One Nanometer PtIr Nanowires as High-Efficiency Bifunctional Catalysts for Electrosynthesis of Ethanol into High Value-Added Multicarbon Compound Coupled with Hydrogen Production

Multicarbon Compound Coupled with Hydrogen Production

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One Nanometer PtIr Nanowires as High-Eﬃciency Bifunctional

Catalysts for Electrosynthesis of Ethanol into High Value-Added

⊥

Kun Yin, Yuguang Chao, Fan Lv, Lu Tao, Weiyu Zhang, Shiyu Lu, Menggang Li, Qinghua Zhang,

Lin Gu, Hongbo Li, and Shaojun Guo*

Cite This: J. Am. Chem. Soc. 2021, 143, 10822 −10827

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ABSTRACT: The electrosynthesis of high-value-added multicarbon compounds coupled with hydrogen production is an eﬃcient

way to achieve carbon neutrality; however, the lack of eﬀective bifunctional catalysts in electrosynthesis largely hinders its

development. Herein, we report the ﬁrst example on the highly eﬃcient electrosynthesis of high-value-added 1,1-diethoxyethane

(

DEE) at the anode and high-purity hydrogen at the cathode using 1 nm PtIr nanowires (NWs) as the bifunctional catalysts. We

demonstrate that the cell using 1 nm PtIr nanowires as the bifunctional catalysts can achieve a reported lowest voltage of 0.61 V to

−

reach the current density of 10 mA cm , much lower than those of the Pt NWs (0.85 V) and commercial Pt/C (0.86 V), and also

can have the highest Faraday eﬃciencies of 85% for DEE production and 94.0% for hydrogen evolution in all the reported

electrosynthesis catalysts. The in situ infrared spectroscopy study reveals that PtIr NWs can facilitate the activation of O−H and C−

H bonds in ethanol, which is important for the formation of acetaldehyde intermediate, and ﬁnally DEE. In addition, the cell using

PtIr NWs as bifunctional catalysts exhibits excellent stability by showing almost no obvious decrease in the Faraday eﬃciency of the

DEE production.

ydrogen as a zero emission renewable energy carrier has

attracted enthusiastic attention because of the increas-

Therefore, controlling the highly selective oxidation of ethanol

to DEE coupled with hydrogen production is of great

signiﬁcance from the viewpoint of eﬃcient energy utilization.

Herein, we design a class of 1 nm PtIr nanowires (NWs) as

advanced bifunctional electrocatalysts for concurrently con-

verting ethanol into value-added DEE and renewable H₂.

Compared with Pt NWs and commercial Pt/C, PtIr NWs

exhibit remarkable catalytic performance for ethanol oxidation

reaction (EOR) and hydrogen evolution reaction (HER) in

acid ethanol solutions (no water inside). Moreover, we

fabricate a two-electrode cell by the use of PtIr NWs/C as

both an anodic catalyst for EOR and a cathodic catalyst for

HER in acid ethanol solutions. The cell requires a lowest

ingly serious energy crisis and environmental contamination

−12

issue.

The electrocatalytic system by coupling H₂

production at a cathode with highly value-added synthesis at

an anode is highly attractive from the viewpoint of atom

3,14

economy.

Ethanol, derived from biomass fermentation, has

been recognized as one of the most renewable energy carriers

15,16

and important green chemicals.

It can serve as liquid fuel

and a versatile precursor for synthesizing ﬁne chemicals.

Ethanol, as a class of abundant renewable green energy, can be

used to produce acetaldehyde, acetic acid, ethyl acetate,

ethylene, ether, 1-butene, 1,3-butadiene, and 1,1-diethoxy-

ethane. Among them, 1,1-diethoxyethane (DEE) is one of the

−2

voltage of 0.61 V to reach 10 mA cm in all the reported

most important ethanol products. In addition, ethanol

contains 13.04 wt % hydrogen, making it a potential hydrogen

storage medium. Hence, ethanol is an ideal choice for highly

catalysts, much lower than those of the Pt NWs (0.85 V) and

commercial Pt/C (0.86 V). The PtIr NWs-based cell can

achieve the best Faraday eﬃciency (FE) of DEE 85% in

value-added conversion concurrent with H production by

ethanol solution containing 0.5 M HClO , much higher than

electrocatalysis.

those of the Pt NWs (40.8%) and commercial Pt/C (23%).

Most importantly, PtIr NWs show excellent stability in the

oxidation of ethanol to DEE by showing almost no obvious

decrease in the FE for the DEE production.

Traditionally, hydrogen production from ethanol will

produce a lot of harmful gases. In industrial production,

ethanol is converted into high-value-added products, however,

18,19

mainly at high temperature and high pressure.

As a safe

and green method, the electrochemical oxidation of ethanol

20−31

Received: May 12, 2021

Published: July 19, 2021

has attracted more and more attention.

Ethanol as a single

reactant by electrochemical synthesis is faced with the problem

of generating lots of byproducts. Direct synthesis or single-step

synthesis of DEE from alcohols is an attractive alternative to

the conventional two-step process and has beneﬁted from the

17−19

lack of any need to use aldehydes or aldehyde derivatives.

2021 American Chemical Society

J. Am. Chem. Soc. 2021, 143, 10822−10827

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Journal of the American Chemical Society

electron microscopy (TEM) (Figure 1 a and Figure S1 ). The

Communication

The ultraﬁne PtIr alloy NWs were synthesized by a colloidal-

chemical approach, using platinum(II) acetylacetonate (Pt-

and Ir (PDF #06-0598) (Figure 1f). An atomistic observation

of randomly selected PtIr NWs (Figure 1g) demonstrates their

polycrystalline nature with abundant atomic steps and grain

boundaries. Besides, smaller-diameter NWs tend to be

defective/disordered. The corresponding energy-dispersive

spectroscopy (EDS) discloses the existence of element Pt and

Ir (Figure 1h).

To illustrate the growth mechanism and critical factors

during the formation process of ultraﬁne nanowires, a series of

products with various experimental conditions were inves-

tigated. The results revealed that PtIr nanoparticles were

formed at the initial stage. Then, the nanoparticle grew into

nanowires along the 1D direction and grew gradually with time

(

acac) ) and iridium(III) 2,4-pentanedionate (Ir(acac) ) as

metal precursors, CO in situ released from molybdenum

hexacarbonyl (Mo(CO) ) and (1-hexadecyl) trimethylammo-

nium bromide (CTAB) as structural directing agents, and

oleylamine as a reducing agent. The as-synthesized product

presents ultraﬁne 1D morphology with a diameter of 1.0 nm

and an average length of 30 nm, determined by transmission

(

Figure S3). During the synthetic process, the content of Ir in

PtIr nanowires increased gradually and reached the maximum

at 5 h (Figure S4). Notably, there were no obvious changes in

the morphology and composition of PtIr nanowires with the

further extension of reaction time. In addition, when the

surfactant and reducing agent were replaced by (1-hexadecyl)

trimethylammonium chloride (CTAC) and tungsten carbonyl

(

W(CO) ), respectively, the products could still maintain the

ultraﬁne 1D feature (Figures S5 and S6). Especially, when the

synthesis was conducted without surfactant addition or using

glucose as the reducing agent, the ultra ﬁne 1D morphology

could not be obtained (Figures S7 and S8). The above results

reveal that the formation of PtIr nanowires is highly dependent

on the use of carbonyl salts and surfactants and mainly follows

the oriented attachment mechanism. As a comparison, Pt

nanowires were synthesized by a standard step without

introducing an Ir precursor (Figure S9).

The electrocatalytic properties of ultraﬁne PtIr nanowires

toward EOR and HER were assessed. Before the electro-

chemical tests, the catalysts were prepared by depositing the

nanowires onto the commercial carbon supports (Ketjen

Black-300J) and subsequently were washed with acetic acid to

remove residual surfactants around the surface of the

nanowires (Figure S10). The resulting carbon supported

nanocrystal catalysts were denoted as PtIr NWs/C and Pt

NWs/C, respectively. To assess the EOR activity, all the

catalysts were ﬁrst pretreated by applying the consecutive

cyclic potential cycles at a sweep rate of 500 mV s⁻until the

cyclic voltammograms (CVs) became stable. We found that

PtIr NWs/C exhibits excellent electrocatalytic performance for

EOR and HER when using sulfuric acid or perchloric acid

electrolytes (Figures S11 −S13 ). For the optimization, the PtIr

NWs with various Pt−Ir atomic ratios (Pt68Ir 32 NWs, Pt78Ir22

Figure 1. Morphology and structure characterization of PtIr NWs. (a)

Transmission electron microscopy (TEM) image, (b) scanning TEM

(

STEM) image and its corresponding STEM-energy-dispersive

spectroscopy (EDS) elemental mappings, (c and d) X-ray photo-

electron spectroscopy (XPS) spectra, (e) high-angle annular dark-ﬁeld

scanning transmission electron microscopy (HAADF-STEM) image,

(f) power X-ray diﬀraction (PXRD) pattern, (g) HAADF-STEM

image, and (h) EDS pattern of PtIr NWs. Note that the Fourier

transform (FFT) images (e₁and e ) were taken from the

corresponding two dashed squares (areas e and e ) in e, and (e )

integrated pixel intensity of crystal phase was taken from the cyan

solid rectangle in e.

high-angle annular dark-ﬁeld scanning transmission electron

microscopy (HAADF-STEM) element mappings conﬁrm the

uniform distribution of Pt and Ir along the PtIr nanowire

(

Figure 1b and Figure S2). The high-resolution X-ray

NWs, and Pt91Ir NWs) were synthesized (Figure S14). The

photoelectron spectroscopy (XPS) of Pt 4f and Ir 4f show

the binding energies of 75.1 and 71.8 eV, assigned to the

electrocatalytic tests revealed that Pt68Ir32 NWs/C exhibited

much higher electrocatalytic performance than Pt78Ir22 NWs/C

32−36

metallic Pt 4f₅_/₂and Pt 4f₇_/₂(Figure 1c),

energies of 64.5 and 61.5 eV, assigned to the metallic Ir 4f

and the binding

and Pt91Ir

NWs/C (Figure S15).

SO ethanol electrolyte, the

In N -saturated 0.5 M H

37−40

and Ir 4f₇_/₂(Figure 1d).

Furthermore, the atomic ratio of

optimal PtIr NWs/C shows the lowest onset potential with the

Pt/Ir was estimated to be 2.1:1 by XPS.

order of PtIr NWs/C < Pt NWs/C ≈ Pt/C (Figure 2a,b).

−

The crystal phase of the PtIr NWs was identiﬁed from the

atomic stacking sequence and the corresponding fast Fourier

transform (FFT) pattern. The FFT patterns, taken from

regions e and e , marked as white dashed squares in Figure

When the current density reaches 30 mA cm , the potential

for EOR of the PtIr NWs decreases by 480 and 470 mV

relative to those of commercial Pt/C and Pt NWs, respectively.

Moreover, PtIr NWs/C delivers the lowest Tafel slope of 220

−

e ,e , show that the PtIr nanowires have fcc phase with two

mV dec in all the investigated catalysts (Figure S16a),

indicating the accelerated EOR kinetics on the ultrathin PtIr

NWs/C structure. In light of the noble metals, such as Pt and

Ir, applied for this catalytic system, we normalized the mass

activities at 0.3 V vs saturated calomel electrode (SCE) on the

basis of the mass of noble metal determined by inductively

typical characteristic diﬀraction patterns of [011] and [001]

zones, and the average lattice spacing of PtIr (200) facets on

one random PtIr NW is 0.18 nm (Figure 1e ). The powder X-

ray diﬀraction (PXRD) pattern of PtIr nanowires shows that

the diﬀraction peaks locate those between Pt (PDF #04-0802)

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Communication

NWs/C (8.87 mA mg_P_t⁻¹) and Pt/C (15.6 mA mg_P_t⁻¹),

respectively.

The durability of as-synthesized catalysts in HER process

was evaluated by applying chronopotentiometry at a current

−

density of 10 mA cm for 27 h. PtIr NWs/C displayed an

almost constant potential during the 27 h test, conﬁrming its

excellent HER stability (Figure 2e). However, the catalytic

performance of Pt NWs/C and commercial Pt/C decreased

signiﬁcantly under the same conditions. In addition, the FE of

PtIr NWs/C was 94% for hydrogen production, higher than

those of Pt NWs/C (87%) and commercial Pt/C (91%),

respectively (Figure 2f). Hence, these results reveal that as-

synthesized PtIr NWs/C has excellent activity and stability and

high selectivity for hydrogen production.

To reveal the essence for the superior electrocatalytic

performance on PtIr NWs/C catalyst, the reaction kinetics of

PtIr NWs/C, Pt NWs/C, and Pt/C were investigated.

Particularly, PtIr NWs/C exhibits Tafel slopes of 220 and

−

86 mV dec for EOR and HER in 0.5 M H SO ethanol

2 4

solution, respectively, much lower than those of Pt NWs/C

and Pt/C, indicating the fastest reaction kinetics of the

synchronous oxidative dehydrogenation of ethanol and HER.

Besides, the Bode plots in the electrochemical impedance

spectra (EIS) reveal that the frequency peak of PtIr NWs/C

decreases and shifts to a higher frequency compared with those

of Pt NWs/C and Pt/C (Figure S21a ), suggesting a decreased

Faradaic resistance and accelerated surface reaction kinetics. In

addition, the Nyquist plot of PtIr NWs/C in the EIS shows the

smallest high-frequency semicircle (Figure S21b ), implying the

smallest charge-transfer resistance and the fastest kinetics.

Inspired by the excellent electrocatalytic performance of PtIr

NWs/C for the anodic EOR and cathodic HER, a two-

electrode electrolyzer employing PtIr NWs/C as both the

anode and the cathode in 0.5 M H SO ethanol electrolyte was

Figure 2. Anodic alcohol oxidation and cathodic HER of diﬀerent

catalysts. (a) Linear sweep voltammetry (LSV) and (b) potential at a

current density of 10 mA cm⁻of PtIr NWs/C, Pt NWs/C, and Pt/C

catalysts for alcohol oxidation in 0.5 M H SO ethanol solution (scan

−

rate: 5 mV s ). (c) LSV and (d) potential at a current density of 10

_m_A_c_m₋2 of PtIr NWs/C, Pt NWs/C, and Pt/C catalysts for HER in

−

.5 M H SO ethanol solution (scan rate: 5 mV s ). (e) Potential−

time curves of PtIr NWs/C, Pt NWs/C, and Pt/C catalysts at a

current density of 10 mA cm . (f) FE for hydrogen production on

PtIr NWs/C, Pt NWs/C, and Pt/C catalysts.

−

constructed (Figure 3a). The PtIr NWs/C catalyst shows a

noticeably decreased potential of 0.61 V at 10 mA cm⁻

(Figure 3b), much lower than those of Pt NWs/C (0.85 V)

and Pt/C (0.86 V) catalysts, respectively (Figure 3c),

indicating its remarkable bifunctional catalytic activity. More-

over, PtIr NWs/C delivers the lowest Tafel slope of 456 mV

coupled plasma optical emission spectroscopy (ICP-OES). PtIr

−

NWs/C exhibits a high mass activity of 55.6 mA mg_P_t₊_I_r

almost 4.7- and 6.3-fold higher than those of Pt NWs/C (11.7

−

−1

mA mg_P_t) and Pt/C (8.7 mA mg_P_t), respectively. Specially,

PtIr NWs/C also exhibits much higher performance than that

of PtIr NPs/C (Figures S17 and S18). This may be attributed

by the fact that PtIr NWs have rich defects and low

crystallinity. It should be noted that the blank carbon paper

shows negligible EOR performance (Figure S19 ). In addition,

the long-term chronoamperometry test in 0.5 M H SO

−1

dec in all the investigated catalysts (Figure S22).

Apart from the cathode product of H , the anode product of

DEE (conﬁrmed by gas chromatography−mass spectrum

(GC−MS)) can also be synchronously detected in the two-

electrode reaction (Figure S23). In addition, the H nuclear

magnetic resonance (NMR) reveals that the methyne group

(CH) can be detected in the solution, further conﬁrming the

formation of DEE during the electrocatalytic process (Figure

S24 ). The FE of DEE is determined by the product yield,

which is quantiﬁed by the standard curve (Figure S25). In the

sulfuric acid ethanol solution, PtIr NWs/C represents a higher

FEs for the production of DEE than those of Pt NWs/C and

Pt/C at a wide potential from 1.2 to 2.0 V (Figure 3e). The

oxidation products of ethanol in the two-electrode system at

diﬀerent potentials were detected by gas chromatography

(Figure 3c and Tables S1 −S3). Compared with the Pt/C

catalyst, PtIr NWs/C and Pt NWs/C display less variation of

FEs with various potentials. The optimized FE on PtIr NWs/C

can reach 77.8% at 1.8 V, which is the highest in all the

catalysts. This indicates that the PtIr NWs catalyst can still

have high selectivity for DEE at a high potential.

ethanol solution revealed that PtIr NWs/C has excellent

durability for EOR (Figure S20).

The HER performance of PtIr NWs/C, Pt NWs/C, and Pt/

C was investigated in N -saturated ethanol solution containing

−

.5 M H SO at a scan rate of 5 mV s (Figure 2c). We found

2 4

that PtIr NWs/C exhibits the highest HER activity among

diﬀerent catalysts and that the onset potential follows the order

of PtIr NWs/C < Pt NWs/C < Pt/C. PtIr NWs/C shows a

−

potential of −150 mV at 10 mA cm , much lower than those

of Pt NWs/C (−280 mV) and commercial Pt/C (−300 mV)

(

Figure 2d). Furthermore, PtIr NWs/C shows the lowest Tafel

−

slope of 186 mV dec in all the investigated catalysts (Figure

S16b ), indicating the fastest HER kinetics on PtIr NWs/C. We

further normalized the mass activities at −0.19 V vs SCE on

the basis of the real mass of noble metal determined by ICP-

OES. PtIr NWs/C exhibits a high mass activity of 89.9 mA

The durability of PtIr NWs/C, Pt NWs/C, and Pt/C

catalysts at various potentials was evaluated in the two-

−

mg_P_t₊_I_r, almost 10.1- and 5.7-fold higher than those of Pt

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J. Am. Chem. Soc. 2021, 143, 10822−10827

process of the Pt/C and PtIr NWs/C catalysts (Figure 4 a,b

Communication

sulfuric acid were added, indicating that the condensation

between acetaldehyde and ethanol was driven by acid-catalysis.

To further conﬁrm the reaction mechanism of electro-

catalytic ethanol dehydrogenation−acetalation, in situ infrared

(

IR) spectroscopy was implemented during the electrocatalytic

Figure 4. Reaction mechanism of oxidative dehydrogenation

acetalization of ethanol. (a and b) In situ FTIR spectra analysis of

the electrocatalytic DEE production over PtIr NWs/C. (c) Possible

pathway of ethanol oxidation to DEE.

Figure 3. Alcohol electrochemical oxidation performance of PtIr

NWs/C // PtIr NWs/C, Pt NWs/C // Pt NWs/C, and Pt/C // Pt/

C. (a) Schematic diagram of the oxidation of ethanol to high-value-

added product and hydrogen production cell. (b) LSV of the PtIr

NWs/C // PtIr NWs/C, Pt NWs/C // Pt NWs/C, and Pt/C // Pt/

−

C cells in 0.5 M H SO ethanol solution at a scan rate of 5 mV s .

and Figure S31). The red shifts of OH and CH in

−

(

c) Potential at j = 10 mA cm , (d) the FEs of DEE in diﬀerent acids

V = 1.4 V), and (e) FEs of DEE at PtIr NWs/C, Pt NWs/C, and Pt/

ethanol vibration over PtIr NWs/C indicate the existence of an

interaction between adsorbed ethanol and PtIr nanowires.

Moreover, there were much higher vibration peaks of OH

C before and after i−t test at 1.0 V (t = 3000 s).

and CH on PtIr NWs/C than on Pt/C, disclosing the

stronger adsorption ability of ethanol on PtIr NWs/C. In

addition, the two gradually enhanced negative IR peaks at 1728

electrode system (Figure 3e). After 3000 s i−t tests, the FEs on

the PtIr NWs/C catalyst had no obvious change, especially in

−

.4 and 2.0 V, implying the excellent stability. From 1.2 to 2.0

and 1180 cm are attributed to the vibrations of CO and

COC bonds, respectively, disclosing the formation of

acetaldehyde intermediate and DEE (Figure 4b). Thereby, the

V, the FE of DEE production based on the PtIr NWs catalyst

after the i−t durability test remained at a high level without

obvious attenuation, which is higher than those of Pt NWs and

Pt/C. Moreover, the synchronous EOR and HER over the PtIr

NWs/C catalyst in a two-electrode electrolyzer can also work

e ﬃ ciently in various inorganic acid ethanol solutions (Figures

S26 −S28). Especially, the PtIr NWs/C catalyst shows the

highest activity in perchloric acid ethanol solution, and the FE

of DEE reaches 85% at 10 mA cm⁻(Figure 3d). The

diﬀerence of FE in diverse acid is probably attributed to their

acidity in ethanol solution, which determines the rate and

intensity of acetalation.

overall process of ethanol converting to DEE and H was

divided into two steps (Figure 4c): (I) Ethanol was

dehydrogenated and converted to acetaldehyde and H on

the anode, and the H was subsequently transported and

reduced to H on the cathode via electrocatalysis; (II) the

generated acetaldehyde was spontaneously converted to DEE

via acid-catalyzed acetalation.

In this contribution, we ﬁrst report the synthesis of 1 nm

PtIr nanowires as advanced bifunctional catalysts for the

concurrent electrolytic production of high-value-added DEE at

an anode and high-purity hydrogen at a cathode. We ﬁnd that

the bifucntional 1 nm PtIr nanowires-based cell can achieve a

reported lowest voltage of 0.61 V for DEE production to reach

In order to understand the mechanism of the DEE

formation by ethanol oxidation, the electrocatalytic conversion

process of ethanol to DEE and H was investigated by the

designed control experiments. Neither DEE nor H can be

−2

a current density of 10 mA cm and the highest FEs of 85%

detected in the two-electrode electrolyzer in the absence of

electricity (Table S3), suggesting that electricity is a

prerequisite in the process of DEE production. When no

acid was added into the ethanol in the two-electrode system,

the ethanol was converted to acetaldehyde and no DEE was

detected in the solution, implying the decisive role of acid

electrolyte for DEE production (Figures S29 and S30 ). In

addition, in the absence of electricity, DEE was detected in the

ethanol and acetaldehyde mixed solution after a few drops of

for DEE production and 94.0% for hydrogen evolution in all

the reported electrosynthesis catalysts. The in situ infrared

spectroscopy study reveals that the OH and CH bonds in

ethanol can be more eﬀectively activated on PtIr NWs than on

Pt/C, which is the key in the following formation of

acetaldehyde intermediate and ﬁnally DEE. The PtIr NWs-

based cell also demonstrates almost no obvious decrease in the

FE of DEE, revealing the robust stability of 1 nm PtIr NWs.

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J. Am. Chem. Soc. 2021, 143, 10822−10827

Journal of the American Chemical Society

https://pubs.acs.org/doi/10.1021/jacs.1c04626.

Communication

ASSOCIATED CONTENT

sı Supporting Information

The Supporting Information is available free of charge at

ACKNOWLEDGMENTS

■

This study was ﬁnancially supported by the National Science

Fund for Distinguished Young Scholars (No. 52025133),

Beijing Natural Science Foundation (JQ18005), Tencent

Foundation through the XPLORER PRIZE, National Natural

Science Foundation of China (22002003), and the China

Postdoctoral Science Foundation (No. 2019TQ0001 and

Discussions of experimental details, ﬁgures of statistics of

diameter and length, STEM-EDX mapping, TEM

images, SEM-EDS images, anodic ethanol oxidation

and cathodic HER polarization curves, PXRD patterns,

EDS patterns, LSV, alcohol oxidation, Tafel slopes, i−t

curves, Bode phase plots, GC signal, GC−MS spectrum,

020M670020).

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