanium dioxide
crystals with tailored facets, Chemical reviews 114 (2014) 9559–9612, https://doi.
org/10.1021/cr400621z.
[17] L.Y. Huang, Q.G. Meng, C.Q. Shang, M.L. Jin, L.L. Shui, Y.G. Zhang, Z. Zhang,
12
Corrosion Science 176 (2020) 108920
Z.H. Chen, M.Z. Yuan, X. Wang, K. Kempa, G.F. Zhou, Modified nanopillar arrays
for highly stable and efficient photoelectrochemical water splitting, Global
Challenges 3 (2019) 1800027, , https://doi.org/10.1002/gch2.201800027.
[18] J.X. Low, B.Z. Dai, T. Tong, C.J. Jiang, J.G. Yu, In Situ irradiated X-ray photo-
electron spectroscopy investigation on a direct Z-scheme TiO2/CdS composite film
photocatalyst, Adv. Mater 31 (2019) 1802981, , https://doi.org/10.1002/adma.
201802981.
[19] Y.R. Wang, J.J. Zhao, X.Q. Xiong, S.W. Liu, Y.M. Xu, Role of Ni2+ ions in TiO2 and
Pt/TiO2 photocatalysis for phenol degradation in aqueous suspensions, Appl. Cata.
B: Environ. 258 (2019) 117903, , https://doi.org/10.1016/j.apcatb.2019.117903.
[20] H. Lu, C. Yang, H. Bao, L. Wang, C. Li, H. Wang, Unusual improvement of pseu-
docapacitance of nanocomposite electrodes: three-dimensional amorphous carbon
frameworks triggered by TiO2 nanocrystals, ACS Appl. Mater. Interfaces 11 (2019)
48039–48053, https://doi.org/10.1021/acsami.9b17595.
[21] J.F. Ren, B. Qian, J.Z. Li, Z.W. Song, L. Hao, J.S. Shi, Highly efficient polypyrrole
sensitized TiO2 nanotube films for photocathodic protection of Q235 carbon steel,
Corros. Sci. 111 (2016) 596–601, https://doi.org/10.1016/j.corsci.2016.06.001.
[22] N. Lv, Y.Y. Li, Z.L. Huang, T. Li, S.Y. Ye, D. Dionysiou, X.L. Song, Synthesis of GO/
TiO2/Bi2WO6 nanocomposites with enhanced visible light photocatalytic degrada-
tion of ethylene, Appl. Cata. B: Environ. 246 (2019) 303–311, https://doi.org/10.
1016/j.apcatb.2019.01.068.
[23] N. Huang, P. Wang, D.L. Jiang, Covalent organic frameworks: a materials platform
for structural and functional designs, Nature Reviews Mater. 1 (2016) 16068,
https://doi.org/10.1038/natrevmats.2016.68.
[24] B.P. Biswal, H.D. Chaudhari, R. Banerjee, U.K. Kharul, Chemically stable covalent
organic framework (COF)-polybenzimidazole hybrid membranes: enhanced gas
separation through pore modulation, Chem. Eur. J. 22 (2016) 4695–4699, https://
doi.org/10.1002/chem.201504836.
[25] X. Zhang, K.N. Chi, D.L. Li, Y. Deng, Y.C. Ma, Q.Q. Xu, R. Hu, Y.H. Yang, 2D-
porphrinic covalent organic framework-based aptasensor with enhanced photo-
electrochemical response for the detection of C-reactive protein, Biosensors &
Bioelectronics 129 (2019) 64–71, https://doi.org/10.1016/j.bios.2019.01.009.
[26] H.Y. Liu, J. Chu, Z.L. Yin, X. Cai, L. Zhuang, H.X. Deng, Covalent organic frame-
works linked by amine bonding for concerted electrochemical reduction of CO2,
Chem. 4 (2018) 1696–1709, https://doi.org/10.1016/j.chempr.2018.05.003.
[27] C. Yang, S. Maenosono, J.G. Duan, X.B. Zhang, COF-derived N.,P co-doped carbon
as a metal-free catalyst for highly efficient oxygen reduction reaction,
ChemNanoMat. 5 (2019) 957–963, https://doi.org/10.1002/cnma.201900159.
[28] J.Q. Lv, Y.X. Tan, J.F. Xie, R. Yang, M.X. Yu, S.S. Sun, M.D. Li, D.Q. Yuan,
Y.B. Wang, Direct Solar-to-electrochemical energy storage in a functionalized
covalent organic framework, Angew. Chem., Int. Ed. 130 (2018) 12898–12902,
https://doi.org/10.1002/ange.201806596.
[29] X. Cao, Z. Wang, Z. Qiao, S. Zhao, J. Wang, Penetrated COF channels: amino en-
vironment and suitable size for CO2 preferential adsorption and transport in mixed
matrix membranes, ACS Appl. Mater. Interfaces 11 (2019) 5306–5315, https://doi.
org/10.1021/acsami.8b16877.
[30] F.M. Zhang, J.L. Sheng, Z.D. Yang, X.J. Sun, H.L. Tang, M. Lu, H. Dong, F.C. Shen,
J. Liu, Y.Q. Lan, Rational design of MOF/COF hybrid materials for photocatalytic
H2 evolution in the presence of sacrificial electron donors, Angew. Chem., Int. Ed.
57 (2018) 12106–12110, https://doi.org/10.1002/anie.201806862.
[31] P.F. Wei, M.Z. Qi, Z.P. Wang, S.Y. Ding, W. Yu, Q. Liu, L.K. Wang, H.Z. Wang,
W.K. An, W. Wang, Benzoxazole-linked ultrastable covalent organic frameworks for
photocatalysis, J. Am. Chem. Soc. 140 (2018) 4623–4631, https://doi.org/10.
1021/jacs.8b00571.
[32] F. Li, D.K. Wang, Q.J. Xing, G. Zhou, S.S. Liu, Y. Li, L.L. Zheng, P. Ye, J.P. Zou,
Design and syntheses of MOF/COF hybrid materials via postsynthetic covalent
modification: an efficient strategy to boost the visible-light-driven photocatalytic
performance, Appl. Cata. B: Environ. 243 (2019) 621–628, https://doi.org/10.
C. Wang, et al.
1016/j.apcatb.2018.10.043.
[33] D.G. Wang, N. Li, Y.M. Hu, S. Wan, M. Song, G.P. Yu, Y.H. Jin, W.F. Wei, K. Han,
G.C. Kuang, W. Zhang, Highly fluoro-substituted covalent organic framework and
its application in lithium-sulfur batteries, ACS Appl. Mater. Interfaces 10 (2018)
42233–42240, https://doi.org/10.1021/acsami.8b14213.
[34] G.L. Chiarello, E. Selli, L. Forni, Photocatalytic hydrogen production over flame
spray pyrolysis-synthesised TiO2 and Au/TiO2, Appl. Cata. B: Environ. 84 (2008)
332–339, https://doi.org/10.1016/j.apcatb.2008.04.012.
[35] J. Tan, S. Namuangruk, W.F. Kong, N. Kungwan, J. Guo, C.C. Wang, Manipulation
of amorphous-to-crystalline transformation: towards the construction of covalent
organic framework hybrid microspheres with NIR photothermal conversion ability,
Angew. Chem., Int. Ed. 55 (2016) 13979–13984, https://doi.org/10.1002/anie.
201606155.
[36] S. Wang, Z.Y. Zhang, H.M. Zhang, A.G. Rajan, N. Xu, Y.H. Yang, Y.W. Zeng,
P.W. Liu, X.H. Zhang, Q.Y. Mao, Y. He, J.J. Zhao, B.G. Li, M.S. Strano, W.J. Wang,
Reversible polycondensation-termination growth of covalent-organic-framework
spheres, fibers, and films, Matter 1 (2019) 1592–1605, https://doi.org/10.1016/j.
matt.2019.08.019.
[37] W.Q. Fan, X.Q. Yu, H.C. Lu, H.Y. Bai, C. Zhang, W.D. Shi, Fabrication of TiO2/RGO/
Cu2O heterostructure for photoelectrochemical hydrogen production, Appl. Cata. B:
Environ. 181 (2016) 7–15, https://doi.org/10.1016/j.apcatb.2015.07.032.
[38] X.Z. Yue, S.S. Yi, R.W. Wang, Z.T. Zhang, S.L. Qiu, Cobalt phosphide modified ti-
tanium oxide nanophotocatalysts with significantly enhanced photocatalytic hy-
drogen evolution from water splitting, Small 13 (2017) 1603301, , https://doi.org/
10.1002/smll.201603301.
[39] X.R. Li, X.T. Wang, X.B. Ning, J. Lei, J. Shao, W.C. Wang, Y.L. Huang, B.R. Hou,
Sb2S3/Sb2O3 modified TiO2 photoanode for photocathodic protection of 304
stainless steel under visible light, Appl. Surf. Sci. 462 (2018) 155–163, https://doi.
org/10.1016/j.apsusc.2018.08.108.
[40] L.F. Cui, J.L. Song, A.F. McGuire, S.F. Kang, X.Y. Fang, J.J. Wang, C.C. Yin, X. Li,
Y.G. Wang, B.X. Cui, Constructing highly uniform onion-ring-like graphitic carbon
nitride for efficient visible-light-driven photocatalytic hydrogen evolution, ACS
Nano 12 (2018) 5551–5558, https://doi.org/10.1021/acsnano.8b01271.
[41] P. Burg, P. Fydrych, D. Cagniant, G. Nanse, J. Bimer, A. Jankowska, The char-
acterization of nitrogen-enriched activated carbons by IR, XPS and LSERmethods,
Carbon 40 (2002) 1521–1531, https://doi.org/10.1016/S0008-6223(02)00004-0.
[42] H.H. Song, Z.Q. Sun, Y. Xu, Y.D. Han, J.L. Xu, J.B. Wu, T. Sun, H. Meng, X. Zhang,
Fabrication of NH2-MIL-125(Ti) incorporated TiO2 nanotube arrays composite an-
odes for highly efficient PEC water splitting, Sep. Purif. Technol. 228 (2019)
115764, , https://doi.org/10.1016/j.seppur.2019.115764.
[43] W. Gao, Y. Tian, H. Liu, Y.Q. Cai, A.F. Liu, Y.L. Yu, Z.S. Zhao, G.B. Jiang,
Ultrasensitive determination of tetrabromobisphenol a by covalent organic frame-
work based solid phase microextraction coupled with constant flow desorption
ionization mass spectrometry, Anal. Chem. 91 (2019) 772–775, https://doi.org/10.
1021/acs.analchem.8b04884.
[44] B.P. Biswal, S. Chandra, S. Kandambeth, B. Lukose, T. Heine, R. Banerjee,
Mechanochemical synthesis of chemically stable isoreticular covalent organic fra-
meworks, J. Am. Chem. Soc. 135 (2013) 5328–5331, https://doi.org/10.1021/
ja4017842.
[45] Q.Q. Zhang, J.X. Wang, X.J. Ye, Z.Z. Hui, L.Q. Ye, X.C. Wang, S.F. Chen, Self-as-
sembly of CdS/CdIn2S4 heterostructure with enhanced photocascade synthesis of
13
Corrosion Science 176 (2020) 108920
Schiff base compounds in an aromatic alcohols and nitrobenzene system with
visible light, ACS Appl. Mater. Interfaces 11 (2019) 46735–46745, https://doi.org/
10.1021/acsami.9b14450.
[46] H. Li, X.T. Wang, L. Zhang, B.R. Hou, Preparation and photocathodic protection
performance of CdSe/reduced graphene oxide/TiO2 composite, Corros. Sci. 94
(2015) 342–349, https://doi.org/10.1016/j.corsci.2015.02.017.
[47] X.T. Wang, X.B. Ning, Q. Shao, S.S. Ge, Z.Y. Fei, J. Lei, B.R. Hou, ZnFeAl-layered
double hydroxides/TiO2 composites as photoanodes for photocathodic protection of
304 stainless steel, Sci. Rep. 8 (2018) 1–8, https://doi.org/10.1038/s41598-018-
22572-7.
[48] M.A. Alpuche-Aviles, Y.Y. Wu, Photoelectrochemical study of the band structure of
Zn2SnO4 prepared by the hydrothermal method, J. Am. Chem. Soc. 131 (2009)
3216–3224, https://doi.org/10.1021/ja806719x.
[49] Y. Yang, Y.F. Cheng, Visible light illuminated high-performance WO3-TiO2-BiVO4
nanocomposite photoanodes capable of energy self-storage for photo-induced
cathodic protection, Corros. Sci. 164 (2020) 108333–108342, https://doi.org/10.
1016/j.corsci.2019.108333.
[50] R. Subasri, S. Deshpande, S. Seal, T. Shinohara, Evaluation of the performance of
TiO2-CeO2 bilayer coatings as photoanodes for corrosion protection of copper,
Electrochem. Solid-State Letters 9 (2006) B1–B4, https://doi.org/10.1149/1.
2133723.
[51] M. Zhang, X.J. Bai, D. Liu, J. Wang, Y.F. Zhu, Enhanced catalytic activity of po-
tassium-doped graphitic carbon nitride induced by lower valence position, Appl.
Catal. B: Environ. 164 (2015) 77–81, https://doi.org/10.1016/j.apcatb.2014.09.
020.
[52] Y.J. Xiao, Y. Qi, X.L. Wang, X.Y. Wang, F.X. Zhang, C. Li, Visible-light-responsive 2D
cadmium-organic framework single crystals with dual functions of water reduction
and oxidation, Adv. Mater 30 (2018) 1803401, , https://doi.org/10.1002/adma.
201803401.
[53] Z.Q. Xu, Z.J. Guan, J.J. Yang, Q.Y. Li, Band positions and photoelectrochemical
properties of solution-processed silver-substituted Cu2ZnSnS4 photocathode, ACS
Appl. Energy Mater 2 (2019) 2779–2785, https://doi.org/10.1021/acsaem.
9b00116.
[54] A. Fu, X. Chen, L.H. Tong, D.F. Wang, L.Q. Liu, J.H. Ye, Remarkable visible-light
photocatalytic activity enhancement over Au/p-type TiO2 promoted by efficient
interfacial charge transfer, ACS Appl. Mater. Interfaces 11 (2019) 24154–24163,
https://doi.org/10.1021/acsami.9b07110.
[55] Y. Xu, M.A.A. Schoonen, The absolute energy positions of conduction and valence
bands of selected semiconducting minerals, Am. Mineral. 85 (2000) 543–556,
https://doi.org/10.2138/am-2000-0416.
[56] O. Kvitek, V. Havelka, M. Vesely, A. Reznickova, V. Svorcik, Preparation of alloyed
and “core-shell” Au/Ag bimetallic nanostructures on glass substrate by solid state
dewetting, J. Alloys Compd. 829 (2020) 154627, , https://doi.org/10.1016/j.
jallcom.2020.154627.
[57] Y. Tachibana, L. Vayssieres, J.R. Durrant, Artificial photosynthesis for solar water-
splitting, Nat. Photonics 6 (2012) 511–518, https://doi.org/10.1038/nphoton.
2012.175.
[58] M.S. Zhu, Z.C. Sun, M. Fujitsuka, T. Majima, Inside cover: Z-Scheme Photocatalytic
water splitting on a 2D heterostructure of black phosphorus/bismuth vanadate
using visible light, Angew. Chem. Int. Ed. 57 (2018), https://doi.org/10.1002/anie.
201800579 2008-2008.
Another random document with
no related content on Scribd:
member of the religious society of Friends. A letter which Mr.
Rittenhouse wrote to his brother-in-law Mr. Barton, in October 1762,
announcing this event, indicates the keenness of his sensibility on
the occasion. Mrs. Shoemaker was a woman of intrinsic worth; she
died in the prime of life; and it is believed, she was the first of Mr.
Rittenhouse’s affectionate little band of brothers and sisters who had
attained to the age of maturity, that he had then lost. After giving a
circumstantial account of his sister’s illness and death, he informs
Mr. Barton, that Mr. Daniel Stanton, an eminent public speaker in the
society of Friends,[100] attended her in her last illness, at her
particular request;—and, added Mr. Rittenhouse, “the same worthy
gentleman who visited her in her sickness, delivered an excellent
exhortation at the grave,—giving, in a few words, a very just
character, I think, of our deceased sister.”

Mr. Shoemaker (who married again) had an only child named

Jacob, by his first wife here mentioned. This son became a young
man of promising character: but, having entered the American army
at the commencement of the revolutionary war, and attained (it is
believed) the rank of captain, under the patronage of his uncle David
Rittenhouse, he was slain in the campaign of 1781, in South-
Carolina. Mr. Rittenhouse was much afflicted by the death of this
gallant young man, who fell in the flower of his age.

An occasion presented itself, in which Mr. Rittenhouse, when only

in the thirty-second year of his age, was employed in transacting an
important piece of business of a public nature: it was as follows.

In consequence of a petition of the Messrs. Penn to the court of

chancery in England, exhibited in the year 1735, it was decreed by
the lord chancellor, in 1750,—That an agreement which had been
entered into between the Penns and Lord Baltimore, concerning the
long-subsisting controversy relative to the boundary lines between
Pennsylvania and Maryland, should be carried into specific
execution: and, accordingly, a final agreement was executed by
those proprietaries of the two provinces, on the fourth day July,
1760.
 In pursuance of the chancellor’s decree, provision was made for
ascertaining and fixing the “circle,” to be “drawn at twelve miles
distance from New-Castle, northward and westward, unto the
beginning of the fortieth degree of north latitude;”—and thence,
running a straight line westward, five degrees in longitude, to be
computed from the eastern boundary; as described in the royal
charter to William Penn. Commissioners were appointed under the
chancery-degree, for settling these boundaries. But nothing was
definitively done in the business, until the eleventh of January, 1769;
when the line which was run by Messrs. Mason and Dixon in the
years 1767 and 1768, in pursuance of the final agreement between
the parties before mentioned, was approved and ratified by the king
in council.

So early, however, as about the close of the year 1763, four or five
years before the running and marking of Mason and Dixon’s line, Mr.
Rittenhouse was employed by the Penn family in making some
geographical arrangements, preparatory to the final establishment of
those boundaries. He was engaged to perform this service, by the
Rev. Mr. Richard Peters, (afterwards D. D. and rector of the united
churches of Christ-Church and St. Peters, in Philadelphia,) who then
officiated as the Governor’s provincial secretary; a gentleman of
learning and great worth; and one who, on various occasions,
manifested a friendship for Mr. Rittenhouse, as well the high opinion
he entertained of his abilities.

The particular department of that business thus committed to Mr.

Rittenhouse, seems to have been the fixing of the Circle,—or at
least, the tracing of its course or route, topographically; and this was,
certainly, a matter of no little difficulty. That this service was
performed to the satisfaction of the then administrators of the
government of Pennsylvania, and that it was an arduous one, will
appear by the following extract of a letter from Mr. Rittenhouse to the
Rev. Mr. Barton, dated the sixteenth of February, 1764.[101]

“I hope,” said he, “you will never believe that I am determined to

disclaim all kind of intercourse” with you: for I can say with the
greatest sincerity there are very few things I so much regret, as that I
have it not in my power to spend a great part of my time with you. My
attention has, for some time past, been engaged with such a
multiplicity of things, that I may with some reason claim your
indulgence for my not writing. Have I not, indeed, an equal right to
complain?—for, I think this letter will balance our accounts, from the
time I last saw you.

“I waited on Mr. Peters, as you desired me to do. He treated me

kindly, and made an offer of doing me some services; for which I am
greatly obliged to him. He likewise paid me for my attendance at
New-Castle, and much more generously than I expected;—though I
found it a very laborious affair; being obliged, singly, to go through a
number of tedious and intricate calculations.”

It appears that about this time, Mr. Rittenhouse’s friends had some
beneficial object in view for him; perhaps some official situation,
which they conceived to be adapted to the nature of his pursuits, and
such as might more permanently promote his interests. But whatever
that object may have been, he seems to have hesitated about it. If it
were a public appointment of a permanent kind, it would probably
have required his removal to the city,—a measure which he did not
contemplate at that time; and he might, besides, have been
disinclined to undertake any official duties, which would be likely to
occupy the greater part of his time. He expressed himself thus to Mr.
Barton, on the subject, in the letter just quoted:—“I am greatly
obliged to you, my dear brother, for pointing out any prospect of
advantage to me: I shall consider the matter you mention in your
last, and let you know my opinion. The objections you have so well
answered, are those which would most readily occur to me.
Considering the crazy state of my constitution, a retired life would
certainly suit me best. Since death, to use John Bunyan’s[102] phrase,
does usually knock at my door once a day, would it not be a folly for
me to take up the load of any public business?”

About three years afterwards, Mr. Rittenhouse seemed to have

been less indisposed to accept of an official situation: and, such was
his high standing with the government and its most influential friends,
there can be very little doubt he could have obtained a respectable
one. It is evident that, at this latter period, when perhaps his health
was improved, he had some particular office in view: because, by a
letter to Mr. Barton, dated January 28th 1767, he said—“I am entirely
satisfied with your proceedings in the affair I recommended to you;
and I shall wait on Mr. Peters. The reputation of the office would be
very agreeable to me; but the execution of it would, I am afraid,
greatly interfere with the other projects you have so much insisted
on.”

Mr. Rittenhouse continued a bachelor until the 20th of February,

1766, when he married Eleanor Colston, daughter of Bernard
Colston, a reputable farmer in the neighbourhood. This person
belonged to the religious society called Quakers; Mr. Rittenhouse
was not himself a member of any particular church: but the marriage
was solemnized at Norriton, by the Rev. Mr. Barton, who went thither
for the purpose at his brother-in-law’s request.

Some time prior to this event, old Mr. Rittenhouse, having

previously made his son David the proprietor of the Norriton farm,
removed with his family to the house he had built[103] on his place in
Worcester township, already mentioned; while the son’s family
occupied the old place of residence: and here our Astronomer
remained about four years after his marriage. It was during this
period, that his reputation as an astronomer became eminently
conspicuous;[104] his name acquired a celebrity even in the old world,
of which his early but now much increased fame, in his native
country, was a sure presage.[105]

About the time that he projected his Orrery (which shall be duly
noticed in its place), it appears he had been speculating on the
doctrine of the compressibility of water. For in a letter to Mr. Barton,
dated from Philadelphia the 27th of March, 1767, he mentions,—that
he had not then met with any person, who had seen Mr.
Kinnersley’s[106] experiment on that theory; but that he understood it
was made with the air-pump, and conjectured it to have been similar
to the one made by a member of the Royal Society, related in
Martin’s Magazine: which is thus quoted in Mr. Rittenhouse’s letter:

“I took a glass ball of about an inch and 6/10 in diameter, which was
joined to a cylindrical tube of 4 inches and 2/10 in length, and in
diameter 1/100 of an inch; and by weighing the quantity of mercury
that exactly filled the ball, and also the quantity that filled the tube, I
found that the mercury in 23/100 of an inch of the tube was the
10000th part of that contained in the ball; and with the edge of a file,
I divided the tube accordingly. This having been done, I filled the ball
and part of the tube with water exhausted of air: Now, by placing this
ball and tube under the receiver of an air-pump, I could see the
degree of expansion of the water, answering to any degree of
rarefaction of the air; and by putting it into a glass receiver of a
condensing engine, I could see the degree of compression of the
water, answering to any degree of condensation of the air, &c.”—
Then adds. Mr. Rittenhouse—“Indeed I do not doubt the
compressibility of water, although the above experiment does not
much please me. If the particles of water were in actual contact, it
would be difficult to conceive how any body could much exceed it in
specific gravity; yet we find that gold does, more than eighteen
times.”

The first academic honour conferred upon our philosopher, was on

the 17th of November, 1767; when the College of Philadelphia, then
in its meridian splendour, bestowed on him an honorary degree of
Master of Arts. Mr. Rittenhouse being present at the commencement
then held, the provost, in conferring this degree, thus addressed him,
—in terms of a just and well merited compliment:

“Sir,—The trustees of this College (the faculty of professors

cheerfully concurring), being ever desirous to distinguish real merit,
especially in the natives of this province,—and well-assured of the
extraordinary progress and improvement which you have made, by a
felicity of natural genius, in mechanics, mathematics, astronomy, and
other liberal arts and sciences, all which you have adorned by
singular modesty and irreproachable morals,—have authorized and
required me to admit you to the honorary degree of Master of Arts, in
this seminary: I de therefore, by virtue of this authority, most
cheerfully admit, &c.”

Mr. Rittenhouse’s great abilities, as an astronomer and

mathematician, being now every where known, he was employed in
the year 1769, in settling the limits between the provinces of New-
York and New-Jersey. The original grant of all the territory, called by
the Dutch New-Netherlands (sometimes Nova-Belgia), was made by
King Charles II. to James Duke of York, on the 12th of March, 1663-
4; and on the 24th of June following, the Duke granted that part of it,
now called New-Jersey, to the Lord Berkeley of Stratton and Sir
George Carteret, jointly. The Dutch reduced the country, in the year
1672; but it was restored by the peace of Westminster, February the
9th, 1673-4. On the 29th of June, in the same year, a new patent
was issued to the Duke of York, for the lands comprised within the
limits described in the former patent. On the 28th of the succeeding
July, the colony of New-Jersey was divided into East and West-
Jersey (hence, generally called the Jersies); and the former was
then granted, by the Duke of York, to Sir George Carteret. In 1675,
West-Jersey, being Lord Berkeley’s moiety of the province, was sold
to John Fenwick, in trust for Edward Bylinge; who assigned his
interest therein to William Penn and others,[107] in trust, for the use of
his creditors. This partition was confirmed in the year 1719, by the
general assembly of the Jersies. But prior to this confirmation, viz.
the 10th of October, 1678, a new grant of West-Jersey was made by
the Duke of York, to the assigns of Lord Berkeley; and on the 1st of
February, 1681-2, East-Jersey was sold and conveyed, in pursuance
of Sir George Carteret’s will, to twelve persons; who, by separate
deeds, conveyed one-half of their several interests in the same to
twelve other persons: and, on the 14th of the next month, the Duke
of York made a new grant of East-Jersey to those twenty-four
proprietors, thereby confirming the same to them. The proprietors of
both the Jersies afterwards became very numerous, by purchase as
well as by descent. This being attended with great inconveniencies,
they finally surrendered the government to the crown, on the 17th of
April, 1702: and from that time, the province of New-Jersey
continued to be a royal government, until the American revolution.

The division-line, between East and West-Jersey, was to run from

the south-east point of Little Egg-Harbour, on Barnegate Creek—
being about midway between Cape-May and Sandy-Hook, to a
creek, a little below Ancocus-Creek, on the river Delaware; thence,
about thirty-five miles in a straight course, along the Delaware, up to
44° 40´ of north latitude.

The province of New-York passed a legislative act on this subject,

in the year 1762; and the New-Jersey Assembly enacted a
corresponding law, in 1764. Five commissioners—namely, John
Stevens, James Parker, Henry Cuyler, William Donaldson, and
Walter Rutherford—were appointed on this business, for the two
provinces: their report was passed upon, by both; and it was
confirmed by the King in council, the 1st of September, 1773. It is
understood, that the division-line between East and West-Jersey
remained unsettled, so late as the year 1789. But it nevertheless
appears, that the territorial boundary between New-York and New-
Jersey was fixed by Mr. Rittenhouse, forty-four years ago.

A recurrence shall now be had to a date anterior to our

Philosopher’s employment in the transaction just mentioned.—Within
the two years preceding that period, two objects of much importance
to astronomical science, claimed a large share of the public
attention, in this country: One of them, especially, had already
actually engaged the investigations of the ablest astronomers of the
other hemisphere, as well as our own; preparatory to the then
approaching event, to which those researches were directed. The
result of the expectations excited by both of those objects proved, on
their final completion, highly honourable to the fame of Mr.
Rittenhouse.

The first of these, in the order of time, was our Astronomer’s

newly-projected Orrery; a general but concise description of which,
was communicated by his friend, the Rev. Dr. Smith, to the
Philosophical Society, on the 21st of March, 1768. Of this fine and
eminently useful piece of mechanism, more particular mention shall
be made in the sequel.

The other circumstance, just referred to, was the then approaching
Transit of Venus over the Sun’s disk; an event which was to take
place on the 3d day of June, 1769: And of Mr. Rittenhouse’s
participation in the arduous labours of the astronomical world, on
that very interesting occasion, the following narrative will furnish
some account.

The American Philosophical Society, in their meeting on the 7th of

January, 1769, had appointed the following gentlemen to observe
that rare phænomenon,[108] as it was aptly styled by Dr. Smith;
namely, the. Rev. Mr. (afterwards Dr.) John Ewing, Mr. Thomas Prior,
Joseph Shippen, jun. Esq., Hugh Williamson, M. D., the Rev. Dr.
Smith, Mr. David Rittenhouse, John Lukens, Esq. and Messrs.
James Alexander, Owen Biddle, James Pearson, John Sellers,
Charles Thomson, and William Poole. The gentlemen thus
nominated were distributed into three committees, for the purpose of
making separate observations at three several places; these were,
the city of Philadelphia, Mr. Rittenhouse’s residence, in Norriton, and
the Light-House near Cape Henlopen, on Delaware Bay. Dr. Ewing,
an able mathematician and very respectable astronomer, had the
principal direction of the Observatory in the City, which was erected
on this occasion in the State-house Gardens; and Mr. O. Biddle, a
person of much ingenuity, had the charge of superintending the
observations at Cape Henlopen. Associated with Mr. Rittenhouse, on
the Norriton committee, were the Rev. Dr. Smith, provost of the
College of Philadelphia, well known as an astronomer and eminently
skilled in the mathematics; Mr. Lukens, then surveyor-general of
Pennsylvania, who possessed considerable abilities in the same
departments of science; and Mr. Sellers, a respectable member of
the provincial legislature, for the county of Chester. The Rev. Mr.
Barton, with some other gentlemen of ingenuity and talents,
voluntarily attended at Norriton, on this occasion; and rendered such
assistance as they could, to the committee.
 As the time approached near, when this extraordinary and almost
unprecedented[109] astronomical phænomenon was to manifest itself,
the public expectation and anxiety, which were before considerable,
became greatly heightened. The ignorant—and those, generally,
unacquainted with the nature of the looked-for event,—hearing much
every where said on the subject, and seeing the preparations making
for the occasion, had their curiosity wonderfully excited. To scientific
men, the inestimable value of the approaching phænomenon
suggested very different sensations. “Its importance to the interests
of Astronomy and Navigation, had,” as Dr. Ewing observed at the
time, “justly drawn the attention of every civilized nation in the world.”
An accurate ascertainment of the Sun’s Parallax,—an important. and
fundamental article in Astronomy, was a desideratum not yet
obtained. Only two Transits of Venus over the Sun, had been
observed, prior to the 3d of June, 1769, since the creation of the
world; and of these, the first alone was seen but by two persons:[110]
Yet, as the learned gentleman just quoted has remarked,—“the
Transits of Venus, alone, afford an opportunity of determining this
problem” (the settling the Parallax of the Sun,) “with sufficient
certainty: and these,” he adds, “happen so seldom, that there cannot
be more than two in one century, and in some centuries none at all.”

To an object, then, of such vast importance to science, were

proportioned the expectations of our Observers. But they could not
fail to experience, at the same time, in common with their
astronomical brethren in other parts of the world, a large portion of
anxious apprehensions, lest a cloudy day—nay, even a solitary
passing cloud,—should baffle entirely their exalted hopes, and
destroy all the fruits of their arduous labours! Yet such an
occurrence, as one or the other of these events, was evidently within
the calculations of a probable incident.

Mr. Rittenhouse participated largely in these blended hopes and

fears. He had, for some time before, been laboriously employed in
making the requisite preparatory observations and calculations: and,
as Norriton was now rendered eminently conspicuous, by being fixed
on as a principal site for observing the very interesting phænomenon
so near at hand, he had been assiduously engaged, at the same
time, in preparing and furnishing an Observatory at that place,
suitable for the occasion. This he began to erect early in November,
1768,—“agreeably,” to use his own words, “to the resolutions of the
American Philosophical Society;” but, through various
disappointments from workmen and weather, he was not enabled to
complete it till the middle of April, 1769.[111]

The Norriton Observatory was commodiously situated near Mr.

Rittenhouse’s mansion, on a pretty elevated piece of ground,
commanding a good range of horizontal view. This temporary edifice
was as well adapted to the purpose for which it was chiefly designed,
as the nature of the materials of which it was constructed, and other
circumstances, would permit. Some monies had been previously
appropriated by the Philosophical Society, towards defraying the
expenses necessarily incident to this occasion, at the three several
places of observation: but the funds of the society, at their disposal
for such purposes, were very limited; and it is believed that the quota
of these funds assigned for the expenditures actually incurred for
making the observations of the transit, at Norriton, was quite
inconsiderable in its amount.

In order that ample justice may be done to the merits of Mr.

Rittenhouse, for all the preparatory arrangements made by him on
this occasion, the reader is here presented with an extract from Dr.
Smith’s subsequent Report, to the Philosophical Society, of the
proceedings of the Norriton Committee, and made in their behalf.—“I
am persuaded” says the doctor, “that the dependance which the
learned world may place on any particular Transit-Account, will be in
proportion to the previous and subsequent care, which is found to
have been taken in a series of accurate and well conducted
observations, for ascertaining the going of the time-pieces, and fixing
the latitude and longitude of the place of observations, &c. And I am
the more desirous to be particular in these points, in order to do
justice to Mr. Rittenhouse, one of the committee; to whose
extraordinary skill and diligence is owing whatever advantage may
be derived, in these respects, to our observation of the Transit
itself.”—“Our great discouragement at our first appointment,”
continues the learned reporter, “was the want of proper apparatus,
especially good Telescopes with Micrometers. The generosity of our
Provincial Assembly soon removed a great part of this
discouragement, not only by their vote to purchase one of the best
reflecting Telescopes, with a Dollond’s micrometer;[112] but likewise
by their subsequent donation of one hundred pounds,” (this was in
sterling money, = $444) “for erecting Observatories and defraying
other incidental expences.[113] It was forseen, that on the arrival of the
Telescope, added to such private ones as might be procured in the
city, together with fitting up the instruments belonging to the
honourable the Proprietaries of the province—viz. the equal Altitude
and Transit Instruments and the large astronomical Sector,—nothing
would be wanted for the city Observatory in the State-House Square,
but a good Time-piece, which was easily to be procured. We
remained, however, still at a loss, how to furnish the Norriton
Observatory:[114] But even this difficulty gradually vanished.”

Thus it appears, that while the public contributions, and such

astronomical instruments suitable for the occasion as were the public
property, were principally at the disposal of the Philadelphia
committee, the Observatory at Norriton—which seems to have been
considered as a private establishment, belonging to an individual,—
depended almost entirely on other resources. Even an excellent
reflecting telescope (though without a micrometer,) the property of
the Library Company of Philadelphia, and to which institution it was a
donation from the Hon. T. Penn,—the same that had been used by
Messrs. Macon and Dixon, when employed in settling the boundary
lines of Pennsylvania and Maryland—was necessarily appropriated
to the use of Mr. Owen Biddle, who was appointed by the Society to
conduct the Observation of the Transit, near Cape Henlopen.

The Norriton Observatory was, notwithstanding, at last completely

furnished with every instrument proper for the occasion. In
consequence of some previous communications made by Dr. Smith
to the Hon. Mr. T. Penn of London, and to the Rev. Mr. Maskelyne,
the British astronomer-royal at Greenwich, the former worthy and
liberal gentleman had sent, for the use of the Norriton committee, a
reflecting Telescope with Dollond’s Micrometer—such as the doctor
had expressed a wish to obtain; and requested, that after the
committee should have made their observations with it, it should be
presented in his name to the College.[115] Through the means of Dr.
Smith, likewise, an astronomical quadrant of two and an half feet
radius, made by Sisson, the property of the East-Jersey
proprietaries, was procured by Mr. Lukens from the Earl of Stirling,
surveyor-general of that province. This had been pretty early sent up
by Mr. Lukens to Mr. Rittenhouse, and was used by him in
ascertaining the latitude of his Observatory.

In addition to these and some other apparatus used at Norriton on

the occasion—a catalogue and description of the whole of which, are
contained in Dr. Smith’s before-mentioned report—the zeal, industry,
and talents of Mr. Rittenhouse enabled him to furnish his
Observatory with the three following described instruments, made by
himself,[116] as described by Dr. Smith.

1. An Equal Altitude Instrument—its telescope three and an half

feet focal length, with two horizontal hairs, and a vertical one in its
focus; firmly supported on a stone pedestal, and easily adjusted to a
plummet-wire four feet in length, by two screws, one moving in a
North and South, the other in an East and West direction.

2. A Transit Telescope, fixed in the meridian, on fine steel points;

so that the hair in its focus could move in no other direction than
along the meridian; in which were two marks, South and North,
about 330 yards distance each; to which it could be readily adjusted
in an horizontal position by one screw, as it could in a vertical
position, by another.

3. An excellent Time-piece—having for its pendulum-rod a flat

steel bar, with a bob weighing about twelve pounds, and vibrating in
a small arch. This went eight days, did not stop when wound up,
beat dead seconds, and was kept in motion by a weight of five
pounds.[117]
 Thus was the Norriton Observatory furnished with all the more
immediately necessary apparatus, in readiness for the important
event which was the main object of these arduous exertions. Much
credit was due to Dr. Smith, much to Mr. Lukens and the other
gentlemen engaged on this occasion, for the assistance which he,
and they, afforded Mr. Rittenhouse. Yet the doctor himself very
candidly says—in reporting the proceedings of the Norriton
committee to the Philosophical Society,—“other engagements did
not permit Mr. Lukens or myself to pay much attention to the
necessary preparations; but we knew that we had entrusted them to
a gentleman on the spot, who had joined to a complete skill in
mechanics, so extensive an astronomical and mathematical
knowledge, that the use, management, and even the construction of
the necessary apparatus, were perfectly familiar to him. Mr. Lukens
and myself could not set out for his house till Thursday, June 1st;
but, on our arrival there, we found every preparation so forward, that
we had little to do, but to adjust our respective telescopes to distinct
vision. He had fitted up the different instruments, and made a great
number of observations, to ascertain the going of his Time-piece,
and to determine the latitude and longitude of his Observatory. The
laudable pains he hath taken in these material articles,” continues
Dr. Smith in his report, “will best appear from the work itself,—which
he hath committed into my hands, with the following modest
introduction; giving me a liberty, which his own accuracy, care and
abilities, leave no room to exercise.”[118]

Norriton, July 18th 1769.

“Dear Sir,

“The enclosed is the best account I can give of the Contacts,

as I observed them; and of what I saw during the interval between
them. I should be glad you would contract them, and also the other
papers, into a smaller compass,—as I would have done myself, if I
had known how. I beg you would not copy any thing merely because
I have written it, but leave out what you think superfluous.—I am,
with great esteem and affection, yours, &c.
 David Rittenhouse.[119]

To Rev. Dr. Smith.”

The result of the Norriton Observations of the Transit of Venus—as

well as those also made under the auspices of the American
Philosophical Society, at Philadelphia and Cape Henlopen—will be
found, in detail, in the first volume of the Transactions of that Society.
[120]
And “the Work itself,” to which Dr. Smith refers, in his Report of
the Proceedings of the Norriton Committee, bears ample testimony
to the transcendent Astronomical Abilities of Mr. Rittenhouse.—Four
days after the Transit, Dr. Smith transmitted to the Hon. Mr. Penn, in
London, a short account of the Norriton Observations, more
particularly mentioning the times of the Contacts, and a few other
circumstances attending them. This was speedily communicated by
Mr. Penn to the Rev. Mr. Maskelyne,[121] the Astronomer Royal; who,
acknowledging the receipt of the communication, by a note, dated at
Greenwich the 2d of August, 1769, says—“I thank you for the
account of the Pennsylvania Observations (of the Transit,) which
seem excellent and complete,[122] and do honour to the gentlemen
who made them[123], and those who promoted the undertaking;—
among whom, I reckon yourself[124] in the first place.”[125]

Here the observation will emphatically apply;—Laus est, â viro

laudato laudari.

Before this interesting occurrence in the life of Mr. Rittenhouse is

finally passed over, the reader’s attention is solicited to the beautiful
and animated description given by Dr. Rush, in his Eulogium, of the
sensations which must have been more particularly experienced by
that extraordinary man, on the near approach of the long-expected
Phænomenon.—“We are naturally led here,” says the learned
Professor, “to take a view of our Philosopher, with his associates, in
their preparations to observe a phænomenon which had never been
seen but twice[126] before, by any inhabitant of our earth, which would
never be seen again by any person then living, and on which
depended very important astronomical consequences. The night
before the long-expected day, was probably passed in a degree of
solicitude which precluded sleep. How great must have been their
joy, when they beheld the morning sun!—‘and the whole horizon
without a cloud;’ for such is the description of the day, given by Mr.
Rittenhouse, in the report referred to by Dr. Smith. In pensive silence
and trembling anxiety, they waited for the predicted moment of
observation: it came,—and brought with it all that had been wished
for, and expected, by those who saw it.—In our Philosopher, it
excited—in the instant of one of the contacts of the planet with the
sun, an emotion of delight so exquisite and powerful, as to induce
fainting. This,” then remarks Dr. Rush, “will readily be believed by
those who have known the extent of that pleasure which attends the
discovery, or first perception of Truth.”

On the 9th of November, following, there was a Transit of Mercury

over the Sun. An account of this phænomenon,—as observed at
Norriton by William Smith, d. d. John Lukens, Esq. and Messrs.
David Rittenhouse and Owen Biddle, the Committee appointed for
that Observation by the American Philosophical Society,—was
drawn up and communicated to the Society, by direction and in
behalf of the Committee, by Dr. Smith: this will be found in the first
volume of the Society’s Transactions. In this report it is remarked,
that—“the first time that ever Mercury was observed on the Sun’s
disk, was by Gassendus at Paris, October 28th 1631, O. S. and that
the Transit of Nov. 9th was the fourth in that class; the two
intermediate ones, each at forty-six years distance, having been
observed by Dr. Halley, in 1677 and 1723.”

Mr. Maskelyne, the celebrated English Astronomer before

mentioned,[127]—in a letter to Dr. Smith, of the 26th of December,
1769—expressed a wish “that the difference of Meridians of Norriton
and Philadelphia, could be determined by some measures and
bearings, within one-fiftieth or one-hundredth part of the whole; in
order to connect,” continues Mr. Maskelyne, “your observations of
the Longitude of Norriton with those made by Messrs. Mason and
Dixon, in the course of measuring the degree of Latitude.”—This
request of the Astronomer Royal was communicated to the
Philosophical Society of Philadelphia; in consequence of which, Dr.
Smith, Mr. Lukens and Mr. Rittenhouse, were appointed to make the
terrestrial measurement required. These gentlemen, having taken to
their assistance Mr. Archibald M’Clean and Mr. Jesse Lukens, two
able and experienced Surveyors, commenced their operations at
Norriton, early on the 2d day of July following, and completed their
survey on the 4th day of that month. The Report of the able
Committee, to which this business was assigned by the American
Philosophical Society, is also contained in the first volume of the
Transactions of that learned Body. After giving various calculations,
resulting from the operations of that committee, the Reporter says
—“Hence, by the above measurement and work, we get Norriton
Observatory 52″ of time West of the Observatory in the State-house
Square; which is exactly what we got by that excellent element, the
external contact of Mercury with the Sun, Nov. 9th 1769.”—“The
external contact,” continues the Reporter, “gave it something more;
owing, no doubt, to the difference that will arise among Observers, in
determining the exact moment when the thread of light is
compleated: and the mean of all our Observations gives the
difference of Meridians, between Norriton and Philadelphia, only 4″
of time more than the terrestrial measurement, and the external
contact of Mercury, gave it,—which may be taken as a very great
degree of exactness; if we consider that the difference of Meridians,
between the long-established Observatories of Greenwich and Paris,
(as Mr. De la Lande writes, Nov. 18th 1762,) was not then
determined within 20″ of time—For, he says, ‘some called it 9′ 15″;
others, 9′ 40″;’ but that he himself commonly used 9′ 20″, though he
could not tell from what Observations it was deduced.[128]—Finally,
the Report fixes Philadelphia to be 5h 0′ 37″, and Norriton, 5h 1′ 29″
West from Greenwich.[129] The Latitude of Norriton, as deduced from
the actual mensuration just mentioned, connected with Observations
previously made by Mr. Rittenhouse—predicated also, in part, on
antecedent Calculations of Messrs. Mason and Dixon, who, (having
been furnished with a complete Astronomical Sector,) had
ascertained the southernmost point of the City of Philadelphia to be
in Latitude 39° 56′ 29″,4. N.—is stated, in the same Report, as being
40° 9′ 31″. It came out, by the measurement, 25″.09 less North, with
respect to the southernmost point of Philadelphia, than Mr.
Rittenhouse’s Observations had given it; and, in making these, he
had no better Instrument than Sisson’s two-and-an half feet
Quadrant. Nevertheless, the framer of the Report remarks, “as both
were fixed by celestial observations and experienced Men, the small
difference ought perhaps to be divided; and if a mean be taken, to
reconcile it with the terrestrial measure, the Lat. of the south point of
Philadelphia would be 39° 56′ 42″; and that of Norriton, 40° 9′ 43″.[130]

The same Volume of the American Philosophical Transactions that

comprehends the communications of these Proceedings—as well as
various Observations, made at different places, on the then recent
Transit of Venus—contains also a Memoir, by Dr. Smith, deducing
the Sun’s Parallax from a comparison of the Norriton and some other
American Observations of the Transit of Venus, in 1769, with the
Greenwich and some other European Observations of the same:
And with this paper, its learned writer has incorporated a
communication, on the same subject, made to him by Mr.
Rittenhouse.

Until about the period at which the latest of these favourite

transactions of Mr. Rittenhouse took place—namely, his geometrical
employment in ascertaining the Latitude and Longitude of Norriton
and Philadelphia, respectively,—he continued to reside on his farm
at Norriton. And here he still carried on, with the aid of some
apprentices and journey-men, his self-acquired occupation of a
Clock and Mathematical Instrument-maker: combining, at intervals,
with these mechanical pursuits, an unceasing attention to his
philosophical studies and researches; and occasionally employing
himself, principally with a view to his health, in some of the
occupations of Husbandry. Ever an economist of Time, of which he
well knew the inestimable value, none of his hours which could be
spared from necessary sleep were suffered to be unemployed. In
this rural abode, he enjoyed the comforts of domestic life amidst his
little family, consisting only of an amiable wife and two young
children. In short, no part of his time was unengaged, or uselessly
passed; although he, not unfrequently, felt the solace of friendly
calls, and was gratified by visits from persons of science, worth, and
distinction.

The writer of these memoirs designed to narrate those

circumstances most worthy of notice, in the Life and character of Mr.
Rittenhouse, in their chronological order; and this plan will be
generally adhered to. Having followed our philosopher in his
astronomical and mechanical pursuits, up to the year 1770, it
therefore becomes proper to recur to a period of his life some few
years earlier, in order to introduce the history of his Orrery,[131] before
mentioned; a piece of mechanism which is admitted, by all
competent judges of its merit, to be one of the greatest of his works.

The Planetarium invented by Mr. George Graham,[132]—and a

model of which was improperly retained by Mr. Rowley, its
constructor,—had, long before the appearance of Mr. Rittenhouse’s
machine, acquired the name of an Orrery; in compliment to Richard
Boyle, Earl of Orrery,[133] who merely patronized the construction of
one, from the artist Rowley’s pirated model. This complimentary
appellation of Mr. Graham’s then newly invented Planetarium is said
to have been bestowed upon it by Lord Orrery’s friend, Sir Richard
Steele:[134] and, the name being thus applied to that machine, all
those of the nature of Planetaria, subsequently constructed,—
however variant in usefulness or design, from the original one
bearing the name of an “Orrery,”—were denominated Orreries.[135] In
compliance, then, with long established usage, Mr. Rittenhouse
modestly called his Planetarian-machine, from the first projection of
it, an Orrery; although the entire merit, both of the invention and
construction, belonged to himself.[136]

It is not ascertained, at what time Mr. Rittenhouse first conceived

the plan of that extensive, complicated and inestimable Orrery, which
he afterwards executed. Probably, he had long thought on the
subject, before he publicly announced his design. It is certain,
however, that before the beginning of the year 1767, there was some
correspondence and some understanding, respecting it, between
himself and the Rev. Mr. Barton. It appears in fact, that, prior to that
period, Mr. Barton had been fully apprized of his brother-in-law’s
desire to carry into effect his meditated design of constructing a
complete Orrery, on a plan entirely new; and that some arrangement
was previously made, between these gentlemen; by which Mr.
Barton undertook to indemnify Mr. Rittenhouse, for such actual
expenditures as he should incur in making the machine and his loss
of time while employed in the work, not exceeding a stipulated sum;
provided he should not be able to dispose of it, when finished, at a
price then fixed on. The prudential caution of our young Philosopher
(then about thirty-four years of age,) and the public spirit of his
friend, grounded on the confidence he had in the artist’s talents and
abilities, were alike evinced on this occasion.

The first written communication made by Mr. Rittenhouse to Mr.

Barton, on the subject of the Orrery, is contained in a letter under the
date of Jan. 28th, 1767: it is in these words:—“I am glad you took the
pains to transcribe, and send me, Martin’s Account of Orreries.”[137]
“Two forms (he says) have principally obtained, the Hemispherical
Orrery and the Whole Sphere. But the idea given us by the former, is
very unnatural and imperfect. An Orrery, then, adapted to an
Armillary Sphere is the only machine that can exhibit a just idea of
the true System of the World.”—“But in my opinion,” says Mr.
Rittenhouse, “the latter is likewise very unnatural; for, what has a
Sphere, consisting of a great number of metaline Circles, to do with
the true System of the World? Is there one real, or so much as
apparent Circle, in it? (the bodies of the Sun and Planets excepted.)
Are they not all merely imaginary lines, contrived for the purpose of
calculation? I did not intend to let one of them have a place in my
Orrery, except the Zodiac, on which I would have the true latitude
and longitude of each planet pointed out by its proper Index.”

“I did not design a Machine, which should give the ignorant in

astronomy a just view of the Solar System: but would rather astonish
the skilful and curious examiner, by a most accurate correspondence
between the situations and motions of our little representatives of the
heavenly bodies, and the situations and motions of those bodies,
themselves. I would have my Orrery really useful, by making it
capable of informing us, truly, of the astronomical phænomena for
any particular point of time; which, I do not find that any Orrery yet
made, can do.”

“But,” continues Mr. Rittenhouse, “perhaps it may be necessary to

comply with the prevailing taste: If so, my plan must be entirely
altered;—and this is a matter that must be settled between you and
me, before I can proceed. However, I shall send you, in my next, a
particular account of my design; such as I would have it, if not limited
by the fear of making it too expensive.—A specimen (if I may so call
it) of the most curious part of it, though much smaller than that
intended for the Orrery, is now in hand, and I hope will soon be
finished.”

To this letter Mr. Barton returned the following answer.

“Lancaster, February 21st, 1767.

“Dear Brother,

“I received, a few days ago, yours of the 28th ult.—after it had

undergone the torture of some Dutchman’s pocket, which compelled
it to force its way through the cover: However, the inside did escape
without many fractures; so that I had the pleasure of getting it into
my hands in such a condition that I could read it.

“Had I known your distress, at the time you received my letter, I

should have sincerely felt for you. I well know the anxiety of an
husband, on such occasions, and my heart will ever join in sympathy
with him: For you, my feelings would have been doubled, as a
husband, as my friend and brother. Glad I am, therefore, that I have
no occasion to condole with you, but rather to rejoice; and I most
sincerely and affectionately congratulate you, on the escape and
recovery of your good girl, and wish you joy of your daughter. I
desire to offer my best regards to sister Nelly, for the compliment she
intended me, had her child been a boy. Her intention was kind, and I
hope to have the continuance of her favourable opinion of me.