Author’s Accepted Manuscript

Anti-Poisoned Oxygen Reduction by the Interface

Modulated Pd@NiO Core@Shell

Yonggang Feng, Chengyong Yang, Wei Fang,

Bolong Huang, Qi Shao, Xiaoqing Huang

www.elsevier.com/locate/nanoenergy

PII: S2211-2855(19)30045-X
DOI: https://doi.org/10.1016/j.nanoen.2019.01.036
Reference: NANOEN3383
To appear in: Nano Energy
Received date: 4 December 2018
Revised date: 9 January 2019
Accepted date: 10 January 2019
Cite this article as: Yonggang Feng, Chengyong Yang, Wei Fang, Bolong
Huang, Qi Shao and Xiaoqing Huang, Anti-Poisoned Oxygen Reduction by the
Interface Modulated Pd@NiO Core@Shell, Nano Energy,
https://doi.org/10.1016/j.nanoen.2019.01.036
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 Anti-Poisoned Oxygen Reduction by the Interface Modulated

Pd@NiO Core@Shell

Yonggang Feng,a Chengyong Yang,a Wei Fang,b Bolong Huang,c* Qi Shao,a and Xiaoqing Huanga*

a
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu

215123, China.
b
Testing & Analysis Center, Soochow University, Jiangsu, 215123, China.
c
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University,

Hung Hom, Kowloon, Hong Kong SAR.

*
To whom correspondence should be addressed.

E-mail: bhuang@polyu.edu.hk; hxq006@suda.edu.cn

Abstract: The methanol (CH3OH) crossover in direct methanol fuel cells is very poisonous to

cathodic noble metal electrocatalysts, which usually leads to serious degradation of electrocatalytic

performance. However, most focus of present research has been concentrated on the persistent

pursuit of enhancing the sluggish ORR reactions while the pivotal methanol crossover has been

left out generally. The “reactivity and anti-poison” dilemma has been approached by many

surface engineering including the development of new membrane with low methanol permeability

or assemble layered structures. As the notable structure-dependent performance in catalytic

reaction, our work has proposed Pd@NiO core@shell as an interface engineering approach that

can significantly inhibit the CO species adsorption while preserving the ORR reactivity, which can

1
also exhibit superior stability even in poisoning circumstances. Herein, we report a series of

unique Pd@NiO-x/C with controlled interface structure to overcome the activity and anti-

poisoning issues of oxygen reduction reaction (ORR), where the optimized Pd@NiO/C exhibits a

high activity of 0.24 A mg-1, excellent tolerance over the CH3OH/CO poisoning as well as superior

stability even in the practical poisoning circumstances, all which are far better than the

commercial Pt/C and Pd/C. DFT calculations reveal that the excellent ORR performance with

effective methanol tolerance become superior with core@shell interfacial engineering. With

effective modulations, the generalized interfacial d-band-offset can be achieved for counteracting

the ORR barriers with extra-high current density. The simultaneously high activity and excellent

anti-poisoning features of the Pd@NiO nanostructure make it a practically potential

electrocatalyst for fuel cell and beyond.

Keywords: Pd@NiO, Core@shell structure, Anti-poisoning, Oxygen reduction reaction, Electrocatalyst

1. Introduction

Noble metals (e.g., Pt and Pd) are the best electrocatalysts for oxygen reduction reaction (ORR)

in direct methanol fuel cells (DMFC), which play significant role in the next generation of sustainability

due to their great potential application as alternative energy sources[1-11]. However, the methanol

(CH3OH) crossover from the anode to the cathode through the polymer membranes, a common

occurrence in DMFC, seriously affects their electrocatalytic efficiency and stability that results from the

noble metal poisoning. Intrinsically, this poisoning phenomenon is related to the strong adsorption of the

CO-like species on noble metal surface[12-14]. To enable noble metal electrocatalysts with excellent anti-

2
poisoning properties, the adsorption of the poisoning species must be restricted or the desorption of the

poisoning species should be accelerated on the noble metal surface.

One strategy to mitigate CH3OH/CO poisoning is to develop Pt-based electrocatalysts with the

intermetallic structure, which can significantly reduce the bridge sites and eliminate the 3-fold hollow

adsorption sites of Pt[15-17]. By the same token, Pt single atom electrocatalysts also display high tolerance

to CH3OH/CO, due to the hard adsorption of CO on single Pt atom sites[18]. The anti-poisoning

capability of above electrocatalysts are essentially because of the weak bonding of poisoning

intermediates via modifying the electronic properties of noble metal surface, while these approaches also

weaken the O2 chemisorption as well as the O-O bond breakage processes that require two adjacent atom

sites[19, 20]
. While the enhancement of anti-poisoning properties of those electrocatalysts is usually

realized at the sacrifice of activity, the development of novel electrocatalysts with high activity and

excellent anti-poisoning simultaneously remains a formidable challenge.

To preserve the O2 adsorption on the noble metal surface but selectively inhibit the CO-like

species adsorption is a feasible strategy. Considering that the mesoporous metal oxides have been

demonstrated to be highly active for CO oxidation[21-23], creating a comprehensive interface between

noble metal and mesoporous metal oxides will presumably overcome the anti-poisoning and activity

issues simultaneously[23-29]. Herein, we constructed a novel Pd@NiO core@shell structure for ORR,

where the open channels structure of NiO shell with the controllable interface regulation boosts their

electrocatalytic performances. The optimized Pd@NiO exhibits the highest ORR activity, 2.2-fold than

the commercial Pt/C. More importantly, it exhibits excellent tolerance to CH3OH/CO during ORR, as

well as superior durability even in poisoning circumstances. DFT calculations reveal that insightful

core@shell interfacial engineered Pd-core enhances the O20→O22- as the prerequisite for efficiently

initiating four-electron ORR. The partially oxidized interfacial contributes an active 2p-orbital-bridge

3
between Pd-4d and Ni-3d for efficient d-d electron-transfer. Interfacial engineering blueprints the d-

band-offset modulation for spontaneously contributing Coulomb-blockade to weaken methanol

adsorption and alleviating intrinsic ORR electrocatalysis barriers with extra-high current density. These

remarkable features of Pd@NiO enable it to be a practically potential electrocatalyst for fuel cell.

2. Experimental section

2.1 Chemicals

Palladium(II) acetylacetonate (Pd(acac)2, 99%), nickel(II) formate dihydrate (Ni(HCO2)2·2H2O,

99%), ascorbic acid (C6H8O6, AA, reagent grade, 99%), oleylamine (CH3(CH2)7CH=CH(CH2)7CH2NH2,

OAm, >70%) and 1-octadecene (CH2=CH(CH2)15CH3, ODE, technical grade, 90%) were purchased

from Sigma-Aldrich. Cyclohexane (C6H12, analytical reagent, >99.5%), ethanol (CH3CH2OH, analytical

reagent, >99.7%), hydrogen peroxide (H2O2, 30.0%) and hydrochloric acid (HCl, analytical

reagent, >99.5%) were purchased from Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China). All

the chemicals were used as received without further purification. The water (18 MΩ/cm) used in all

experiments was obtained by passing through an ultra-pure purification system (Aqua Solutions).

2.2 Characterizations

The samples were prepared by dropping cyclohexane or ethanol dispersion of samples onto

carbon-coated copper transmission electron microscope (TEM) grids using pipettes and dried under

ambient condition. Low-magnification TEM was conducted on a HITACHI HT7700 transmission

electron microscope at an acceleration voltage of 120 kV. High-magnification TEM and scanning TEM

(STEM) were conducted on an FEI Tecnai F20 transmission electron microscope at an acceleration

voltage of 200 kV. X-ray diffraction (XRD) pattern was collected on X’Pert-Pro MPD diffractometer

(Netherlands PANalytical) with a Cu Kα X-ray source (λ = 1.540598 Å). The concentration of catalyst

4
was determined by the inductively coupled plasma optical emission spectrometer (Varian 710-ES). All

the X-ray photoelectron spectroscopy (XPS) of these catalysts was collected by XPS (Thermo Scientific,

ESCALAB 250 XI).

2.3 Preparations of Pd@Ni NPs

In a typical preparation of Pd@Ni core@shell NPs, 3.5 mg Pd(acac)2, 5 mg Ni(HCO2)2·2H2O,

36 mg AA, 2.5 mL OAm and 2.5 mL ODE were added into a vial (volume: 30 mL). After the vial had

been capped, the mixture was ultrasonicated for around 0.5 h. The resulting homogeneous mixture was

heated from room temperature to 170 °C for around 0.5 h and kept at 170 °C for 5 h in an oil bath. After

cooling to room temperature, the colloidal products were collected by centrifugation, and washed with

cyclohexane/ethanol (volume ratio 1/9) mixture for three times.

2.4 Preparations of Pd@NiO-x/C NPs

In a typical preparation of Pd@NiO-x/C, the Pd@Ni core@shell NPs were dispersed in 5 mL

cyclohexane, and then added into 15 mL ethanol solution with 5 mg C dispersed under stirring. After

stirring for 1 h, Pd@Ni/C were collected by centrifugation and dried in 60 °C for 5 h. The Pd loading of

the catalyst was controlled to be 20 wt%. The obtained Pd@Ni/C was redispersed in 5 mL ethanol and

treated with different amount of H2O2 (0.1 mL, 0.3 mL and 0.5 mL) in autoclave at 100 ºC for 1 h to

generate Pd@NiO-x/C (Pd@NiO-0.1/C, Pd@NiO-0.3/C and Pd@NiO-0.5/C). The Pd@NiO-x/C was

collected by centrifugation and dried in 60 °C for 5 h.

2.5 Preparations of Pd@NiO-0.3/C-HCl NPs

In a typical preparation of Pd@NiO-0.3/C-HCl, the Pd@NiO-0.3/C was dispersed in 5 mL

ethanol. 0.1 mL HCl was then added to the solution with stirring. After stirring for 0.5 h, Pd@NiO-

5
0.3/C-HCl was collected by centrifugation, and washed with H2O/ethanol mixture and dried in 60 °C for

5 h.

2.6 Electrochemical measurements

A three-electrode cell was used for the electrochemical measurements. A glassy-carbon electrode

(GCE) (diameter: 5 mm, area: 0.196 cm2) from Pine Instruments was used as the working electrode, a

saturated calomel electrode (SCE) was used as the reference electrode and a Pt wire was used as the

counter electrode, respectively. To prepare the catalyst-coated working electrode, the catalyst was

dispersed in a mixture containing isopropanol and Nafion (5%) to form a 0.20 mgPd or Pt mL-1 dispersion.

10 µL dispersion of catalysts (0.20 mgPd or Pt mL-1) was deposited on a glassy carbon electrode to obtain

the working electrode after the solvent was dried at room temperature. The cyclic voltammetry (CV)

was carried out at room temperature in 1 M KOH solution. The potential scan rate was 50 mV s-1 for CV

measurement. ORR measurement was conducted in a 0.1 M KOH solution purged with O 2 during the

measurement. The scan and rotation rate for ORR measurement were 10 mV s-1 and 1600 rpm,

respectively. The methanol tolerance tests were conducted at the same condition with ORR

measurement but adding 0.1 M, 0.3 M and 0.5 M CH3OH into electrolyte, respectively. The CO

tolerance tests were conducted at the same condition with ORR measurement but purging CO to

saturation simultaneously. The accelerated durability tests were performed at room temperature in 0.1 M

KOH solutions by applying the cyclic potential sweeps between 0.6 and 1.0 V versus RHE at a sweep

rate of 100 mV s-1 for 10,000 cycles. The anti-poisoning durability tests were performed at room

temperature in O2-saturated 0.1 M KOH and 0.5 M CH3OH solutions through chronoamperometric (CA)

measurements for 10,000 s. All electrochemical experiments were performed at room temperature. For

comparison, the commercial Pt/C was used as the baseline catalyst, and the same procedures described

above were applied to the electrochemical measurements.

6
2.7 DFT calculations

We carried the DFT+U calculations by CASTEP code[30] by the rotationally invariant Hubbard-U

theory[31]. The Hubbard-U parameter self-consistently determined for the pseudized Pd-4d and Ni-3d

orbital by our linear response method for U determination[32-34]. The geometry optimization used the

Broyden-Fletcher-Goldfarb-Shannon (BFGS) algorithm through all calculations. The PBE functional

was chosen for PBE+U calculations with a plane-wave basis set cutoff energy of 750 eV. The ensemble

DFT (EDFT) method[34] is used for improving convergence of transition metal-based system.

For the Pd-core model, we inherit the previous work for a good continuation. The supercell of Pd

(100) surface within fcc-lattice was chosen and set the size of 3×3×1 (108 atoms, i.e. Pd108) with 6 layers

thick. The vacuum thickness is fixed to be 15 Å to adopt the addition NiO layers. We only allow the top

two layers to be varied freely. For the NiO-shell model, we found the rocksalt NiO (100) matches well

to the Pd (100). Accordingly, the NiO shell layer is built with the same lattice parameters fixed. To

model the cavity area of the as-synthesized porous shell layer, we create a series of models with vacant

areas, and finally determined at the volume of 8.62×6.04×8.62 (Å3), and overall with 4 layers thick.

For the Monkhorst-Pack k-poing sampling, the reciprocal space integration was performed using

the the mesh of 2×2×1[35] with Gamma-center-off, which was self-consistently selected for total energy

minimization. With these special k-points, the total energy is converged to less than 5.0x10-7 eV per

atom. The Hellmann-Feynman forces on the atom were converged to less than 0.001 eV/Å.

The Ni, Pd, O, and H norm-conserving pseudopotentials are generated using the OPIUM code in

the Kleinman-Bylander projector form[36], and the non-linear partial core correction[37] and a scalar

relativistic averaging scheme[38] are used to treat the (Ni, Co) spin-orbital coupling effect. We chose the

(3d, 4s, 4p), (4d, 5s, 5p), (2s, 2p) and (1s) states as the valence states of Ni, Co, O, and H atoms

7
respectively. The RRKJ method is chosen for the optimization of the pseudopotentials[39]. The Hubbard

U parameter has been self-consistently determined based on our previous developed method[40]. For the

all of the electronic states calculations in Pd@NiO models, we use the self-consistent determination for

the U correction on the localized 4d orbitals to correct the on-site Coulomb energy of the electron

spurious self-energy. By that method, the Hubbard U parameters on the half-filled shell of 4d10 orbitals

of Pd is self-consistently determined to be Ud=10.13 eV, and Ud=5.58 eV for Ni-3d8. Meanwhile, to

stabilize the hole states induced by the O-2p orbitals, we self-consistently chose the Up=4.23 eV for O-

2p4 orbitals in the anti-ferromagnetic NiO lattice, based on our devised linear response method[40].

Here we answer the mechanistic reason for choosing the porous NiO as shell for the core@shell

system based on the Pd-core (Fig. 7e). For our modeled system, the Fermi levels of Pd and NiO relative

to the vacuum reference level have been shown respectively. The work functions for the Pd-core and

NiO porous shell parts are 4.92 eV and 6.61 eV by our calculations. Note, their d-bands dominate the

most portions of their valence bands from both parts. The valence band offset (VBO) is represented by

the d-band-offset (Vd) from both core and shell. The Pd-4d band edge relative to the vacuum level is

updated as Ecore=Vd,core+Φcore=5.92 eV. The Ni-3d band edge from NiO relative to the vacuum level is

Eshell=Vd,shell+Φshell=0+6.61=6.61 eV, where the work function is contributed by the as-synthesized

porous NiO shell with lower-coordinated Ni-exposed cavity region. Experimentally, for the NiO the

work function was reported from 4.7 eV to 5.0 eV with enhanced O2-plasma treatment[41]. Further air-

exposed oxidation leads to the hydroxide termination and the related work function will be modified

from 5.2 eV to 5.6 eV. The in-situ oxidized NiO can possess even higher as 6.7 eV. Our calculation

shows the porous oxidized NiO with Ni-exposed cavity is 6.61 eV and ordinary NiO slab model with

non-polar surface is from 4.53 eV to 5.40 eV depends on the different lattice distortions, showing a good

8
agreement with reported experiments[42]. The physicochemical trend is still correct despite of rigid

systematic errors.

Now the goal is to modulate the work function to induce the band offset appropriately via

element selection and advanced synthesis technology. The differences in work functions and band

offsets result in the interface potential barrier with barrier height of Ubh. The electrons are therefore from

the core into the shell regions with additional potential of Ubh for the following catalysis. As we further

compared, the catalytic reaction preference is further dominated by the trade-off between Ubh and Uab

(activation barrier height for intermediate steps), in terms of downhill, uphill and thermoneutral

processes, respectively.

3. Results and Discussion

3.1 Preparations and characterizations of Pd@Ni NPs and Pd@NiO-x NPs.

The Pd@NiO-x nanoparticles (NPs) were created by a two-step post-oxidizing procedure (Fig.

1a). The Pd@Ni core@shell NPs were initially prepared by co-reduction of palladium(II)

acetylacetonate (Pd(acac)2) and nickel(II) formate dihydrate (Ni(HCO2)2) using ascorbic acid (AA) as

the reducing agent (see Experimental section), which are highly monodisperse with an average particle

size of 22 nm (Fig. 1b). The atomic ratio of Pd to Ni is 1 : 1, as confirmed by transmission electron

microscopy energy-dispersive X-ray spectroscopy (TEM-EDS) and inductively coupled plasma optical

emission spectrometer (ICP-AES) results (Fig. S1a). The X-ray diffraction (XRD) of Pd@Ni NPs shows

two obvious sets of diffraction patterns, which can be indexed to face-centered cubic (fcc) Pd and fcc Ni

(Fig. S1b). The interplanar spacing of 0.203 nm is assigned to the (111) plane of fcc Ni (Fig. S2a). An

obvious core@shell structure of Pd@Ni NP is clearly observed from scanning TEM EDS (STEM-EDS)

elemental mappings (Fig. 1c). The line-scan analysis reveals the thickness of Ni shell is about 2.5 nm

(Fig. 1d and S2c). To utilize the unique Pd@Ni NPs for efficient ORR, the thick Ni shell has to be

9
modified due to their serious hindrance to the accessibility of O2 to the active Pd core. Considering that

Ni can be readily transformed into the porous NiO through simple oxidation treatments,43-45 the Pd@Ni

NPs were treated with H2O2 firstly. As expected, the distinct boundary between Pd core and porous NiO

shell can be observed (Fig. 1e). The ratio of Pd to Ni has no noticeable change, while the NiO phase is

clearly observed (Fig. S1c and d). The interplanar spacings of 0.239 nm assigned to (101) plane of NiO

are detected from high resolution TEM (HRTEM) image (Fig. S2b). The STEM-EDS elemental

mappings and line-scan analysis further show the formation of NiO shell with thickness of about 2.5 nm

(Fig. 1f and 1g and S2d). These results collectively confirmed the successful construction of Pd@NiO

core@shell NPs through a facile H2O2 treatment over Pd@Ni NPs.

3.2 Preparation and characterization of Pd@NiO-x/C.

To make real ORR electrocatalysts, we loaded the Pd@Ni NPs on the carbon black (Vulcan

XC72R carbon, C) and also treated with H2O2. The oxidation degree of Ni shell was controlled by

controlling the amounts of H2O2 (0.1 mL, 0.3 mL and 0.5 mL) and denoted as Pd@NiO-0.1/C,

Pd@NiO-0.3/C and Pd@NiO-0.5/C, respectively. As shown in Fig. 2a and Figs. S3-5, all the Pd@NiO-

x/C exhibit obvious core@shell structure. The phase transformations of the Pd@NiO-x/C were

confirmed by X-ray diffraction (XRD) (Fig. 2b). Only weak NiO peaks are detected in Pd@NiO-0.1/C.

With deepening the oxidation degree, the NiO peaks become much stronger in Pd@NiO-x/C, until the

formation of PdO in Pd@NiO-0.5/C. X-ray photoelectron spectroscopy (XPS) studies were also carried

out to investigate the surface properties of Pd@NiO-x/C. We can see that, compared to the only

existence of Pd0 in the pristine Pd@Ni/C, Pd2+ could be detected in Pd@NiO-x/C, especially for

Pd@NiO-0.5/C (Fig. 2c). The sharp increase of Pd2+ species in Pd@NiO-0.5/C is contributed to the

excessive oxidation of the Pd core, being consistent with the XRD results. As shown in Fig. 2d, Ni0 is

observed in Pd@Ni/C and Pd@NiO-0.1/C, due to the presence of intact/residual Ni shell, while only

10
Ni2+ exists in Pd@NiO-0.3/C and Pd@NiO-0.5/C, indicating the complete formation of NiO shell with

deepening the oxidation degree.

3.3 ORR performances of Pd@NiO-x/C.

The successful creation of Pd@NiO-x/C with precise NiO shell and interface regulation is

expected to enhance its electrocatalytic performance. We initially assessed their ORR activities in

alkaline condition. The typical cyclic voltammogram (CV) curves for Pd@Ni/C, Pd@NiO-x/C, the

commercial Pt/C and Pd/C (Fig. S6) are shown in Fig. 3a. The current density of the reduction peak of

PdO at around 0.7 V vs. reversible hydrogen electrode (RHE) increases considerably along with

deepening the oxidation degree of Ni shell, indicating more exposure of Pd active sites. The polarization

curves of these electrocatalysts for ORR and corresponding electron transfer number (n) calculated from

the tests performed on a rotating ring-disk electrode (RRDE) are provided in Fig. 3b and c, respectively.

For Pd@Ni/C and Pd@NiO-0.1/C, 2-electron pathway is dominant in their ORR processes, due to the

existence of intact/residual Ni shell. However, Pd@NiO-0.3/C and Pd@NiO-0.5/C show obvious 4-

electron pathway for ORR, same as the commercial Pt/C and Pd/C, revealing a distinct change of ORR

selectivity after the oxidation treatment (Fig. 3b and c). The half-wave potentials (E1/2) and mass

activities of different electrocatalysts are summarized in Fig. 3d. It is apparent that E1/2 shows a

dramatic increase from Pd@NiO-0.1/C (0.71 V) to Pd@NiO-0.5/C (0.87 V). To be specific, Pd@NiO-

0.3/C exhibits the highest mass activity (0.24 A mgPd-1) among these electrocatalysts, which is 2.2-fold

higher than the commercial Pt/C (0.11 A mgPt-1). It is worth noting that the activity of Pd@NiO-0.5/C

(0.13 A mgPd-1) is lower than that of Pd@NiO-0.3/C (Fig. 3c and d), mainly attributing to the over

oxidation of the Pd core (Fig. 2b and c). This fact implies that the ORR activity of Pd@Ni/C could be

triggered tremendously by the precise oxidation treatment.

11
3.4 The anti-poisoning properties of Pd@NiO-x/C.

To evaluate the anti-poisoning properties of these elctrocatalysts, the poisoning circumstances

were simulated by introducing CH3OH or CO in ORR conditions. Significantly, Pd@NiO-0.3/C shows

high tolerance to CH3OH and CO in O2-saturated solution (Fig. 4a), while the commercial Pt/C and

Pd/C exhibit high electrooxidation activities for CH3OH and CO (Fig. 4b and Fig. S7d). Although the

high tolerance to CH3OH and CO is also observed for Pd@Ni/C and Pd@NiO-0.1/C (Fig. S7a and b),

the inertness of Ni shell to CH3OH and CO plays the decisive role, as confirmed by their much lower

ORR activities and distinct 2-electron pathway (Fig. 3c). For Pd@NiO-0.3/C and Pd@NiO-0.5/C, their

excellent anti-poisoning properties are more likely derived from the fine modification of NiO shell. To

prove this assumption, HCl treatment of Pd@NiO-0.3/C was carried out to reveal the contribution of

NiO shell (see Experimental section). After destructing the NiO shell of Pd@NiO-0.3/C (Fig. S8),

more stronger reduction peak of PdO could be detected in the Pd@NiO-0.3/C-HCl compared with

Pd@NiO-0.3/C (Fig. S9). The Pd@NiO-0.3/C-HCl delivers similar ORR activity but much worse

tolerance to CH3OH and CO (Fig. 4c), indicating the critical role of NiO shell on enhancing the anti-

poisoning property. The CO stripping voltammetry was further used as a probe reaction for studying the

CO adsorption capacity of these electrocatalysts. Compared with the commercial Pt/C and Pd/C (Fig.

S10), the CO oxidation peak of Pd@NiO-x/C is dramatically restricted and the voltammetric profile is

essentially unchanged (Fig. 4d and Fig. S11), while a sharp peak ascribes to the oxidation of absorbed

CO is detected on Pd@NiO-0.3/C-HCl, indicating that the presence of NiO shell greatly inhibits the CO

adsorption. Therefore, the excellent anti-poisoning property of the Pd@NiO-0.3/C is primarily

originated from the intrinsic weak adsorption of CO.

Encouraged by the above results, we further assessed the durability of Pd@NiO-0.3/C, Pd@NiO-

0.3/C-HCl and the commercial Pt/C by scanning 10,000 cycles in alkaline electrolyte with the sweeping

12
potential from 0.6 V to 1.0 V vs. RHE (Fig. 5). As shown in Fig. 5a, Pd@NiO-0.3/C exhibits high

durability with only 8.8 % mass activity lose after 10,000 continuous cycles. As for the commercial

Pt/C, only 60.2 % mass activity can be maintained after 10,000 CV cycles (Fig. 5b). In addition, the

Pd@NiO-0.3/C-HCl exhibits worse durability than the Pd@NiO-0.3/C (Fig. 5c), revealing that NiO

shell also plays an important role on enhancing the electrocatalytic durability. These electrocatalysts

after the durability tests were also evaluated, where the morphology and composition of Pd@NiO-0.3/C

were largely maintained due to the protection of NiO shell (Fig. S12). More detailed characterizations

reveal that a certain amount of PdO was formed on the surface of Pd@NiO-0.3/C after durability test

(Fig. S13). In contrast, the obvious aggregations were observed for both Pd@NiO-0.3/C-HCl (Fig. S14)

and the commercial Pt/C (Fig. S15). Motivated by the excellent anti-poisoning properties of Pd@NiO-

0.3/C, the long-term operation stability test of these electrocatalysts was further performed in 0.1 M

KOH with 0.5 M CH3OH by chronoamperometric (CA) measurement, simulating practical poisoning

circumstances in DMFC. Significantly, after 10,000 s CA test, Pd@NiO-0.3/C still retain 93% of the

initial current, whereas there are nearly 56% and 76% current losses for Pd@NiO-0.3/C-HCl and the

commercial Pt/C, respectively, further confirming the excellent durability of Pd@NiO-0.3/C even in the

poisoning circumstances (Fig. 5d).

3.5 Discussion.

The highly efficient ORR performances with excellent methanol tolerance were further

interpreted by DFT calculations (Fig. 6a, left). The bonding (filled-states) and anti-bonding (empty-

states) orbitals near the Fermi level (EF) illustrate that Pd-core shows an electron-rich character, while

the NiO shell exhibits electron-deficit character, respectively (Fig. 6a, right). Interfacial valence d-

band-offset variation trends have been analyzed (Fig. 6b-e). The Pd-4d band gradually downshifts

towards deeper electron-rich level, from about EV-2.2 eV (interface) to EV-4.1 eV (bulk), where the

13
EV=0 for EF. This potentially enhances the efficiency of O20→O22- at the initial adsorption step without

O-O cleavage (Fig. 6b). The Ni-3d band varies in opposite trend with promoted towards higher levels

close to the EF (from EV-2.4 eV to EV-0.6 eV). The Ni-oxidation state distinctly stays above the EF while

nearly diminished at the interface region by the lower-coordinated Ni sites in the cavity. The interfacial

Ni-sites are responsible for stabilizing the OH- from H2O-splitting, owing to the substantial p-d

overlapping (Fig. 6c). Further cavity size-dependent electronic characters are reflected by the PDOSs

variations. With increasing sizes, the p and d bands turn to be completely overlapped. This will avoid

producing over-binding effect by the additional p-states guaranteeing efficient core@shell charge-

transfer (Fig. 6d). Meanwhile, individual contributions on the p-bands from different O-species show

that the 2p-bands of the O2 and H2O overlapping with Pd-4d band critically benefit initial O2 adsorption

and efficient charge-transfer, and optimize the ORR in energy by stabilizing (OOH-). We see bulk O-2p

band (NiO) stays deeply relative to EF, while interfacial O-2p are settled higher than the octahedral O-2p

with wider orbital coverage. This denotes an active 2p-orbital-bridge for efficient d-d electron-transfer

between Pd and Ni sites (Fig. 6e).

We continued on the ORR-pathway and CH3OH-adsorption (Fig. 7a-c). The initial adsorption of

O2 and H2O is key for promoting the activities of ORR, which is -2.84 eV at the electrode potential of

U=0 V. The overall reaction pathway is found to be energetically favorable with a deep gain of -5.47 eV.

The only barrier (0.51 eV) locates at the (*OOH-+OH-+H2O+2e-) formed from (*O22-+2H2O+2e-). The

following steps towards final 4OH- are all found to be downhill in trend. We notice the barrier is an

intrinsic and U-independent, which will be alleviated by the core@shell interfacial engineering. The

overall pathway indicates a small over-potential (around 0.4 V~0.5 V) can be achieved within the

Pd@porous NiO system (Fig. 7a). We also compared the (OH-)-chemisorption (Fig. 7b). The

adsorptions at these sites are all favorable and the (OH-)Ni shows two times closer to the thermoneutral

14
line (∆G=0 eV), indicating a high yielding rate from the shell, since the lower coordinate Ni sites

surpasses the Pd sites with its desorption activity (Fig. 7b). Regarding the (CH3OH)-adsorbing behavior,

we have comprehensively tested many possible sites and configurations between Pd@NiO and Pd

surface. From the Pd@NiO, the level starts from -0.45 eV to -1.04 eV presenting a weak adsorption,

which is 2 to 3 times higher than the initial O2-adsorption (ORR). On the contrary, it is from -2.08 eV to

-3.09 eV in Pd-surface, which is almost 2 to 7 times stronger than the Pd@NiO. Therefore, an efficient

methanol tolerance has been ensured in Pd@NiO (Fig. 7c). From local structural configurations, we

show the O-O bond can be well preserved when the O2 has been stably adsorbed on the Pd-core.

Throughout a transition step, the OOH- has been favorably formed at the Ni-site without over-binding

induced O-O cleavage. We find the O2- can be adsorbed on the Pd-core indicating a generalized

electron-transfer trend. The (OH-)-desorption rests on the weak chemisorption energy in NiO, which will

effectively redistributes the OH- (Fig. 7d). We further reason the interfacial engineering mechanism in

Pd@NiO (Fig. 7e). With aligned vacuum level (see Experimental Section), d-band-offsets with

different work functions will synergistically promote electrons injecting into shell with gained potential

of Ubh=-0.69 eV. This will not only counteract the ORR barrier Uab=0.51 eV, but also provide even

lower potential gaining trend, contributing a high electron current density for following catalysis. By

analyzing the electronic structures and energetic characters, we interpret the core@shell engineered Pd-

related catalyst system can achieve both high electronic activities for ORR performance and effective

cathodic methanol tolerance simultaneously. We point out that, currently, it is extremely difficult to use

current conventional experimental techniques to explore the interfacial catalysis activities in-depth.

4. Conclusion

In conclusion, a unique class of Pd@NiO core@shell NPs has been successfully designed to

overcome the anti-poisoning and activity issues of ORR. The optimized Pd@NiO/C largely outperforms

the commercial Pt/C and Pd/C in both electrocatalytic activity and poisoning tolerance to CH 3OH/CO.

15
More significantly, Pd@NiO/C exhibits superior stability even in poisoning circumstances. DFT

calculations reveal that effective core@shell interfacial engineering will efficiently tuned the Pd-core to

enhance the O22- adsorption without O-O cleavage and substantially weakens the CH3OH chemisorption

to promote the O-species evolutions. The observed highly efficient electron-transfer is reached via d-d

transfer from interfacial oxidation states. A generalized blueprint has been proposed that interfacial

engineering will lead to an intrinsic d-band-offset for future effectively minimizing the electrocatalysis

barriers with extra-high current density at even lowered potential. The simultaneously high activity and

excellent anti-poisoning properties of Pd@NiO/C makes it a practically potential electrocatalyst for fuel

cell and beyond.

Acknowledgement

The authors thank the Ministry of Science and Technology (2016YFA0204100, 2017YFA0208200), the

National Natural Science Foundation of China (21571135), Young Thousand Talented Program, Jiangsu

Province Natural Science Fund for Distinguished Young Scholars (BK20170003), the Priority Academic

Program Development of Jiangsu Higher Education Institutions (PAPD), and the start-up supports from

Soochow University.

Author contributions

X.H. conceived and supervised the research. X.H. and Y.F. designed the experiments. X.H., Y.F., C.Y.,

W.F. and Q.S. performed most of the experiments and data analysis. B.H. performed the DFT

simulations. X.H. and Y.F. wrote the paper. All authors discussed the results and commented on the

manuscript.

Additional information

16
Supplementary Information is linked to the online version of this paper.

Competing financial interests

The authors declare no competing financial interests.

Reprint and permissions information is available online.

Correspondence and requests for materials should be addressed to B.H.( bhuang@polyu.edu.hk) or X.H.
(hxq006@suda.edu.cn).

17
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Figures

Fig. 1. Morphological and structural characterizations of Pd@Ni NPs and Pd@NiO-0.3 NPs. (a)

Schematic illustration of the creation of Pd@NiO core@shell structure. (b) TEM image, (c) STEM-EDS

elemental mappings and (d) STEM-EDS line-scan of Pd@Ni NPs. (e) TEM image, (f) STEM-EDS

elemental mappings and (g) STEM-EDS line-scan of Pd@NiO-0.3 NPs.

24
Fig. 2. Morphological and structural characterizations of Pd@NiO-x/C. (a) TEM image of

Pd@NiO-0.3/C, (b) XRD patterns of Pd@Ni/C and Pd@NiO-x/C. XPS spectra of (c) Pd 3d and (d) Ni

2p of Pd@Ni/C and Pd@NiO-x/C.

25
Fig. 3. ORR performances of Pd@NiO-x/C. (a) CV curves in N2-saturated 1 M KOH at a scan rate of

50 mV s-1, (b) polarization curves in O2-saturated 0.1 M KOH at a scan rate of 10 mV s-1 and rotation

speed of 1600 r.p.m, (c) the electron transfer number from the tests performed on RRDE and (d) the

comparison of half-wave potential and mass activity (NA: no activity) of Pd@Ni/C, Pd@NiO-0.1/C,

Pd@NiO-0.3/C, Pd@NiO-0.5/C, the commercial Pt/C and Pd/C.

26
Fig. 4. The anti-poisoning properties of Pd@NiO-x/C. The response of (a) Pd@NiO-0.3/C, (b) the

commercial Pt/C and (c) Pd@NiO-0.3/C-HCl to CO (saturated) and CH3OH (0.5 M) in O2-saturated 0.1

M KOH. (d) CO stripping measurements of Pd@NiO-0.3/C and Pd@NiO-0.3/C-HCl recorded in 0.1 M

KOH at 20 mV s-1 with (the first cycle) and without (the second cycle) a CO absorbed layer. CO was

dosed for 30 min before each measurement.

27
Fig. 5. The durability tests of Pd@NiO-x/C. ORR polarization curves of (a) Pd@NiO-0.3/C, (b) the

commercial Pt/C and (c) Pd@NiO-0.3/C-HCl before and after 10,000 cycles. The insets show

corresponding mass activities at 0.9 V vs. RHE before and after 10,000 cycles. (d) Chronoamperometric

responses of Pd@NiO-0.3/C, Pd@NiO-0.3/C-HCl and the commercial Pt/C at 0.75 V vs. RHE in O2-

saturated 0.1 M KOH with 0 M CH3OH and 0.5 M CH3OH.

28
 a

b c d e

Fig. 6. Interface structures and the electronic properties. (a) Left: The side-view of the Pd@porous

NiO interface system (core@shell model). Right: The real-spatial contour plots for the bonding and anti-

bonding orbitals near the EF. (b) The evolutions of projected density of states (PDOSs) for the Pd-4d

badns from different layers of Pd-core region. (c) The evolutions of PDOSs for the Ni-3d bands from

different positions of the porous NiO shell-model. (d) The PDOSs for the overall p and d bands of the

core@shell model regarding the cavity size dependent effect. (e) The PDOSs for different p-band ranges

of the *O2, H2O, *OOH-, *OH-, and different O sites from NiO shell, respectively.

29
a e CH3OH H2O

No Adsorption

Slide Away

Porous Direct Poisoning

NiO Shell Reaction Catalyst

Interface

Pd Core Pristine Pd

b c Interface
Barrier Catalyst Poisoning
Anti-Poisoning

Band Offset
Interface Interface
Barrier Engineering

Anti-Poisoning Trade Off

Ubh vs Uab

Fig. 7. Energy profile for mechanism. Reaction energy pathway for catalytic ORR under alkaline

condition with consideration of the electrode potentials (both U=0 V and U=0.401 V). (b) The

chemisorption of (OH-) comparison between the Ni and Pd sites. (c) The chemisorption summary and

comparison for the CH3OH between the core@shell and plain Pd systems. (d) The evolutions of the

local structural configurations for demonstrating the ORR process within the core@shell model under

alkaline condition. (e) The interface band offset model to interpreting the mechanism for the core@shell

engineering in order to further promote electronic activities transfer between interfaces, as well as

further energetically support to overpass the reaction activation barrier.

30
TOC

CH3OH H2O

No Adsorption

Slide Away

Porous Direct Poisoning

NiO Shell Reaction Catalyst

Interface

Pd Core Pristine Pd

Interface
Barrier Catalyst Poisoning
Anti-Poisoning

Synopsis: The interface band offset model to interpreting the mechanism for the core@shell engineering

in order to further promote electronic activities transfer between interfaces, as well as further

energetically support to overpass the reaction activation barrier.

31
Biosketch

Yonggang Feng is currently a Ph.D. candidate under the supervision of Prof.

Huang in College of Chemistry, Chemical Engineering and Materials Science
in Soochow University. He received his M.S degree in Soochow University,
China in 2018 and B. S. degree in Jiaxing University, China in 2015. His
major is inorganic chemistry and he is now focused on the design of noble
metal nanomaterials for electrocatalysis and energy conversion.

Chengyong Yang is currently a Master candidate under the supervision of

Prof. Huang in College of Chemistry, Chemical Engineering and Materials
Science in Soochow University. He received his B.S degree in Huaiyin
Normal University, China in 2017. His major is inorganic chemistry and he is
now focused on the design of noble metal nanomaterials for energy and
environment applications.

32
 Dr. Bolong Huang received PhD in 2012 from University of Cambridge, and
he obtained BSc in condensed matter physics from Department of Physics,
Peking University 2007. Following a systematic training period as research
assistant in Chemistry Department in Peking University, and in Hong Kong, he
was starting-up his independent research as PI in the the Hong Kong
Polytechnic University in 2015. His main research fields are DFT calculations
on rare earth functional nanomaterials, defect theory of solid functional
nanomaterials, DFT calculation development based on ab-initio electronic self-
energy corrections, and semi-core orbital corrections as an implement in time-
dependent DFT theory.

Dr. Qi Shao received her Ph.D. degree in applied physics from City University of
Hong Kong in 2016. Now she is an assistant professor in Professor Huang’s group
at College of Chemistry, Chemical Engineering and Materials Science, Soochow
University. Her current research interests are focusing on non-noble metal based
catalysts for electrochemical applications.

33
 Dr. Xiaoqing Huang is currently a Professor at College of Chemistry,
Chemical Engineering and Materials Science, Soochow University. He
obtained his B.Sc. in chemistry education from Southwest Normal University
(2005) and Ph.D. in organic chemistry from Xiamen University (2011) under
the supervision of Profs. Nanfeng Zheng and Lansun Zheng. Then he joined
Profs. Yu Huang and Xiangfeng Duan’s group as a postdoctoral research
associate from September 2011 to June 2014 at University of California, Los
Angeles. His current research interests are in the design of nanoscale materials
for heterogenous catalysis, electrocatalysis, energy conversion and beyond.

Highlights:
The “reactivity and anti-poison” dilemma has been approached by interfacial engineering.
A series of controlled interface structures overcome the activity and anti-poisoning issues of oxygen
reduction reaction (ORR), where exhibits a high activity of 0.24 A mg-1.
Generalized interfacial d-band-offset can be achieved for counteracting the ORR barriers with extra-
high current density.
The simultaneous high activity and excellent anti-poisoning features make it a practically potential
electrocatalyst for fuel cell and beyond.

34