In Situ Derived Bi Nanoparticles Confined in Carbon Rods as an Efficient Electrocatalyst for Ambient N2Reduction to NH3

E ﬃ cient Electrocatalyst for Ambient N Reduction to NH ₃

Article

In Situ Derived Bi Nanoparticles Conﬁned in Carbon Rods as an

Fengyi Wang, Longcheng Zhang, Ting Wang, Fang Zhang, Qian Liu, Haitao Zhao, Baozhan Zheng,*

Juan Du,* and Xuping Sun *

Cite This: https://doi.org/10.1021/acs.inorgchem.1c01130

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sı Supporting Information

ABSTRACT: Electrocatalytic N reduction is deemed as a prospec-

tive strategy toward low-carbon and environmentally friendly NH₃

production under mild conditions, but its further application is still

plagued by low NH yield and poor faradaic eﬃciency (FE). Thus,

electrocatalysts endowing with high activity and satisfying selectivity

are highly needed. Herein, Bi nanoparticles in situ conﬁned in carbon

rods (Bi NPs@CRs) are reported, which are fabricated via thermal

annealing of a Bi-MOF precursor as a high-eﬃciency electrocatalyst

for artiﬁcial NH₃synthesis with favorable selectivity. Such an

electrocatalyst conducted in 0.1 M HCl achieves a high FE of

−

−1

1.50% and a large NH yield of 20.80 μg h mg

at −0.55 and

cat.

−

0.60 V versus reversible hydrogen electrode, respectively, which also

possesses high electrochemical durability.

INTRODUCTION

nanosheet, mosaic Bi nanosheet, and Bi nanodendrite.

■

Apart from precisely tuning the morphology, researchers also

focus on decreasing the size or increasing the dispersity of Bi

nanoparticles (Bi NPs).

reducing the size of catalysts or increasing the dispersity can

eﬃciently increase the surface area of catalysts, thus exposing

more active sites, leading to enhancement of electrochemical

performances.

tion caused by downsizing particle size and intrinsic low

conductivity impose the electrochemical performance of Bi

As one of the most essential raw materials, NH has been

extensively employed to make fertilizer and pharmaceutical

40,41

−3

Previous research reported that

production.

Moreover, it also can be used as an ideal green

carbon-free energy carrier and potential transportion fuel.

Nevertheless, industrial scalable production of NH₃is

commonly through the Haber−Bosch process with H and

N as synthesis gas, which is operated at severe synthetic

conditions, accompanied by massive CO emission. There-

fore, an energy-saving and environmentally friendly approach

41,42

However, major problems of self-aggrega-

21,35

NPs.

Aimed at overcoming these problems hereinbefore,

for NH synthesis is in urgent demand.

using a carbon matrix as a conductive skeleton can improve its

electrical conductivity and support the active particles to

restrain their aggregation. Moreover, in situ forming Bi NPs

conﬁned in a carbon scaﬀold would suppress the further

growth of Bi NPs to reduce the size to some extent. So, it is

promising to design Bi NPs conﬁned in carbon rods derived

from a MOF as electrocatalyst for the NRR, which, however,

has not been reported before.

Electrochemical N reduction is an alternative route for

−10

realizing sustainable ambient NH synthesis,

yet the high

chemical inertness of a NN triple bond is hard to break in a

1−13

chemical reaction.

It is reported that noble metals can

eﬃciently activate N , but their practical scalable applications

in N reduction reaction (NRR) are still restricted by high cost

4−18

and scarcity.

Research focus of NRR has thus transferred

19−32

into noble-metal-free alternatives.

Herein, we report that Bi NPs uniformly entrapped in MOF

derived carbon rods (Bi NPs@CRs) can perform favorable

NRR performance under ambient conditions. When tested in

Bi-based catalysts are appealing for an intriguing candidate

for an eﬃcient NRR electrocatalyst due to their intrinsic

catalytic activity, earth-abundance, low cost, and eco-friend-

3−36

liness.

Meantime, Bi as a main group metal with tunable

Received: April 12, 2021

p-electron density can selectively promote the reductive

absorption of N to form N H* but has no eﬀect on the

binding energy of the later intermediates, and also conﬁnes the

surface electron accessibility, thus suppressing the HER

7,38

process.

Currently, encouraging advances have been

gained for the NRR on Bi-based electrocatalysts such as Bi

XXXX American Chemical Society

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

.1 M HCl, a high FE (11.50%) and a large NH yield (20.80

and O (Figure 2 a). Figure 2 b reveals the XPS spectrum in the

Article

X-ray (EDX) elemental mapping images further indicates that

Bi NPs are uniformly distributed in the carbon framework

(Figure 1h).

The X-ray photoelectron spectroscopy (XPS) survey

spectrum of Bi NPs@CRs shows three elements of Bi, C,

−

−1

μg h mg

) for Bi NPs@CRs have been achieved at −0.55

cat.

and −0.60 V versus reversible hydrogen electrode (RHE),

respectively.

RESULTS AND DISCUSSION

■

The Bi NPs@CRs were synthesized via thermal solvent

reﬂuxing, followed by a facile annealing method in an Ar

atmosphere as illustrated in Figure 1 a. The X-ray diﬀraction

Figure 2. (a) XPS survey spectrum of Bi NPs@CRs in Bi 4f (b), C 1s

(c), and O 1s (d) regions.

Bi 4f region, revealing two distinct peaks with binding energies

BEs) of Bi 4f₇_/₂and 4f₅_/₂located at 159.2 and 164.5 eV,

respectively. These results are corresponding to the BEs for Bi

(

46,47

metal, which is in accordance with XRD and TEM data.

Figure 1. (a) Brief illustration of the synthesis process of Bi NPs@

CRs. (b) XRD pattern, (c, d) SEM images, (e, f) TEM images, and

Figure 2c shows the region of C 1s; the peak values of BEs

situated in 284.8, 286.2, and 288.1 eV belong to the single

bonds of C−C and C−O and the double bond of CO in the

(

g) selected area diﬀraction of Bi NPs@CRs. (h) STEM image and

the elemental mapping images of Bi, C, O, for Bi NPs@CRs.

carbon framework, respectively. The results of Figure 2d

show that the O 1s region spectrum has three obvious peaks at

530.0, 531.8, and 533.8 eV, which are ascribed to the Bi−O,

(

XRD) pattern of the as-synthesized Bi-MOF using an organic

ligand (H BTC) as linker shows typical diﬀraction peaks,

which are consistent with reported theoretical data (Figure

OC, and O−C bonds, respectively. The Bi−O bond may

be attributed to superﬁcial oxidation of as-prepared material.

The electrocatalytic NRR characteristics of Bi NPs@CRs in

0.1 M HCl electrolyte were implemented in an electrolytic cell

disconnected through a Naﬁon membrane (117). Carbon

paper was used as conductive matrix to deposit the Bi NPs@

3,44

S1 ).

In terms of Bi NPs@CRs, the noticeable diﬀraction

peaks of Figure 1b at 27.2°, 37.9°, 39.6°, 48.7°, and 55.6° are

indexed to the (012), (104), (110), (202), and (024) planes of

the Bi phase (JCPDS No. 44-1246), respectively. The wide

peaks ranging from 20° to 30° may be ascribed to the carbon

−2

shell forming in the annealing process. Furthermore, the

morphology and structure of the Bi-MOF and Bi NPs@CRs

were investigated through scanning electron microscopy

CRs (loading amount of Bi NPs@CRs/CP: 0.1 mg cm ),

which serves as working electrode. Saturated KCl solution

ﬁlling in Ag/AgCl behaves as reference, yet a graphite rod

acted as counter electrode. Additionally, the RHE scale is

commonly used to calibrate all applied potentials during the

electrocatalytic process. Linear sweep voltammetry of Bi NPs@

CRs/CP performed in 0.1 M HCl electrolyte with high purity

SEM) and transmission electron microscopy (TEM). Figure

S2 shows that the precursor of Bi-MOF presents a rod

structure with a smooth surface. After annealing, the Bi NPs@

CRs still hold the rod morphology as presented in Figure 1c,

but the Bi NPs are evenly conﬁned into the carbon framework

observed from the high-magniﬁcation SEM image (Figure 1d).

The TEM (Figure 1e) with low magniﬁcation and the high-

resolution TEM (HRTEM) presented in Figure 1f demon-

strate that the Bi NPs are entrapped by a carbon layer with a

thickness of less than 10 nm. Moreover, the selected-area

electron diﬀraction (SAED) pattern shown in Figure 1g reveals

that the interlayer distance of lattice fringes is 0.32 and 0.23

nm, which are indexed to the (012) and (104) planes of metal

Bi. Besides, the STEM coupled with related energy dispersive

N and Ar as supplied gas until saturated is illustrated in Figure

S3; the red curve gained by N -bubbling has a slightly higher

catalytic current, conﬁrming Bi NPs@CRs/CP has catalytic

activity for N conversion to NH under moderate conditions.

The indophenol blue method is utilized for the determi-

nation of generated NH , while the approach of Watt and

Chrisp is used to examine the potential byproduct of N H .

The corresponding calibration curves are provided in Figures

S4 and S5. The chronoamperometry curves of Bi NPs@CRs/

CP displayed in Figure 3a are operated at a set of potentials

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

in Figure 4 a. Moreover, the electrochemical tests are

Article

The N source is required to further validate that the

generated NH indeed originated from the electrocatalytic N

reduction process. We ﬁrst conﬁrmed whether nitrate and

nitrite existed in the supernatant of as-annealed Bi NPs@CRs;

−

the results of Figures S12 and S13 indicated that the NO and

−

NO₂in the supernatant of washed material were indeed not

present after the annealing procedure, which eliminates nitrate

and nitrite contribution to NRR. After that, several control

experiments are conducted at −0.6 V, such as under open

circuit and Ar-saturated electrolyte. Obviously, no distinct NH

is determined under open circuit and Ar conditions as shown

Figure 3. (a) Chronoamperometry data of Bi NPs@CRs/CP at a set

of potentials. (b) UV−vis spectra of the electrolytes after NRR

electrolysis kept for 2 h. (c) Gained NH yields and FEs of Bi NPs@

CRs/CP at certain potentials. (d) Gained corresponding NH amount

with Bi NPs@CRs/CP, Bi NPs/CP, and CP at −0.60 V vs RHE.

from −0.50 to −0.7 V in acidic electrolyte (HCl, pH = 1),

inletting N until saturated for 2 h. After that, the color reagent

of as-prepared indophenol was utilized to dye with the

electrolytes after electrolysis in dark circumstance, and UV−vis

absorption spectra in diﬀerent potentials can be observed from

Figure 3b. According to relevant calibration curves (Figure

Figure 4. (a) UV−vis absorption spectra of the electrolytes colored

with indophenol reagent utilizing Bi NPs@CRs/CP at diﬀerent

S4 ), the calculated average values of NH yields and FEs for Bi

NPs@CRs/CP are plotted in Figure 3c.

performing conditions. (b) Gained NH yields and FEs of Bi NPs@

Clearly, a high NH yield of 20.80 μg h_m_g−1 for Bi

−

cat.

CRs/CP under N - and Ar-dominated electrolytes for 2 h. (c) Six

NPs@CRs/CP delivers at −0.60 V, yet the high FE of 11.50%

is achieved at −0.55 V, both of which are superior to previous

reported data based on aqueous NRR catalysts (Table S1). As

circulating measurements of Bi NPs@CRs/CP at −0.60 V. (d) The

chronoamperometry curve for Bi NPs@CRs/CP at −0.60 V for 24 h.

presented, the NH yields and corresponding FEs reduce

obviously when the potential value exceeds −0.60 V; these

conducted in N

for 2 h. As expected, the NH

electrolyte with N as feeding gas (Figure 4b). Furthermore,

N and N isotopic labeling experiments were also conducted

and Ar as supplying gas after electrolysis

results may be ascribed to the competitive process toward

can only be detected in

HER. Furthermore, the possible byproduct of N H has not

been detected as illustrated in Figure S6, manifesting that Bi

NPs@CRs/CP has excellent selectivity for NH₃.

to conﬁrm the source of NH . The H nuclear magnetic

The excellent NRR performance of Bi NPs@CRs needed to

be further con ﬁ rmed through a series of control experiments.

Bi NPs (Figures S7 and S8 ) were synthesized through a

hydrothermal approach. As a comparison, the NRR properties

of blank CP and Bi NPs/CP are then contrasted with those of

Bi NPs@CRs/CP at −0.60 V. Obviously, these results

illustrated in Figure 3d demonstrate that blank CP and Bi

NPs/CP yield 0.23 and 1.69 μg at −0.60 V through electrolysis

kept for 2 h, respectively. Such values are inferior to that of Bi

NPs@CRs/CP (4.03 μg) under the same conditions. The

prominent enhancement of NRR performance for Bi NPs@

CRs/CP may be ascribed to the Bi NPs with an average size

counted by 28.7 nm uniformly distributed on carbon rods; this

feature facilitates more active sites exposure, thus beneﬁting

resonance ( H NMR) spectroscopy of Figure S14 manifests

that NH with doublet coupling (J = 72 Hz) or NH with

triplet coupling (J = 52 Hz) only can be observed under N₂

or N as the feeding gas. The above experimental results

forcefully manifest that the NH₃detected by UV−vis

absorption spectra is indeed derived from the NRR of Bi

NPs@CRs in N -saturated solution. Taking into consideration

the small amounts of ammonia in air or gas supplied (N /Ar),

high-purity (99.999%) N or Ar gas ﬂowed into the H-type cell

with 0.1 M HCl as electrolyte without applied potential.

Corresponding UV−vis curves demonstrate that no obvious

NH was detected in air and N /Ar (Figure S15 ).

Stability as another key advantageous feature also can be

used for assessing the catalyst performance. Thus, six recycling

experiments as presented in Figure 4c were conducted in 0.1

M HCl electrolyte. Small ﬂuctuation can be observed on NH₃

yields and FEs. Furthermore, the corresponding current

density and UV −vis absorption spectra also display slight

variation (Figure S16a,b). Besides, the chronoamperometry

curves (Figure 4d) display mild variation even after 24 h of

electrolysis. Also, the Bi NPs@CRs/CP electrolyzed for 24 h

the NRR progress as displayed in Figures S9 and S10 . In

order to verify the reliability of spectrophotometry, ion

chromatography is oﬀered to analyze the NH yields and

related FEs at diﬀerent applied potentials. The data of ion

chromatography illustrated in Figure S11 are comparable with

the counterpart obtained through the method of indophenol

blue.

Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

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Article

was further performed in fresh HCl solution (pH = 1). UV−vis

absorption spectra (Figure S17) illustrate that the absorbance

spectra of initial and after electrolysis for 24 h have no

apparent decrease. These experimental results reveal that Bi

NPs@CRs/CP has excellent electrochemical durability for

NRR at ambient conditions. Furthermore, the XRD pattern

and SEM image of Bi NPs@CRs/CP after long-term NRR

tests also were performed. Figures S18 and S19 demonstrated

that Bi NPs@CRs/CP possesses high structure stability for the

Haitao Zhao − Materials and Interfaces Center, Shenzhen

Institutes of Advanced Technology, Chinese Academy of

Sciences, Shenzhen 518055, Guangdong, China

https://pubs.acs.org/10.1021/acs.inorgchem.1c01130

Notes

The authors declare no competing ﬁnancial interest.

N reduction.

ACKNOWLEDGMENTS

■

CONCLUSION

This work was supported by the National Natural Science

Foundation of China (U1833124 and No. 21876117) and

Shanghai Scientiﬁc and Technological Innovation Project (No.

■

To sum up, well-dispersed Bi NPs conﬁned in a carbon

framework have been successfully prepared by a Bi-MOF

precursor using thermal annealing. This catalyst shows

favorable NRR electrochemical performance. In acid solution

8JC1410604).

(

0.1 M HCl), the as-fabricated electrocatalyst gained a high

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AUTHOR INFORMATION

■

(

Corresponding Authors

Baozhan Zheng − College of Chemistry, Sichuan University,

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Juan Du − College of Chemistry, Sichuan University, Chengdu

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Longcheng Zhang − College of Chemistry, Sichuan University,

Chengdu 610064, Sichuan, China; Institute of Fundamental

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Technology of China, Chengdu 610054, Sichuan, China

Ting Wang − Institute of Fundamental and Frontier Sciences,

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