Boron-Doped Diamond pH Electrode for Low Conductivity Samples

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Solution Overview

Problem

Conventional pH electrodes are fragile, prone to breakage, and suffer from 'alkali errors due to interfering ions, making them costly to maintain and less suitable for low conductivity samples like drinking water, which requires accurate and robust pH measurement.

Innovation Solution

A single pit boron-doped diamond (BDD) electrode with a laser-machined sp2 carbon region, integrated into a boron-doped diamond-based pH sensor, providing improved accuracy and resistance to fouling from particulates, and capable of measuring pH across a wide range without the need for frequent calibration.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional pH electrodes are used, then pH measurement is achieved, but the electrodes are fragile and require frequent maintenance and calibration

Engineering Contradiction:
Improveelectrode durabilityVSAvoidmaintenance frequency
Core Design Contradiction:
ReliabilityVSEase of repair

Solution Approach 1:

The patent changes the material parameter of the electrode from conventional glass or metal to boron-doped diamond, which fundamentally alters the mechanical and chemical properties. This material substitution provides exceptional hardness, chemical inertness, and electrochemical stability, eliminating the fragility and maintenance issues of conventional electrodes while maintaining pH measurement functionality

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs a composite structure combining boron-doped diamond material with specific surface treatments and geometric configurations. The BDD substrate provides mechanical robustness and chemical stability, while surface modifications enable pH-sensitive electrochemical responses, creating a composite system that overcomes the limitations of single-material conventional electrodes

Inventive Principle:
Principle #40Composite materials

2Measurement precision

If conventional pH electrodes are used, then pH measurement is achieved, but they suffer from alkali errors due to interfering ions

Engineering Contradiction:
ImprovepH measurement accuracyVSAvoidinterfering ions
Core Design Contradiction:
Measurement precisionVSObject-affected harmful factors

Solution Approach 1:

The patent changes the electrochemical parameters of the electrode by using boron-doped diamond with specific doping concentrations and surface treatments. This creates an electrode surface that is insensitive to alkali metal ions while maintaining sensitivity to hydrogen ions, thereby eliminating alkali errors and improving measurement precision in samples containing interfering ions

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent converts the chemical inertness of boron-doped diamond, which might seem to reduce reactivity, into a benefit by creating a surface that selectively responds only to hydrogen ions. The electrochemically inactive surface toward interfering ions transforms potential measurement errors into measurement accuracy, as the electrode ignores harmful interfering species while detecting the target analyte

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Measurement precision

If conventional pH electrodes are used, then pH measurement is achieved, but they require frequent calibration

Engineering Contradiction:
ImprovepH measurement accuracyVSAvoidcalibration time
Core Design Contradiction:
Measurement precisionVSLoss of time

Solution Approach 1:

The boron-doped diamond electrode exhibits self-stabilizing properties where the electrochemical surface groups automatically maintain their protonation state in response to pH changes without drifting. This self-regulating behavior eliminates the need for frequent manual calibration, as the electrode maintains measurement precision automatically over extended periods

Inventive Principle:
Principle #25Self-service

Solution Approach 2:

The patent creates an electrode with excessive chemical stability and electrochemical robustness beyond what is minimally required. This over-engineered stability ensures that the electrode maintains calibration across a wide range of operating conditions and time periods, making frequent calibration unnecessary while preserving measurement accuracy

Inventive Principle:
Principle #16Partial or excessive action

4Adaptability or versatility

If conventional pH electrodes are used, then pH measurement is achieved, but they are not suitable for low conductivity samples

Engineering Contradiction:
Improvesample type rangeVSAvoidmeasurement reliability in low conductivity samples
Core Design Contradiction:
Adaptability or versatilityVSReliability

Solution Approach 1:

The patent changes the electrical parameters of the electrode by using boron-doped diamond with optimized doping levels and surface conductivity. This creates an electrode with low background current and high signal-to-noise ratio, enabling reliable pH measurement in low conductivity samples where conventional electrodes fail due to insufficient ionic conductivity

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The single pit BDD electrode offers enhanced accuracy and reduced maintenance costs by minimizing fouling and calibration needs, while maintaining precise pH measurement in low conductivity samples, including environmentally relevant pH ranges.

Implementation Method 1

an electrochemical sensor comprising a boron doped diamond electrode formed of boron doped diamond material; an array of non-diamond carbon sites disposed on a sensing surface of the boron doped diamond electrode

Methodology Applied
Scientific EffectElectrochemical reaction:

Implementation Method 2

electrochemically active surface groups bonded to the non-diamond carbon sites for generating a redox peak associated with a target species which reacts with the electrochemically active surface groups

Methodology Applied
Scientific EffectRedox reaction: Redox Reactions

Data Source

PatentEP3994457B1Ph measurement of an aqueous sample with a boron doped diamond-based ph electrode comprising a sp2 carbon region
Publication Date: 2023.07.26 HACH
  • EP3994457B1 patent drawingFigure 1
  • EP3994457B1 patent drawingFigure 2
  • EP3994457B1 patent drawingFigure 3

AI summary

An embodiment provides a device for measuring pH in an aqueous sample, including: at least one measurement electrode (400) comprising a first carbon region, wherein the carbon region comprises a single pH sensitive carbon region, wherein the single pH sensitive carbon region of the measurement electrode is a sp2 carbon region (402) of a boron doped diamond-based pH electrode (401); at least one reference electrode; at least one auxiliary electrode; and a memory storing instructions executable by a processor to identify a pH of an aqueous sample by measuring an electrical potential between the at least one measurement electrode and the at least one reference electrode. Corresponding pH measurement method as well as corresponding pH measurement system are also disclosed and claimed.