R ES E A RC H

MEMBRANES inhibitor. Because the acyl chloride has very lit-

tle solubility in water, the polymerization occurs
predominantly on the organic side of the inter-
Polyamide membranes with face. Initially, the activator reacts with the locally
available inhibitor in the reaction zone, later it

nanoscale Turing structures for diffuses to penetrate more deeply into the re-
action zone, and finally, a cross-linked PA mem-
brane forms across the region of pore openings
water purification of the PSU support (figs. S4 to S11 and table S1).
This PA membrane formed by a conventional
Zhe Tan,1 Shengfu Chen,1 Xinsheng Peng,2 Lin Zhang,1* Congjie Gao1,3
interfacial polymerization reaction is not of Turing
type, for there are not appropriate differences
The emergence of Turing structures is of fundamental importance, and designing these between the diffusion coefficients of the activa-
structures and developing their applications have practical effects in chemistry and tor and the inhibitor. During the reaction, the
biology. We use a facile route based on interfacial polymerization to generate Turing-type aqueous solution of the activator is confined
polyamide membranes for water purification. Manipulation of shapes by control of reaction
within surface nanometer-sized pores of the PSU
conditions enabled the creation of membranes with bubble or tube structures. These support, where physical obstruction blocks dis-
membranes exhibit excellent water-salt separation performance that surpasses persed aqueous-phase movement and slows the
the upper-bound line of traditional desalination membranes. Furthermore, we show the activator transport. The diffusion coefficient
existence of high water permeability sites in the Turing structures, where water transport
of the organic molecules is around 10−5 cm2 s–1,
through the membranes is enhanced. whereas the diffusion of the dispersed aqueous
phases in the organic phase can be as low as

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10−6 cm2 s–1 (fig. S12). When a certain amount of

A
lan Turing’s 1952 paper (1), “The chemi-
cal basis of morphogenesis,” theoretically
analyzed how two chemical substances, ac-
tivator and inhibitor (2) (Fig. 1A), can, un-
der certain conditions, react and diffuse
with each other to generate spatiotemporal sta-
tionary structures. Turing’s ideas have profoundly
influenced theoretical understanding of pattern
formation in chemical (3) and biological (4, 5)
systems, but it was not until nearly 40 years after
his paper was published that experimental evi-
dence was obtained for the chlorite-iodide-malonic
acid (CIMA) reaction (6, 7). About 10 years later,
stationary Turing states were also observed in the
Belousov-Zhabotinsky (BZ) reaction microemulsion
consisting of reverse micelles (8). Recently, a va-
riety of two- and three-dimensional stationary
structures were studied in chemical (9, 10) and
biological (11–15) systems.
Turing structures typically emerge in reaction-
diffusion processes far from thermodynamic equi-
librium (1), in which the diffusion coefficient of
the inhibitor must be larger than that of the
activator, resulting in the “local activation and
lateral inhibition” phenomenon (Fig. 1B) that
underlies diffusion-driven instability (2). How-
ever, this condition is not easily satisfied in homo-
geneous solutions, for most chemical reactions
involve small molecules with similar or inappro-
priately differing diffusion coefficients. In the
classic Turing systems, two main approaches have
been developed to selectively control the effective
diffusion coefficients of reactants: (i) Introduce a
macromolecule that reversibly binds the activa-
tor, like starch or polyvinyl alcohol (PVA) in the
CIMA reaction, and (ii) use a heterogeneous fine-
ly dispersed multiphase reaction system in which macromolecule, PVA, was added to the aqueous
the activator resides in a low-mobility phase, such solution, it interacted with the activator via hy-
as when polar BZ reagents are confined within drogen bonding and increased solution viscosity,
nanosized aqueous droplets (6–10). On the basis further reducing the diffusion rate of the acti-
of theoretical analyses and experimental obser- vator (fig. S13). Through the synergetic effects of
vations, we successfully applied these chemical the physical obstruction and chemical interac-
and physical approaches to aqueous-organic inter- tion, the systems meet appropriate differences
facial polymerization and developed a facile route in the diffusion coefficients of the activator and
to generate nanoscale Turing structures with high inhibitor (21, 22), leading to a diffusion-driven
water permeability under ambient conditions. instability and generating nanoscale spotted (Fig.
Interfacial polymerization is a reaction-diffusion 1D) and striped (Fig. 1E) Turing structures.
process far from thermodynamic equilibrium Atomic force microscopy (AFM) measurements
(16). It is based on the Schotten-Baumann re- (Table 1) show that the surfaces of membranes
action, in which the irreversible polymerization with the nanoscale spotted (TS-I) and striped
of two fast-reacting multifunctional monomers (TS-II) Turing structures are relatively rough
occurs near the interface of two immiscible phases and heterogeneous. The measured average root
of a heterogeneous liquid system (17, 18). This mean square roughnesses were 22 and 32 nm,
technique has been used to prepare reverse os- respectively, which is quite different from that
mosis and nanofiltration membranes for large- of traditional semiaromatic PA membrane (figs.
scale and low-cost water purification applications S14 and S15 and table S2) with a relatively smooth
(19, 20). In a typical membrane synthesis (fig. S1), and homogeneous surface (23). The spotted and
organic amines are dissolved in water while acyl striped structures have virtually the same height,
chlorides are dissolved in an organic solvent, and whereas the surface area increase of TS-II is ap-
a very thin insoluble polyamide (PA) membrane proximately two times greater than that of TS-I,
forms on top of a porous support (figs. S2 and S3). suggesting that the continuous striped structures
In our experiment, piperazine (PZ) is the activa- have a larger surface area relative to the discrete
tor, and trimesoyl chloride (TMC) is the inhibitor spotted structures in the scan area. To further
(Fig. 1C). The reaction is initiated when the top investigate the nanoscale Turing structures,
surface of a porous polysulfone (PSU) support the membranes were characterized by scanning
containing an aqueous solution of the activator electron microscopy (SEM) and transmission
comes in contact with an organic solution of the electron microscopy (TEM) analyses. The SEM
Table 1. Surface properties of the Turing-type PA membranes. Comparison of the surface
properties of the spotted and striped Turing structures. These results were acquired from AFM
measurements over a scanning area of 5 mm by 5 mm. Reported are the averages and standard deviations.

1
Key Laboratory of Biomass Chemical Engineering, College of Root mean square Surface area
Chemical and Biological Engineering, Zhejiang University, Sample AFM scans Height (nm)
Hangzhou 310027, China. 2School of Materials Science and roughness (nm) increase (%)
Engineering, Zhejiang University, Hangzhou 310027, China.
3 TS-I 12 137 ± 34 21.7 ± 6.6 18.7 ± 5.3
National Engineering Research Center for Liquid Separation .....................................................................................................................................................................................................................
Membrane, Hangzhou 310012, China. TS-II 12 119 ± 21 32.2 ± 8.5 35.5 ± 9.7
.....................................................................................................................................................................................................................
*Corresponding author. Email: linzhang@zju.edu.cn

Tan et al., Science 360, 518–521 (2018) 4 May 2018 1 of 4

R ES E A RC H | R E PO R T

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Fig. 1. Turing-type structures in interfacial polymerization. (A) Sche-
matic diagram of activator-inhibitor interaction in a reaction-diffusion
process. Reactions leading to Turing structures rely on competing
activation (red) and inhibition (blue) kinetic pathways. (B) Spatial
representation of local activation and lateral inhibition. In two dimensions,
Turing structures generally consist of spots or stripes. (C) Schematic
illustration of interfacial polymerization Turing system. The inhibitor (TMC)
is dissolved in the organic phase (top), and the activator (PZ) and the
macromolecule (PVA) are dissolved in the aqueous phases (bottom). The
membrane (PA) with nanoscale Turing structures forms on the porous
support (PSU). (D and E) AFM topography images of the Turing-type PA
membranes. Bright yellow and orange regions correspond to the formed
solid-state nanoscale Turing structures. Initial concentrations for nano-
scale spots (D) are [TMC] = 6 mM, [PZ] = 28 mM, and [PVA] = 12 mM,
and for nanoscale stripes (E), [TMC] = 8 mM, [PZ] = 23 mM, and [PVA] =
32 mM. Scan area is 2 mm by 2 mm.

A C

1 µm 1 µm 200 nm 200 nm

Resin Resin

Polyamide Polyamide

B D
Void Void

200 nm 200 nm 200 nm Polysulfone 200 nm Polysulfone

Fig. 2. Electron micrographs of the Turing-type PA membranes. (C and D) Projected area TEM images (C) and cross-sectional TEM
(A) Low-magnification SEM images of the two membrane surfaces. images (D), showing the internal characteristics and three-dimensional
(B) High-magnification SEM images of the two different structures. morphologies of the two structures.

Tan et al., Science 360, 518–521 (2018) 4 May 2018 2 of 4

R ES E A RC H | R E PO R T

A
Water-salt selectivity, Pw/Ps C D
6.0% 12.8%

TS-II

TS-I
Upper-bound line

Trade-off line
200 nm 200 nm

E F

Water permeability, Pw(cm2/s)

B

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50 nm 50 nm

Water flow Nanoparticle Polyamide Support

Fig. 3. Spatial distribution of water permeability sites in the dynamic filtration experiments with GNPs and the transport of water
Turing-type PA membranes. (A) Correlation between water permeability across the Turing-type PA membranes. (C to F) Projected area TEM
and water-salt selectivity for the Turing-type PA membranes [TS-I (blue images showing nanoparticle deposition on the surfaces of the Turing-type
diamond) and TS-II (red star)] and other nanofiltration membranes PA membranes after 10-min filtration tests (1.0 × 1012 particles ml–1,
(open circles). These data were obtained from water-salt separation 25°C, 4.8 bar). In (C) and (D), GNP percent surface area coverage is
tests (2000 ppm MgSO4, 25°C, 4.8 bar). The dashed red line is the given in the upper right corner of each image. In (E) and (F),
permeability-selectivity trade-off for traditional semiaromatic PA high-resolution TEM images of outlined areas from (C) and (D),
membranes, and the solid black line is the empirical upper-bound respectively, show spatial distribution of nanoparticle deposition patterns
relationship (26). Ps, salt permeability. (B) Schematic diagrams of the and Turing structures.

images show that both structures are uniformly

distributed throughout the membranes (Fig. 2A), Table 2. Separation performance of the Turing-type PA membranes. The operating pressure
which is consistent with the corresponding AFM was controlled at 4.8 bar, and the temperature was maintained at 25°C by a heat exchanger. The
measurements. A closer look at the membrane feed flow rate was 6 liters min–1, and the concentrations of salts in the feed solutions were
surfaces (Fig. 2B) reveals that the nanoscale 2000 parts per million. All measurements were made 1 hour after starting the filtration to stabilize
Turing structures generally consist of close-packed the membrane performance. The rejections were calculated on the basis of the electrical
hexagonal arrays or interconnected labyrinthine conductivities of feed and permeate solutions.
networks (figs. S16 to S18), with diameters ranging
between 60 and 80 nm (fig. S19). The TEM ana-
lyses not only present the external features on TS-I TS-II
the surfaces of the membranes but also provide Solute Flux Flux
morphology information on the internal char- Rejection (%) Rejection (%)
(liters m–2 hour–1) (liters m–2 hour–1)
acteristics of the structures. Projected area (Fig.
2C) and cross-sectional TEM (Fig. 2D) micro- NaCl 64 ± 6 51.2 ± 2.3 124 ± 11 49.6 ± 2.0
.....................................................................................................................................................................................................................
graphs show that there are two types of voids in MgCl 2 60 ± 5 88.1 ± 1.6 114 ± 12 91.2 ± 1.2
.....................................................................................................................................................................................................................
the Turing structures, with diameters ranging CaCl 2 58 ± 5 88.0 ± 1.5 117 ± 10 92.7 ± 1.5
.....................................................................................................................................................................................................................
from 30 to 40 nm (fig. S20). The thickness of the MgSO 4 63 ± 7 98.5 ± 0.5 125 ± 14 99.2 ± 0.1
.....................................................................................................................................................................................................................
Turing-type PA membranes is about 20 nm or Na 2SO4 61 ± 4 99.1 ± 0.2 119 ± 11 99.6 ± 0.1
.....................................................................................................................................................................................................................
less, two times thinner than that of traditional
semiaromatic PA membranes (24). In three di-
mensions, the Turing structures are bubble or
tube shaped, like Turing patterns in the BZ micro- membranes exhibit excellent separation perform- higher water permeability invariably leads to
emulsion system (25). ance, surpassing the water-salt separation upper- lower water-salt selectivity (27). Additionally,
We evaluated separation performance of the bound line (Fig. 3A) of traditional nanofiltration tube-structured membrane TS-II exhibits higher
two membranes by saltwater desalination tests membranes (26). Counterintuitively, water per- water flux and similar salt rejections compared
and explored structure-property relationships in meability and water-salt selectivity are both high, to that of bubble-structured membrane TS-I un-
these membranes for water purification. The in contrast to the trade-off behavior of traditional der the same test conditions (Table 2). The water
water and salts transport data show that both polymer membranes (tables S3 and S4), where flux of TS-II is as high as 125 liters m–2 hour–1,

Tan et al., Science 360, 518–521 (2018) 4 May 2018 3 of 4

R ES E A RC H | R E PO R T
which is approximately two times higher than
that of TS-I. This result correlates well with the
excess surface area ratio of the membranes, in-
dicating that the Turing structures have a large
effect on the water flux. On the basis of these
observations, we hypothesized that there must
be some specific sites with relatively higher water
permeability in the Turing structures and that
these high-permeability sites lead to membranes
with an enhanced water transport property.
To verify this hypothesis, we used gold nano-
particles (GNPs) as probes in combination with
microscopy methods to visually examine the
spatial distribution of water permeability sites
in the Turing-type membranes (Fig. 3B). GNPs
are negatively charged under neutral conditions,
and both membranes showed essentially the
same surface charge behavior as GNPs (table S5).
Consequently, for deposition to occur (figs. S21
and S22), drag forces had to overcome repulsive
forces originating from nanoparticle-membrane
electrostatic interactions (28, 29). Projected area
TEM micrographs revealed that the deposition
of GNPs was not uniformly distributed across
the membrane surfaces. Nanoparticle surface area
coverage for TS-I and TS-II were 6.0 (Fig. 3C) and
12.8% (Fig. 3D), respectively. GNPs deposited
in specific areas of the membrane surfaces and
formed clusters, leaving other areas of the surfaces
uncovered or with considerably fewer sparsely
distributed GNPs (figs. S23 and S24 and tables S6
and S7). Most of GNPs were deposited around
bubble (Fig. 3E) or tube structures (Fig. 3F),
which provides visual evidence supporting the
existence of relatively higher water permeability
sites in the nanoscale Turing structures (figs. S25
and S26).
Tan et al., Science 360, 518–521 (2018) 4 May 2018
Our work demonstrates that Turing structures
can be produced by interfacial polymerization
when appropriate initial conditions are created.
Microscopic characterization of the Turing-type
membranes reveals that the spatial distribution
of relatively higher water permeability sites agrees
well with the corresponding Turing structures
at the nanoscale. These unusual nanostructures,
which are generated by diffusion-driven instability,
enable outstanding transport properties in both
water permeability and water-salt selectivity.
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AC KNOWLED GME NTS
We thank X. A. Zhao for helpful discussions and L. He, J. Hong,
N. H. Rong, S. D. Shen, H. Wang, Y. Xu, M. J. Yu, and H. J. Zhang
for technical assistance. Funding: This work was supported by
the National Natural Science Foundation of China (nos. 51578485
and 21671171) and the National Basic Research Program of
China (no. 2015CB655303). Author contributions: Z.T. performed
Downloaded from http://science.sciencemag.org/ on May 3, 2018
the experiments. Z.T., S.F.C., X.S.P., and L.Z. designed the
experiments and analyzed the data. All authors discussed
the results and wrote the manuscript. Competing interests:
L.Z., Z.T., and S.F.C. are inventors on patent application
201810120316.x submitted by Zhejiang University, which
covers Turing-type polyamide membranes. Data and materials
availability: All data are available in the manuscript or in the
supplementary materials.
SUPPLEMENTARY MATERIALS
www.sciencemag.org/content/360/6388/518/suppl/DC1
Materials and Methods
Supplementary Text
Figs. S1 to S26
Tables S1 to S7
References (30–39)
1 December 2017; accepted 21 March 2018
10.1126/science.aar6308
4 of 4
Polyamide membranes with nanoscale Turing structures for water purification
Zhe Tan, Shengfu Chen, Xinsheng Peng, Lin Zhang and Congjie Gao

Science 360 (6388), 518-521.

DOI: 10.1126/science.aar6308

Turing structures at the nanoscale

Turing structures arise when imbalances in diffusion rates make a stable steady-state system sensitive to small
heterogeneous perturbations. For example, Turing patterns occur in chemical reactions when a fast-moving inhibitor
controls the motion of a slower-moving activator. Tan et al. grew polyamide membranes by using interfacial
polymerization, where the reactions occur at the interface between oil and water layers. The addition of polyvinyl alcohol
to the aqueous phase reduced the diffusion of the monomer. This process generates membranes with more bumps,

Downloaded from http://science.sciencemag.org/ on May 3, 2018

voids, and islands, which prove to be better for water desalination.
Science, this issue p. 518

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SUPPLEMENTARY http://science.sciencemag.org/content/suppl/2018/05/02/360.6388.518.DC1
MATERIALS

REFERENCES This article cites 31 articles, 9 of which you can access for free
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